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Baltic Polymer Symposium 2013
VILNIUS UNIVERSITY
KAUNAS UNIVERSITY OF TECHNOLOGY
PROGRAMME
Trakai, Lithuania
September 18-21, 2013
1
Scientific Committee International Advisory Board
Chairman
Prof. Ričardas Makuška
Vilnius University, Lithuania
Members
Prof. Juozas Vidas Gražulevičius
Prof. Albertas Malinauskas
Prof. Martins Kalnins
Dr. Janis Zicans
Prof. Andres Opik
Prof. Andres Krumme
Kaunas University of Technology, Lithuania
Riga Technical University, Latvia
Institute of Chemistry, Center for Physical
Sciences and Technology, Lithuania
Riga Technical University, Latvia
Tallinn University of Technology, Estonia
Organizing Committee
Chairman
Prof. Ričardas Makuška
Secretary
Dr. Tatjana Kochanė
Members
Prof. Saulutė Budrienė
M. Sc. Česlav Višnevskij
Assoc. Prof. Aušvydas Vareikis
M. Sc. Irina Gerasimčik
2
Sponsor Page
The support of Baltic Polymer Symposium 2013 by the following organizations
and companies is greatly acknowledged:
RESEARCH COUNCIL OF
LITHUANIA
Gedimino pr. 3,
LT-01103 Vilnius
Lithuania
http://www.lmt.lt
UAB „THERMO FISHER
SCIENTIFIC BALTICS“
V.Graičiūno str. 8
LT-02241 Vilnius
Lithuania
http://www.fermentas.lt
UAB "NEO GROUP"
Silutes str. 9
LT-95346 Rimkai
Dovilai sen.
Klaipeda district,
Lithuania
www.neogroup.eu
UAB „LAISVA LINIJA“
Mokslininkų str. 12A
LT-08412 Vilnius
Lithuania
http://www.laisvalinija.com
MALVERN INSTRUMENTS Ltd
Enigma Business Park
Grovewood Road
Malvern
Worcestershire WR14 1XZ
United Kingdom
http://www.malvern.com
POSTNOVA ANALYTICS
GmbH
Max-Planck-Straße 14
86899 Landsberg am Lech
Germany
www.postnova.com
3
CONFERENCE PROGRAMME
Wednesday, 18th SEPTEMBER, 2013
15.00-19.00
19.00
Registration (Trasalis Resort & SPA, Trakai )
WELCOME DRINK (Restaurant “Winter Garden”, Trasalis)
4
Thursday, 19th SEPTEMBER, 2013
Hall SKAISTIS
Registration (Trasalis Resort & SPA )
OPENING CEREMONY
8.00-9.00
9.00-9.15
ORAL SESSION I
Chairman: Prof. R. Makuška
INVITED LECTURES
9.15-9.45
NANOMECHANICAL PROPERTY MAPPING OF
POLYMER COMPOSITES
O. Krivosheeva1, M. Sababi1, G. Dunér1, E. Thormann1,
Sh. Jafarzadeh1, F. Zhang1, J. Pan1, A. Dedinaite1,2,
and P. M. Claesson1,2
25
1
Division of Surface and Corrosion Science, Department of Chemistry, School of Chemical Sciences,
Royal Institute of Technology,Stockholm, Sweden
2
SP Technical Research Institute of Sweden,Chemistry, Materials and Surfaces, Stockholm, Sweden
9.45-10.15
AQUEOUS LUBRICATION BY ADSORBED POLYMER
LAYERS
A.Dėdinaitė,1,2 X.Liu1, M.Rutland1,2, E.Thormann1, Č.Višnevskij3,
R. Makuška3, and P.M. Claesson1,2
26
1
KTH Royal Institute of Technology, School of Chemical Sciences and Engineering, Department of
Chemistry, Surface and Corrosion Science, Stockholm, Sweden.
2
Materials and Surfaces, SP Technical Research Institute of Sweden, Stockholm, Sweden
3
Department of Polymer Chemistry, Vilnius University, Vilnius, Lithuania
10.15-10.45 POLYANILINE: ITS BIRTH, LIFE, AND PASSING AS
STUDIED BY RAMAN SPECTROSCOPY
A. Malinauskas
27
Department of Organic Chemistry, Institute of Chemistry, Center for Physical Sciences and
Technology, Vilnius, Lithuania
10.45-11.15 COFFEE BREAK
ORAL SESSION II
Chairman: Prof. J. V. Gražulevičius
INVITED LECTURES
11.15-11.45 SPECTROELECTROCHEMISTRY AS USEFUL
TECHNIQUE FOR ANALYSIS OF CONJUGATED
POLYMERS
M. Łapkowski, P. Data, and W. Domagala
28
Faculty of Chemistry, The Silesian University of Technology, Gliwice, Poland
29
11.45-12.15 ELECTROCHEMICAL REDUCTION OF HALOGENATED
ARYL DIAZONIUM SALTS ULTRATHIN ORGANIC
LAYERS ON AU AND SI SURFACES
X. Zhang1, V. Syritski2, J. Reut2, F. Rösicke1, G. Sun3, K. Hinrichs3,
S. Janietz4 and J. Rappich1
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut für Silizium-Photovoltaik,
Berlin, Germany
2
Department of Materials Science, Tallinn University of Technology, Tallinn, Estonia
3
Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Department Berlin, Berlin, Germany
4
Fraunhofer Institute for Applied Polymer Research, Department Polymer Electronics, Potsdam,
Germany
1
12.15-12.45 LOW MOLECULAR GLASSES AS A PROMISING CLASS
OF MATERIALS FOR PHOTONIC APPLICATIONS
M. Rutkis
30
Institute of Solid State Physics, University of Latvia, Latvia
12.45-14.00 LUNCH
5
ORAL SESSION III
Hall SKAISTIS
Chairman: Prof. A. Malinauskas
INVITED LECTURES
14.00-14.30 SUSTAINABLE, FUNCTIONAL NANOFIBRES BY
ELECTROSPINNING
A. Krumme
31
14.30-15.00 ENGINEERING COMPLEX MACROMOLECULAR
ARCHITECTURES BY PRECISION POLYMERIZATION
D. Gromadzki
32
McGill University, Canada
ORAL PRESENTATIONS
15.00-15.15 DECOMPOSITION OF THE TRIPLE-DETECTION SEC
CURVES OF LINEAR AND BRANCHED POLYMERS
M. Netopilík
35
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Prague, Czech
Republic
15.15-15.30 ORGANOBORANE
WONDERLAND:
FROM
THE
VIEWPOINT OF A UNIQUE INITIATOR OF RADICAL
POLYMERIZATION
S.Kanno
36
Polymer Chemistry Laboratory, Tohoku Seikatsu Bunka University, Sendai, Japan
15.30-15.45 INITIATOR TYPE INFLUENCE ON PROPYLENE OXIDE
POLYMERS OF AND STAR-SHAPED DOPED
POLYETHERS FOR INDUSTRIAL APPLICATION
A.S. Swinarew1, S. Golba1, J. Gabor1, M. Łężniak1, T. Flak1,
B. Swinarew2, Z. Grobelny3
37
1
Institute of Materials Science, University of Silesia, Katowice, Poland
Institute for Engineering of Polymer Materials and Dies, Paint and Plastics Department, Gliwice,
Poland
3
Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
2
15.45-16.00 SUPRAMOLECULAR HYDROGELS. SELFORGANIZATION PROCESSES
S. Khizhnyak1, P. Pakhomov1, M. Ovchinnikov2, P. Komarov1
1
2
38
Department of Physical Chemistry, Tver State University, Tver, Russia
Department of Scientific Research, Tver StateMedical Academy, Tver, Russia
16.00-16.15 HIGHLY DURABLE DYE-SENSITIZED SOLAR CELLS
UTILIZING BIO-COMPATIBLE AND PHOTOCROSSLINKABLE ACRYLIC-BASED HYDROGEL
L.-Y. Chen, S.-H. Huang
39
Department of Photonics, National Sun Yat-sen University, Kaohsiung, Taiwan
16.15-16.30 POLYMER MATERIALS FOR ADVANCED LITHIUM
BATTERIES
V. Barsukov, V. Khomenko, I. Senyk, E. Senyn and
V. Tverdokhleb
40
Department of Electrochemical Power Engineering & Chemistry, Kiev National University of
Technologies and Design (KNUTD), Kiev, Ukraine
16.30-18.00 COFFEE BREAK AND POSTER SESSION I
GALA DINNER (Trasalis Resort & SPA)
19.00
6
Hall AKMENA
THE SPECIAL SESSION OF THE PROJECT "CENTRE OF EXCELLENCE
IN ORGANIC SEMICONDUCTOR RESEARCH" (FP7-REGPOT-2011-1)
ORAL PRESENTATIONS
Chairman: Prof. J. V. Gražulevičius
14.00-14.25 SYNTHETIC METHODOLOGIES TOWARDS NEW
HETEROHELICENES
W. Dehaen
Department of Chemistry K. U. Leuven, Belgium
14.25-14.50 ORGANIC SMALL MOLECULES FOR PHOTONIC
APPLICATIONS: FROM SOLAR CELLS TO MICRO
LASERS
H. Froeb
TU Dresden, Institut f. Angewandte Photophysik, Germany
14.50-15.15 HYDROGEN-BONDING OF METHOXY GROUPS VERSUS 63
CHARGE TRANSPORTING PROPERTIES:
EXPERIMENTAL AND THEORETICAL APPROACH
G. Sini
Laboratoire de Physicochimie des Polymères et des Interfaces (LPPI),
Université de Cergy-Pontoise, France
15.15-15.40 ORGANIC SOLAR CELLS: CORRELATION BETWEEN
PERFORMANCE AND DENSITY-OF-STATES
J. Puigdollers
Dept Eng Electrònica and CrNE Universitat Politècnica Catalunya
15.40-16.05 To be anounced
J. Blochwitz-Nimoth
NOVALED AG, Germany
16.05-16.30 RECENT PROGRESS IN THE ACTIVIETIES OF THE
CEOSER PROJECT
J. V. Gražulevičius
Kaunas University of Technology, Lithuania
7
Friday, 20th SEPTEMBER, 2013
ORAL SESSION IV
Hall SKAISTIS
Chairman: Prof. A. Krumme
INVITED LECTURES
9.00-9.30
TAILORING DENDRITIC STRUCTURES FOR THE USE
IN EPOXY THERMOSETS
À. Serra
33
Department of Analytical and Organic Chemistry, Rovira i Virgili University, Tarragona,
Catalonia, Spain
9.30-10.00
APPROACHES FOR FABRICATING HIGH-EFFICIENCY
OLEDs
J. Jou
34
Department of Materials Science and Engineering, National Tsing-Hua University, Hsin-chu,
Taiwan
ORAL PRESENTATIONS
10.00-10.15 MOLECULARLY IMPRINTED POLY(MPHENYLENEDIAMINE) FILMS AS A SENSING LAYER
FOR ANTIBIOTIC DETECTION
A. Tretjakov1, V. Syritski1, J. Reut1, Y. Zhang1, A. Öpik1,
K. Hinrichs2, J. Rappich3
41
Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn,
Estonia
Leibniz - Institut für Analytische Wissenschaften - ISAS - e.V., Department Berlin, Albert-EinsteinStr. 9, 12489 Berlin, Germany
3Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut für Silizium-Photovoltaik,
Kekuléstr. 5, 12489 Berlin, Germany
10.15-10.30 CARBAZOLE BASED HOLE CONDUCTING MATERIAL
FOR EFFICIENT SOLID-STATE DSSC: AN
ALTERNATIVE TO SPIRO-OMETAD
B. Schmaltz1, M. Degbia1,A. Tomkeviciene2, G. Puckyte2,
A. Michaleviciute2,E. Gurskyte2, J. Grazulevicius2, J. Bouclé3,
F. Tran Van1
42
1
Laboratoire PCM2E, Parc de Grandmont, Tours, France
Department of Organic Technology, Kaunas University of Technology, Kaunas, Lithuania
3
Institut XLIM UMR 7252, Limoges, France
2
43
10.30-10.45 ELECTROCHEMICAL AND
SPECTROELECTROCHEMICAL CHARACTERIZATION
OF CHOSEN BISAXIALLY COORDINATED RUTHENIUM
PHTHALOCYANINES AND THEIR LIGANDS
K. Lenartowicz1, P. Data1,2, M. Łapkowski1,2
1
Centre of Polymer and Carbon Materials of the Polish Academy of Sciences,
Zabrze, Poland
2
Department Of Chemistry, Silesian University of Technology, Gliwice, Poland
10.45-11.00 THE INFLUENCE OF LINKING TOPOLOGIES ON THE
PROPERTIES OF THE DENDRIMERS WITH DIFFERENT
CORES AND FLUORENE SIDE ARMS
N. Kukhta, J. Simokaitiene, J. Grazulevicius, J. Ostrauskaite
44
8
ORAL SESSION V
Hall SKAISTIS
Chairman: Prof. M. Rutkis
ORAL PRESENTATIONS
11.30-11.45 GLASS-FORMING DENDRITIC DERIVATIVES OF
TRIPHENYLAMINE
T.Matulaitis, V. Mimaitė, J. V. Gražulevičius
45
11.45-12.00 AN ELECTROCHEMICAL AND
SPECTROELECTROCHEMICAL INVESTIGATION OF
CARBAZOLE AND TRIPHENYLAMINE DERIVATIVES
CONTAINING SELENOPHENE UNITS
P.Pander1, P. Data1,2
46
1
Silesian University of Technology, Faculty of Chemistry, Strzody 9, 44-100 Gliwice, Poland
Centre of Polymer and Carbon Materials of the Polish Academy of Sciences, Zabrze, Poland
2
12.00-12.15 SPECTROELECTROCHEMICAL INVESTIGATION OF
NOVEL POLYTELLUROPHENE DERIVATIVES
P. Data1,2, P. Pander1, A. Swist3
47
1
Silesian University of Technology, Faculty of Chemistry, Strzody 9, 44-100 Gliwice, Poland
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34,
41-819 Zabrze, Poland
3
Wroclaw University of Technology, Faculty of Chemistry, Wybrzeze Wyspianskiego 27, 50-370
Wroclaw, Poland
2
12.15-12.30 INFLUENCE OF REDUCING AGENT AND
TEMPERATURE ON SILVER NANOPARTICLES
SYNTHESIS IN BRANCHED DEXTRANPOLYACRYLAMIDE MATRICES
N. Kutsevol1,M. Bezuglyi1, 2, T. Bezugla1, O. Korichenska1
1
2
48
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv,Ukraine
12.30-12.45 SYNTHESIS AND PROPERTIES OF NOVEL STARSHAPED MOLECULES BASED ON CARBAZOLE
A. Brzęczek1, P. Data1,2, K. Walczak1, M. Łapkowski1,2
49
1
Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland
2
13.00-14.00 LUNCH
14.00-15.00 COFFEE TIME AND POSTER SESSION II
9
ORAL SESSION VI
Hall SKAISTIS
Chairman: Prof. À. Serra
ORAL PRESENTATIONS
15.00-15.15 PECULIARITIES OF ACID DOPING OF POLYANILINE
OLIGOMERS WITH LOW-MOLECULAR WEIGHT AND
POLYMERIC ACIDS
O.E.Bogomolova, A.A. Savelyeva, V. G. Sergeyev
50
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia
15.15-15.30 CATIONIC POLYMERIZATION OF VINYL MONOMERS
USING COMPLEXES OF AlCl3 WITH ETHERS: FROM
FUNCTIONAL OLIGOMERS TO SUSTAINABLE
PLASTICS
S.V. Kostjuk1, I.V. Vasilenko1, D.I. Shiman1, Y.A. Veraksa1,
A.N. Frolov1, N.A. Kukhta1,2
51
1
Research Institute for Physical Chemical Problems of the Belarusian State University, Minsk,
Belarus
2
Faculty of Chemical Technology, Kaunas University of Technology, Kaunas, Lithuania
15.30-15.45 EFFECT OF MOLECULE STRUCTURE AND PACKING
ON PHOTO- AND ELECTROPHYSICAL PROPERTIES OF
ORGANIC THIN FILMS
A. Kukhta, P. Kuzhir
52
Institute for Nuclear Physics, Belarusian State University, Minsk, Belarus
15.45-16.00 THE EFFECT OF ANISOMERIC CARBONACEOUS
NANOFILLERS ON THE RELAXATIONAL BEHAVIOUR
OF THERMOPLASTIC POLYMERS
T. Ivanova1, J. Zicans1, J. Bitenieks1, R. Merijs Meri1,
S. Maksimenko2, P. Kuzhir2
53
1
Institute of Polymer Materials, Riga TechnicalUniversity, Riga, Latvia
Institute for Nuclear Problems, Belarus State University, Minsk, Belarus
2
16.00-16.30 CLOSING SESSION
16.30
GUIDED TOUR TO TRAKAI CASTLE AND
DEGUSTATION OF NATIONAL TARTARIAN FOOD
10
ORAL SESSION VII
Hall AKMENA
Chairman: Prof. V. Jankauskaitė
ORAL PRESENTATIONS
10.00-10.15 INFLUENCE OF THE SILVER NANOPARTICLES
CONCENTRATION ON POLYMER/SILVER
NANOCOMPOSITE PROPERTIES
J. Pudlauskaitė1, V. Jankauskaitė1, P. Narmontas2, I. Prosyčevas 2
1
2
Faculty of Design and Technologies, Kaunas University of Technology, Kaunas, Lithuania
Institute of Materials Science, Kaunas University of Technology, Kaunas, Lithuania
10.15-10.30 SOME FEATURES OF STARCH GELATINIZATION
J.Galkin1, E. Mažonienė1,2, J.Liesienė1
1
2
54
55
Department of Organic Chemistry, Kaunas University of technology, Kaunas, Lithuania
AB Amilina, Panevėžys, Lithuania
10.30-10.45 IMPROVED PHYSICAL-MECHANICAL PROPERTIES OF
BIODEGRADABLE PAPER BY ADDING
NANOPARTICLES FROM LIGNOCELLULOSE
L. Vikele, I. Birska, A. Treimanis, M. Laka, S. Chernyavskaya
56
Latvian State Institute of Wood Chemistry, 27 Dzerbenes Street, Riga, Latvia
10.45-11.00 HEMICELLULOSES FROM DIFFERENT RESOURCES –
COMPARISON OF PROPERTIES
J.Zoldners1, J.Kuncēvičs1,T.Kiseļeva1, L.Stiebra1
1
57
Latvian State Institute of Wood Chemistry Riga, Latvia
ORAL SESSION VIII
Chairman: Prof. A. Dėdinaitė
ORAL PRESENTATIONS
11.30-11.45 ADVANCES IN LIGHT SCATTERING FOR POLYMER
CHARACTERISATION
S. Olivier,P. Clarke, M. Pothecary, M. Nicholls, S. Ball
58
Malvern Instruments, Grovewood Road, Malvern, WR14 1XZ, United Kingdom
11.45-12.00 AUTOMATED 2-DIMENSIONAL CHROMATOGRAPHY
FOR THE CHARACTERIZATION AND
DEFORMULATION OF COMPLEX POLYMERS AND
BLENDS
A. Williams
59
PSS Polymer Standards Service, D-55120 Mainz, Germany
12.00-12.15 PET WASTE “BACK” INTEGRATION AND POLYOL
PRODUCTION. NEW SUSTAINABLE PETBASED POLYOLS FOR PRODUCTION OF RIGID PUR
FOAMS
P. Žutautas1, U.Cabulis2
1
2
-
NEO GROUP, Silutes str. 9, Rimkai LT-95346, Klaipeda district, Lithuania
Polymer Laboratory, Latvian State Institute of Wood Chemistry, Riga, Latvia
12.15-12.30 PROJECT EVOLUTION: ELECTRIC VEHICLE CONCEPT 60
THROUGH BIO-SUSTAINABLE MATERIALS
M.Kirpluks, U.Cabulis
Polymer Laboratory, Latvian State Institute of Wood Chemistry, Riga, Latvia
11
12.30-12.45 RECYCLED POLYETHYLENE TEREPHTHALATE
BASED HYBRID NANOCOMPOSITES: STRUCTURE AND
PROPERTIES
G. Japins1, R. Berzina1, J. Zicans1, R. Merijs Meri1, V. Kalkis2,
I. Reinholds2
61
1
Institute of Polymer Materials, Riga Technical University, Riga, Latvia
Department of Chemistry, University of Latvia, Riga, Latvia
2
12.45-13.00 INVESTIGATION OF DISPERSE DYES APPLICATION
FOR COTTON BLENDED FABRIC COLOURATION
A. Borisova, S.Reihmane
62
12
List of Posters
POSTER SESSION I
POLYMER SYNTHESIS, PROPERTIES AND MODIFICATION
1. PATTERING IN POLYMERIC NANOCOMPOSITES BY PULSE
LASER
R. Bakanas1,2, S. Zacharovas2, P. Narmontas3, V. Jankauskaitė1
64
1
Faculty of Design and Technologies Kaunas University of Technology, Kaunas, Lithuania
JSC “Geola Digital”, Vilnius, Lithuania
3
Institute of Materials Science Kaunas University of Technology, Kaunas, Lithuania
2
2. THE CREATING ORDERED OFNANOSTRUCTURE: CONTROL
OF SELF-ORGANISATION IN BOTTOM-UP APPROACH
M.Yu. Barabash, D.A.Grynko, G.G. Vlaykov
65
Technical Center of NAS of Ukraine, Kyiv, Ukraine
3. ARYLETHYNYL-SUBSTITUTED FLUORENES AS EFECTIVE
HOLE-TRANSPORTING MATERIALS
M. Baronaitė, J. Simokaitienė, J. V. Gražulevičius, D. Volyniuk
66
4. FORMATION OFSILVER NANOPARTICLES: INFLUENCE OF
THE STRUCTURE OF THE POLYMER MATRIXAND THE
SYNTHESIS TEMPERATURE
N. Kutsevol1, T. Bezugla1, M. Bezuglyi1,2, V. Chumachenko1
1
2
67
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv,Ukraine
5. SYNTHESIS AND CHARACTERIZATION OF NOVEL
POLY(AMIDOAMINE)
A. Bočkuvienė, I. Vinkevičiūtė, A. Vareikis
68
6. GLASS-FORMING PHENANTHROIMIDAZOLE-BASED
DERIVATIVES AS POTENTIAL CHARGE TRANSPORTING
MATERIALS FOR ORGANIC ELECTRONICS
R. Butkutė, R. Lygaitis, J.V. Gražulevičius
69
7. ARYLFLUORENYL SUBSTITUTED
METOXYTRIPHENYLAMINE MOLECULAR GLASSES FOR
OPTOELECTRONIC APPLICATIONS
M. Čekavičiūtė, J. Simokaitienė, J. V. Gražulevičius, D. Volyniuk
70
8. THERMAL BEHAVIOR OF ACRYLONITRILE COPOLYMERS
WITH LOW CONTENT OF VINYL MONOMER PREPARED VIA A
RAFT TECHNIQUE
E. Chernikova1, A. Baskakov2, S. Kishilov1, A. Plutalova1, Yu. Kostina2
1
71
Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
2
9. SYNTHESIS OF BRUSH COPOLYMERS CONTAINING ANIONIC
SIDE CHAINS VIA ISARA ATRP
G. Ciuta, M. Savickaite, S. Ketleriute, C.Visnevskij, R. Makuska
1
72
10. SYNTHESIS AND PROPERTIES OF DIFFERENTLY
SUBSTITUTED DERIVATIVES OF CYANURIC ACID
A. Dainyte1, D. Gudeika1, J.V.Grazulevicius1
73
1
Kaunas University of Technology Department of Organic Technology, Kaunas, Lithuania
11. INFORMATION MEDIA BASED ON ELECTRONS DONOR
74
13
OLIGOMERS
N.A. Davidenko, Yu.P. Getmanchuk, E.V. Mokrinskaya,
L.R. Kunitskaya, I.I. Davidenko, V.A. Pavlov, S.L. Studzinsky,
N.G.Chuprina
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine
12. EFFECT OF LIPID MOLECULE GEOMETRY ON STRUCTURE
AND PROPERTIES OF LIPOSOME–POLYCATION COMPLEXES
A.A. Efimova, D.A. Pyatnikova, A.A.Yaroslavov
75
Polymer Department, M.V.Lomonosov Moscow State University, Moscow, Russia
13. SYNTHESIS AND PROPERTIES OF
TRIS(CYCLOPENTADIENYL)ZIRCONIUM
TETRAKIS(PENTAFLUOROPHENYL)BORATE
D.P. Fedorov1, 2, V.Ya. Churkina1, E.I. Knerelman1, V.D. Makhaev1,
Yu. I. Zlobinskiy1, I.V. Sedov1, 2
76
1
Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Russia
Departmentof Fundamental Physics and Chemical Engineering, Moscow State University, Russia
2
14. SYNTHESIS OF N-VINYL SUCCINIMIDE POLYMERS FOR BIOMEDICAL APPLICATIONS VIA RAFT POLYMERIZATION IN
BULK
A. Gostev1,E. Sivtsov1, E. Parilova2, E. Chernikova3
77
1
Plastics Technology Department, Saint-Petersburg State Institute of Technology, Russia
Institute of Macromolecular Compounds of the RAS, Saint-Petersburg, Russia
3
2
15. NEW ELECTRO-ACTIVE MATERIALS FOR ORGANIC LIGHT
EMITTING DIODES
D. Tavgeniene1, G. Krucaite1, R. Griniene1, D. Rasymaite1,
S. Grigalevicius1*, J.H. Jou2
78
1
Department of Materials Science and Engineering, National Tsing-Hua University, Taiwan
2
16. ELECTRO-ACTIVE POLYMERS CONTAINING
ELECTRONICALLY ISOLATED N-PHENYL-N-NAPHTYLAMINE
FRAGMENTS
E. Zaleckas1, R. Zostautiene1, L. Liu2, B. Zhang2, Z. Xie2,
S. Grigalevicius1
79
1
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, Changchun, China
2
17. VISUALIZATION OF STRUCTURAL REARRANGEMENTS
DURING ANNEALING OF SOLVENT-CRAZED ISOTACTIC
POLYPROPYLENE
T. E.Grokhovskaya, A.L.Volynskii, , A.I.Kulebyakina, A.A.Efimova,
A.V. Bol’shakova, and N.F. Bakeev
80
Polymer Department, M.V.Lomonosov Moscow State University, Moscow, Russia
18. SYNTHESIS AND PROPERTIES OF GLASS-FORMING
NAPHTHALIMIDE COMPOUNDS CONTAINING CARBAZOLE
MOIETIES
D. Gudeika1, J.V. Grazulevicius1, A. Miasojedovas2, S. Jursenas2
81
1
Institute of Applied Research, Vilnius University, Vilnius, Lithuania
2
19. THE EFFECT OF ADDITION OF IONIC LIQUID ON THE
ELECTROSPINNING CONDITIONS OF SAN SOLUTIONS AND
THE MORPHOLOGY OF OBTAINED NANOFIBERS
V. Gudkova1, M. Viirsalu1, M.Rikko2, E.Tarassova2, T.Märtson2,
A. Krumme2
82
1
Department of Polymer Materials, Tallinn University of Technology, Tallinn, Estonia
14
2
20. Synthesis and properties of new phenanthroimidazole-based monomer
and polymer
A. Ivanauskaitė, R. Lygaitis and J. V. Gražulevičius
83
21. THE MODIFICATION THE POLYAMIDE FILMS BY LAYERS OF
METAL SELENIDE
R. Ivanauskas, I. Ancutienė, L. Samardokas, A. Ivanauskas
84
Department of Inorganic Chemistry, Kaunas University of Technology, Kaunas, Lithuania
22. SYNTHESIS OF MULTIBLOCK COPOLYMERS BY RAFT USING
LINEAR MULTIFUNCTIONAL CHAIN TRANSFER AGENTS
J. Jonikaitė-Švėgždienė, T. Krivorotova, T. Joskaudas, R. Makuška
85
23. UNIQUE PROPERTIES OF IONIC LIQUIDS AS A NOVEL
INITIATOR OF RADICAL POLYMERIZATION
S. Kanno
86
Polymer Chemistry Laboratory, Tohoku Seikatsu Bunka University, Sendai, Japan
24. ENHANCING THE SURFACE CHARGE OF BCTMP OF ASPEN
WITH SUPERCRITICAL CO2 TREATMENT
K. Kärner1, R. Talviste1, K. Viipsi2, U. Kallavus1
1
2
Centre for Materials Research, Tallinn University of Technology, Tallinn, Estonia
Laboratory of Inorganic Materials, Tallinn University of Technology, Tallinn, Estonia
25. LIGHT EMMITING DENDRONIZED OLIGOPHENYLENES WITH
ACETYLENE GROUPS
I. A. Khotina1, M. A. Babushkina1, N. S.Kushakova1, A. I.Kovalev
1
87
88
A.N.Nesmeyanov Institute of organoelement compounds RAS, Moscow, Russia
26. RAFT COPOLYMERIZATION OF PEO MACROMONOMERS IN
THE PRESENCE OF TRITHIOCOMPOUNDS
V. Klimkevičius, R. Makuška
89
27. THERMAL OXIDATION AND INVESTIGATION OF
COMMERCIAL POLYPROPYLENE
R. Alaburdaitė1, V. Krylova2
1
2
90
Department of General Chemistry, Kaunas University of Technology, Kaunas, Lithuania,
28. ELECTROACTIVE THIOPHENE- AND PHENOTHIAZINE-BASED
HYDRAZONE MONOMERS
R. Laurinavičiūtė, J. Ostrauskaitė, J. V. Gražulevičius
91
29. THE INFLUENCE OF CHAIN MICROSTRUCTURE ON SELFORGANIZATION OF COPOLYMERS IN SEMIDILUTE
SOLUTIONS
E. Litmanovich
92
Polymer Chair, Chemical Faculty, Moscow State University, Moscow, Russia
30. RADICAL POLYMERIZATION OF ACRYLIC MONOMERS IN
THE PRESENCE OF COPPER (II) IONS IN AQUEOUS
SOLUTIONS
E. Sivtsov, A. Logunova, A. Gostev
93
31. MIXED POLYMER MICELLES WITH SEGREGATING
AMPHIPHILIC CORONA
E. A. Lysenko1, A.M. Rumyantsev2, E.Yu. Kramarenko2, A.B. Zezin1
1
2
94
Chemical Department, Moscow State University, Moscow, Russia
Physical Department, Moscow State University, Moscow, Russia
15
32. GLASS-FORMING TRIPHENYLAMINE DERIVATIVES AS HOLE
TRANSPORTING MATERIALS
V. Mimaite1, J.V. Grazulevicius1, V. Jankauskas2
1
2
95
Department of Solid State Electronics, Vilnius University, Vilnius, Lithuania
33. COPPER NANOPARTICLE EFFECT ON THE PROPERTIES OF
PERIODICAL STRUCTURE FORMED ON PHOTORESIST
P. Narmontas1, J. Pudlauskaitė2, V. Jankauskaitė2, E. Giškonis3,
I. Prosyčevas1
96
1
Institute of Materials Science, Kaunas University of Technology, Kaunas, Lithuania
3
Department of General Chemistry, Kaunas University of Technology, Kaunas, Lithuania
2
34. THE COMPETITIVE INTERACTIONS OF POLYANIONIC
HYDROGELS WITH WATER-SOLUBLE
INTERPOLYELECTROLYTE COMPLEXES RICH IN THE
LINEAR POLYCATIONS
O.A. Novoskoltseva, V.B. Rogacheva, A.B. Zezin
97
Department of Polymer Science, Faculty of Chemistry, Lomonosov Moscow State University,
Russia, Moscow, Russia
35. COMPETITIVE REACTIONS IN THE TRIPLE SYSTEM,
CONTAINIG POLY(ACRYLIC ACID) STAR, LINEAR, AND
CROSS-LINKED POLYELECTROLYTES
T. V. Panova and A. B. Zezin
98
Polymer Department, Faculty of Chemistry, M.V. Lomonosov Moscow State University, Moscow,
Russia
36. POLYTHIONIC COMPOUNDS AS PRECURSORS FOR THE
FORMATION OF SOME METAL CHALCOGENIDE LAYERS ON
POLYAMIDE 6 SURFACE
V. Janickis, R. Stokienė, N. Petrašauskienė, S. Žalenkienė
99
37. ALUMINUM COMPLEXES WITH PHENOXY-IMINE AND SALEN
LIGANDS AS CATALYSTS FOR RING-OPENING
POLYMERIZATION OF -CAPROLACTONE AND D,L-LACTIDE
Yu.A. Piskun 1, I.V. Vasilenko 1, S.V. Kostjuk 1, K.V. Zaitsev 2
100
1
Research Institute for Physical Chemical Problems of the Belarusian State University,
Minsk, Belarus
2
Moscow State University, Department of Chemistry, Moskow, Russia
38. THE COMPOSITE MATERIALS OF POLYANIONS AND MULTIWALLED CARBON NANOTUBES: SYNTHESIS AND
PROPERTIES
O. Pyshkina, N. Volosova, V. Sergeyev
101
Department of Polymer Science, Faculty of Chemistry, Lomonosov Moscow State University,
Russia, Moscow
39. SYNTHESIS OF GLASS-FORMING CARBAZOLE DERIVATIVES
BY THE METHOD OF CLICK CHEMISTRY
G. Samulionytė, J. Simokaitienė, J. V. Gražulevičius
102
40. MULTIARM STAR WITH POLY(ETHYLENEIMINE) CORE AND
POLY(ε-CAPROLACTONE) ARMS AS MODIFIERS OF
DIGLYCIDYLETHER OF BISPHENOL A THERMOSETS CURED
BY 1-METHYLIMIDAZOLE
C.Acebo1, X. Fernández-Francos1, F.Ferrando2, A. Serra1, J.M.Salla3,
X.Ramis3
103
1
Department of Analytical and Organic Chemistry, Universitat Rovira i Virgili, Tarragona, Spain
Department of Mechanical Engineering, Universitat Rovira i Virgili, Tarragona, Spain
3
Thermodynamics Laboratory, ETSEIB Universitat Politècnica de Catalunya, Barcelona, Spain
2
16
41. CATIONIC POLYMERIZATION OF ISOBUTYLENE BY
AlCl3/ETHER COMPLEXES IN NON-POLAR SOLVENTS
D. I. Shiman, I. V. Vasilenko, A. N. Frolov, S. V. Kostjuk
104
Belarus
42. SYNTHESIS OF CHARGE -TRANSPORTING MOLECULAR
GLASSES BY THE MOTHOD OF CLICK CHEMISTRY
G. Šimkus1, A. Tomkevičienė1, J. V. Gražulevičius1
1
105
Department of Organic Technology, Kaunas University of Technology, Kaunas, Lithuani a
43. SYNTHESIS OF COMPOSITIONALLY HOMOGENEOUS
GRADIENT COPOLYMERS VIA RAFT POLYMERIZATION
E. Sivtsov1, A. Gostev1, E. Chernikova2
106
1
2
44. SYNTHESIS AND PROPERTIES OF
SPIRO(FLUORENE-9,9'-XANTHENE)-BASED MONOMERS
J. Songaila, J. Ostrauskaitė, J. Simokaitienė, J. V. Gražulevičius
107
45. INVESTIGATION OF ELECTRO-ACOUSTIC EFFECTS IN
ORGANIC STRUCTURE
N. Kus1, P. Stakhira1, D. Volyniuk1,2, V. Cherpak1, J.V. Grazulevicius2,
N.A. Kukhta2, G. Barylo1, Z. Hotra1,3
108
1
Lviv Polytechnic National University, Lviv, Ukraine
3
Rzeszów University of Technology, Rzeszów, Poland
2
46. SYNTHESIS AND PROPERTIES OF INDOLO[3,2-b]CARBAZOLE
MONOMERS AND CROSS-LINKED POLYMERS FOR
OPTOELECTRONIC DEVICES
E. Stanislovaitytė1, J. Simokaitienė1, J.V. Gražulevičius1
109
1
47. LOW-MOLAR-MASS AND POLYMERIC GLASS FORMING
CARBAZOLE DERIVATIVES CONTAINING TRI- AND
TETRAPHENYLETHYLENE GROUPS FOR OPTOELECTRONICS
J. Šutaitė1, A. Tomkevičienė1, J. V. Gražulevičius1
1
110
48. SYNTHESIS OF CATECHOLIC GROUPS CONTAINING
COPOLYMERS OF DMAEMA
M. Kirsnytė, V. Pamedytytė, A. Vareikis
111
49. RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE
INITIATED BY FUNCTIONALIZED ALUMINUM ALKOXIDES: A
SIMPLE ROUTE TO THE BIODEGRADABLE
MACROMONOMERS
I.V. Vasilenko1, Yu.A. Piskun1, S.V. Kostjuk1, K.V. Zaitsev2
112
1
Belarus
2
Chemistry Department, Moscow State University, Moscow, Russia
50. THE EFFECT OF ALKALI CATALYST CONTENT AND WATER
CONTENT IN ORGANOSOLVE WHEAT STRAW LIGNIN ON
PROCESS OF IT OXYPROPYLATION AND CRARACTERISTICS
OF LIGNOPOLYOLS OBTAINED
A. Arshanitsa, L. Vevere, G.Telysheva.
113
Latvian State Institute of Wood Chemistry, Riga, Latvia
51. AMPHIPHILIC MULTIBLOCK-COPOLYMERS: SYNTHESIS AND
PROPERTIES
114
17
D. Vishnevetsky, E. Chernikova
Polymer Department, Faculty of Chemistry, Moscow State University, Moscow, Russia
52. SUPPLEMENTAL REDOX INTERMEDIATES ENHANCING SARA
ATRP OF HYDROPHYLIC MONOMERS IN AQUEOUS
SOLUTIONS
C. Visnevskij, R. Makuska
115
53. PREPARATION AND INVESTIGATION OF PLANE POLYMERIC
BRUSHES WITH BRUNCHES OF PBLG AND PLGA ON SI
SURFACE.
E. Vlasova, B. Volchek, E. Pruchkina
116
Institute of Macromolecular Compounds, Russian Academy of Sciences, Saint-Petersburg, Russia
54. ELECTRO-ACTIVE POLYMERS CONTAINING
FRAGMENTS
E. Zaleckas1, R. Zostautiene1, L. Liu2, B. Zhang2, Z. Xie2,
S. Grigalevicius1
117
1
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, Changchun, China
2
55. XRD STUDY OF CdSe-CdS FILMS ON POLYAMIDE
CONVERSION INTO Ag2Se-Ag2S FILMS
S. Žalenkienė, V. Krylova
118
56. SYNTHESIS AND PROPERTIES OF ARYLMETHYLENE-1,3INDANDIONE BASED MONOMERS
V. Zilinskaite, A. Tomkeviciene, D. Gudeika, J.V. Grazulevicius
119
57. SYNTHESIS AND FUNCTIONALISATION OF NEW
PYRROLO[2,3-F]INDOLO BUILDING BLOCKS
M. Vlasselaer, W. Dehaen
University of Leuven , Belgium
58. HIGHLY EFFICIENT INTRINSIC PHOSPHORESCENCE FROM
A -CONJUGATED POLYSILANE POLYMER
A. Kadashchuk1,2, Yu. Skryshevski1, S. Toliautas3, J. Sulskus3, L.
Valkunas3, S. Nespurek4
178
1
Institute of Physics, National Academy of Sciences of Ukraine, 03028 Kyiv,
Ukraine, [email protected]
2
Polymer and Molecular Electronics Department, IMEC, B-3001, Leuven, Belgium
3
Faculty of Physics, Vilnius University, LT-10222 Vilnius, Lithuania
4
Institute of Macromolecular Chemistry, Academy of Sciences of Czech Republic, Prague, Czech
Republic
18
POSTER SESSION II
PLASTICS, COMPOSITES, RECYCLING AND APPLICATION
1. MOISTURE INFLUENCE ON MECHANICAL PROPERTIES OF
THE CNT/EPOXY RESIN NANOCOMPOSITE WITH
DIFFERENT NANOFILLER CONTENT
A. Borisova, T. Glaskova, A. Aniskevich
120
Institute of Polymer Mechanics, University of Latvia, Riga, Latvia
2. MICROSTRUCTURE AND PROPERTIES OF BACTERIAL
CELLULOSE
L. Belkova1, R. Treimane2, P. Semjonovs2, I. Denina2, A. Treimanis1,
U. Grinfelds1
121
1
Latvia University Institute of Microbiology and Biotechnology, Riga, Latvia
2
3. ELECTRODEPOSITION OF CdSe NANOFIBERS AS PHOTOACTIVE MATRIX FOR POLYMER SOLAR CELLS
J. Kois1, S. Bereznev1, J. Gurevits1, E. Mellikov1, A. Öpik1
1
122
4. FORMATION AND CHARACTERIZATION OF PECTIN-ZEIN
MICROSPHERES
J.T. Bobokalonov1, J. Liesiene1, Z.K. Mukhidinov2, G.F. Kasimova2,
A.S. Nasriddinov2
123
1
Institute of Chemistry named after V.I. Nikitin, Academy of Sciences, Dushanbe, Republic of
Tajikistan
2
5. COLOUR PROPERTIES OF DYED RAW LINEN FABRIC
PRETREATED WITHENZYMES
A.Bernava, S. Reihmane
124
6. THE EFFECT OF NANOSTRUCTURED OXIDE BASED
MODIFIER ON THE STRUCTURE AND PROPERTIES OF
THERMOPLASTIC POLYMERS
I. Bockovs1, R. Merijs Meri1, J. Zicans1, R. Berzina1, J. Krastins2,
I. Zalite2
125
1
Institute of Inorganic Chemistry, Riga Technical University, Salaspils, Latvia
2
7. DEVELOPMENT OF A SURFACE IMPRINTING STRATEGY
BASED ON A COVALENTLY IMMOBILIZED PROTEIN
R. Boroznjak, A. Tretjakov, V. Syritski, J. Reut and A. Öpik
126
8. THE INVESTIGATION OF KNITTED MATERIALS BONDED
SEAMS STRENGTH UNDER BIAXIAL TENSION
G. Busilienė, E. Strazdienė, V. Urbelis
127
Department of Clothing and Polymer Products Technology, Kaunas University of Technology,
Kaunas, Lithuania
9. MULTIFUNCTIONAL BLENDS FOR COMPACT WET
FINISHING OF LEATHERS
M.Crudu1, C.Gaidau1, A. Crudu1, M. Popescu2, M. Ionescu3
128
1
INCDTP-Leather and Footwear Research Institute (ICPI), Bucharest, Romania
S.C. PIELOREX SA Jilava, Romania
3
SC EUROPLASTIC LTD, Bucharest, Romania
2
10. LEATHER FINISHING WITH FILM FORMING POLYMERS
DOPED WITH NANO PHOTOCATALYSTS
C. Gaidau, A. Petica, M. Fleancu, C.Sendrea, A.M.Mocioiu1,
129
19
M. Ionescu2
Department of Leather Research, 1INCDTP-ICPI Division, Bucharest, Romania,
2
S.C. EUROPLASTIC L.T.D., Bucharest, Romania
11. NEW GUANIDINE-CONTAINING POLYMER SORBENTS
M. Gorbunova, T. Batueva
130
Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
12. NEW LUPANE-CONTAINING POLYMERS FOR MEDICAL
APPLICATION
M. Gorbunova, G. Krainova, I. Tolmacheva, V. Grishko
131
13. NANOSTRUCTURED ZnO CONTAINING ELASTOMERE
MODIFIED POLYOXYMETHYLENE COMPOSITES
A.Grigalovica1, R.Merijs Meri1, J.Zicans1, J.Grabis2
1
132
2
14. CELLULOSE-BASED HYDROGELS FOR WOUND DRESSING
S. Gustaite1, J. Kazlauske1, J. Liesiene1, M. Nasiri Boroumand2,
V. Dutschk2
133
1
Kaunas University of Technology, Kaunas, Lithuania
Twente University, Enschede, Netherlands
2
15. CHARACTERIZATION OF STYRENE COPOLYMER BASED
NANOCOMPOSITES WITH NANOSTRUCTURED CLAY
J. Bitenieks1, R. Berzina1, T. Ivanova1, R. Merijs Meri1, J. Zicans1,
V. Kalkis2
134
1
2
16. PROPERTIES OF POLYURETHANES BASED ON TALL OIL
ESTERS WITH INTUMESCENT FLAME RETARDANTS
V. Yakushin, I. Sevastyanova, D. Vilsone, M. Kirpluks
135
17. STRUCTURE AND PROPERTIES OF SILICONE ELASTOMERS
AND SILVER NANOPARTICLES COMPOSITES
V. Jankauskaitė, A. Lisauskaitė
136
Faculty of Design and Technologies Kaunas University of Technology, Kaunas, Lithuania
18. STUDIES OF BLENDS OF POLY (VINYL ALCOHOL) AND POLY
(VINYL ACETATE)
N. Jelinska1, M.Kalnins1, E.Auzins1, A. Kovalovs2
1
2
137
Institute of Materials and Structures, Riga Technical University, Riga, Latvia
19. POLYOLEFIN/NANOCLAY NANOCOMPOSITE FILMS FOR
PACKAGING EXPLOITATION PROPERTIES
J. Kajaks, K. Kalniņš, E.Sidorovs
138
20. NATURAL OIL BASED POLYMERS WITH PHOSPHOESTER
CROSS-LINKS
S. Kašėtaitė, J. Ostrauskaitė, J.V. Gražulevičius
139
21. OPTIMAL DESIGN OF POLY (VINYL ALCOHOL)/POLY
(VINYL ACETATE) BLENDS FILMS BASED ON THE
PLANNING OF EXPERIMENTS
A. Kovalovs1, A. Chate1, N. Jelinska2
1
2
140
22. DEFORMATION CHARACTERISTICS OF GENUINE LEATHER,
MANUFACTURED USING NATURAL MINERALS
141
20
O.P. Kozar1, O.R. Mokrousova 2, V.P. Konoval3
1. Mukachevo State University, Mukachevo, Ukraine
2. Kyiv National University of Trade and Economics, Kyiv, Ukraine
3.Kyiv National University of Technologies and Design, Kyiv, Ukraine
23. EXTRACTION METHODS OF FRUCTO-OLIGOSACCHARIDES
FROM JERUSALEM ARTICHOKE TUBERS
T. Krivorotova1, J. Sereikaite1, P. Glibowski2
142
1
Department of Chemistry and Bioengineering, Vilnius Gediminas Technical University, Vilnius,
Lithuania
2
Department of Milk Technology and Hydrocolloids, University of Life Science, Lublin, Poland
24. SELF-ASSEMBLING DIBLOCK COPOLYMERS AS VEHICLES
FOR POORLY SOLUBLE DRUGS
L. Kunitskaya, T. Zheltonozhskaya
143
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine
25. SURFACE ROUGHNESS AND WETTABILITY OF WOOD
SAMPLES DEPENDING OF THE COATING
L. Laiveniece1, A. Morozovs2
144
1
Forest Faculty, Latvia University of Agriculture, Jelgava, Latvia
Faculty of Food Technology, Latvia University of Agriculture, Jelgava, Latvia
2
26. POLY(URETHANE-UREA) MICROCAPSULES FOR
IMMOBILIZATION OF MALTOGENASE
S. Maciulyte, G. Valungeviciute, J. Razumiene, I. Sakinyte,
T. Kochane, I. Gerasimcik, S. Budriene
145
27. EFFECT OF POLYMERIC COMPOUNDS ON ISOELECTRIC
POINT OF COLLAGEN
L. Maistrenko, O. Andreyeva
146
Department of Leather and FurTechnology, Kyiv National University of Technologies and Design,
Kyiv, Ukraine
28. ESTIMATION OF ELECTROSPUN WEB FROM PA6.6
NANOFIBRES
J. Malašauskienė, R. Milašius
147
Department of Textile Technology, Kaunas University of Technology, Kaunas,
Lithuania
29. SOME FUNCTIONAL PROPERTIES OF COMPOSITE
MATERIAL FROM RECYCLED TIRES IN WATER MEDIUM
R. Plesuma, L. Malers
148
Department of Polymer Material Technology, Riga Technical University, Riga, Latvia
30. STRUCTURE AND PROPERTIES OF LIQUID CRYSTAL
MODIFIER AND LAYERED SILICATE CONTAINING
POLYMER HYBRID COMPOSITES
R. Merijs Meri1, J. Zicans1, T. Ivanova1, I. Elksnite1, M. Kalnins1,
V. Kalkis2
149
1
2
31. THE INVESTIGATION OF WATER SORPTION ON THE
ANTIMICROBIAL TREATED PLAIN AND PLATED KNITS
A. Mickevičienė, R. Treigienė
150
Department of Textile Technology, Kaunas University of Technology, Kaunas, Lithuania
32. TRANSFORMATION OF COLLAGEN HIERARCHICAL
STRUCTURE AT NANO- AND MICROLEVELS INFLUENCED
BY MODIFIED MONTMORILLONITE
O. Mokrousova1, Yu. Dzyazko2
151
1
Kiev National Trade and Economics University
V.I. Vernadskii Institute of General & Inorganic Chemistry of the NAS of Ukraine
2
21
33. RIGID POLYURETHANE FOAMS FROM OXYPROPYLATED
WHEAT STRAW LIGNIN
A. Paberza, A. Arshanitsa, U. Cabulis
152
34. CELLULOSE/HYDROXYAPATITE FRAMEWORKS FOR BONE
TISSUE REGENERATION
O. Petrauskaite1, J. Liesiene1, I. Jaruseviciute1, G. Juodzbalys2,
J. Maminskas2, A. Stumbras2, P. Daugela2
1
2
153
Lithuanian University of Health, Department of Maxillofacial Surgery, Lithuania
35. APPLICATIONOF COLLAGEN-CONTAINING WASTE TO
PRODUCEOF BIOPOLYMERSAND COMPOSITES
WITHPREDICTABLE PROPERTIES
V. Plavan
154
Department of Leather & Fur Technologies and Department ofTechnological Safety, Kiev
National University of Technologies & Design, Kiev, Ukraine
36. CATALYTIC CURING OF EPOXY RESIN APPLICABLE FOR
THE RESTORATION OF GLASS ARTEFACTS
D. Ragauskienė, J. Laurinavičiūtė
155
37. SILICON COLLOIDS LIGHT/UV STABILISERS OF
POLYSTYRENE AND POLYPROPYLENE
M. Bermejo1, M. Schmitt1, S. Sánchez-Ballester1 O. Gil-Castell1,
R.Teruel-Juanes1, M. Rosado-Gil1, L. Santonja-Blasco1, A. MartínezFelipe1, I. Rodrigez2, F. Meseguer2A. Ribes-Greus1
156
1
Instituto de Tecnología de los Materiales (ITM), Universitat Politècnica de València (UPV)
Camino de Vera S/N, 46022 Valencia, Spain
2
Unidad Asociada CSIC-UPV Universitat Politècnica de València, Avda Tarongers s/n, 46022,
Valencia, Spain
38. BLENDS OF PAA AND IONOMERS LC COPOLYMERS FOR
ELECTROLYTES IN DMFC AND DEFC
P. Fernandez1, T.Lamberty1, S. Sánchez-Ballester1 O. Gil-Castell1,
R.Teruel-Juanes1, M. Rosado-Gil1, A. Martínez-Felipe1, V. Soria2,
A. Ribes-Greus1
157
1
Camino de Vera S/N, 46022 Valencia, Spain,
2
Institut de Ciència dels Materials (ICMUV), Universitat de València (UVEG)
39. INFLUENCE OF MALEIC ANHYDRIDE AS COUPLING AGENT
IN PLA/SISAL BIOCOMPOSITES UNDER HYDROTHERMAL
DEGRADING CONDITIONS
J. Alonso, C. Moran, O. Gil-Castell, S. Sánchez-Ballester, R.TeruelJuanes, M. Rosado-Gil1, J.D. Badia, A. Martínez-Felipe, A. RibesGreus
158
40. INFLUENCE OF SISAL FIBERS ON THERMAL
DECOMPOSITION OF POLI(HYDROXIBUTYRATE-COVALERATE) BIOCOMPOSITES
O. Gil-Castell, M. Rosado-Gil, S. Sánchez-Ballester, R.Teruel-Juanes,
C. Moliner-Estopiñán, A. Martínez-Felipe, J.D. Badia, A. RibesGreusa
159
41. THE EFFECT OF COUPLING AGENTS ON THE PHYSICAL
AND MECHANICAL PROPERTIES OF WOOD-PLASTIC
160
22
COMPOSITES
K. Saar, I. Repeshova, K. Liimand, T. Poltimäe, J. Kers
42. INVESTIGATION OF APPLICATION OF PEDOT-PSS ON
ANTISTATIC TEXTILES
A. Sankauskaitė1, P. Bekampienė1, S. Varnaitė-Žuravliova1,
I. Prosyčevas2, M. D. Tumėnienė1, A. Abraitienė1
161
1
Textile Institute of Center for Physical Sciences and Technology, Kaunas, Lithuania
Institute of Materials Science Kaunas University of Technology, Kaunas, Lithuania
2
43. INFLUENCE OF CHITOSAN CONTENT ON SURFACE
ACTIVITY OF LIGNIN-BASED POLYELECTROLYTE
COMPLEX
V. Shakels1, G. Shulga1, S. Livcha1, M. Dzenis2
162
1
Riga Technical University, Riga, Latvia
2
44. EFFECT OF STORAGE TIME ON THE AQUEOUS SOLUTION
PROPERTIES OF POLYELECTROLYTE COMPLEX BASED ON
SODA LIGNIN
G. Shulga, S. Vitolina, B. Neiberte, A. Verovkins, J. Brovkina,
S. ivcha, V. Shakels
163
45. THE EFFECT OF RECYCLING DURATION AND FILLING ON
THE PROPERTIES OF POLYCAPROLACTONE-BASED
THERMOPLASTIC POLYURETHANE
V. Skrockienė, K. Žukienė, A. Lisauskaitė
164
Kaunas, Lithuania
46. HIGH DENSITY RIGID POLYURETHANE FOAMS OBTAINED
FROM RESIDUES OF PET INDUSTRY AND MODIFIED WITH
CLOISITE TYPE NANOPARTICLES
L. Stiebra, U. Cabulis, M. Kirpluks
165
47. IMMOBILIZATION AND CATALYTIC PROPERTIES OF
MALTOGENIC α-AMYLASE ON PUU MICROPARTICLES
A. Strakšys1,A. Dulko1, J. Razumiene2, I. Sakinyte2, T. Kochane1,
S. Budriene1
166
1
Institute of Biochemistry, Vilnius University, Vilnius, Lithuania
2
48. THE EFFECT OF PLASMA TREATMENT ON THE TENSILE
PROPERTIES OF NATURAL FIBER REINFORCED PLA
COMPOSITES
A. Širvaitienė1, V. Jankauskaitė1, P. Bekampienė2
1
2
SRI Center for Physical Science and Technology Textile Institute, Kaunas, Lithuania
49. MICROBIOLOGICAL INVESTIGATION OF SHORT TIME
PRESERVED SKIN
J. Širvaitytė1, K. Beleška1, V. Valeikienė1, V. Valeika2,
R. Alaburdaitė2
1
2
167
168
Department of Organic Technology, Kaunas University of Technology, Kaunas Lithuania
50. BIODEGRADBLE POLYMER COMPOSITES CONTAINING
NUTRIENTS FOR SLOW RELEASE FERTILISERS
J. Treinyte1, V. Grazuleviciene1, M. Gumbyte2
169
1
Institute of Environment and Ecology, Aleksandras Stulginskis University, Akademija, Kaunas
region, Lithuania
23
2
Laboratory of Chemical and Biochemical Research for Environmental Technology, Aleksandras
Stulginskis University, Akademija, Kaunas region, Lithuania
51. EFFECT OF FINISHING TREATMENT ON YARN PULLOUT
BEHAVIOUR IN TERRY FABRICS
S. Petrulytė, A. Veličkienė, D. Petrulis
170
Department of Textile Technology, Kaunas University of Technology, Kaunas, Lithuania
52. POLYETHYLENIMINE FOR USE AS A COAGULANT FOR
EXTRACTING WOOD BIOMASS FROM WASTEWATER
S. Vitolina, G. Shulga, B. Neiberte, S. Reihmane
171
53. ELECTROPHOSPHORESCENT DIODES BASED ON Ir(Fppy)3.
D. Volyniuk1,2, P. Stakhira2, J.V. Grazulevicius1, V. Cherpak2,
J. Keruckas1,Z. Hotra2,3, M. Hladun4
172
1
3
4
European University, Lviv, Ukraine
2
54. NANOCOMPOSITES BASED ON POLYURETHANE AND ON
MESOPOROUS SILICON DIOXIDE MODIFIED WITH METAL
OXIDES
Volkova E.R.
173
55. STRUCTURE–PROPERTY RELATIONSHIPS OF
POLYURETHANE COMPOSITES SYNTHESIZED USING
VARIOUS OLIGODIOLS
Volkova E.R.
174
56. RIGID POLYURETHANE FOAMS OBTAINED FROM BYPRODUCTS OF PET PRODUCTION
V. Zeltins1, U. Cabulis1, I. Vitkauskiene2
1
2
175
UAB NEO Group, Rimkai, Dovilai sen. Klaipeda district, Lithuania
57. MOLECULAR DYNAMICS STUDIES OF HYDRATION AND
PHASE BEHAVIOUR OF OXYETHYLATED GLYCEROL
AQUEOUS SOLUTIONS
E. Zhivotova1, V. Andrushchenko2
176
1
Department of Physics, National University of Pharmacy, Kharkov, Ukraine,
Department of Molecular Spectroscopy, Institute of Organic Chemistry and Biochemistry,
Academy of Sciences, Prague, Czech Republic
2
58. THE EFFECT OF UNIAXIAL PRETENSION UPON
MULTILAYER TEXTILE SYSTEMS BIAXIAL STRENGTH
PARAMETERS
D. Zubauskiene, E. Strazdiene, V. Urbelis
177
Kaunas, Lithuania
24
NANOMECHANICAL PROPERTY MAPPING OF POLYMER
COMPOSITES
O. Krivosheeva1, M. Sababi1, G. Dunér1, E. Thormann1, S. Jafarzadeh1, F. Zhang1,
J. Pan1, A. Dedinaite1,2,*, and P. M. Claesson1,2
1
Division of Surface and Corrosion Science, Department of Chemistry, School of Chemical Sciences, Royal
Institute of Technology, SE-100 44 Stockholm, Sweden
2
SP Technical Research Institute of Sweden,Chemistry, Materials and Surfaces, Box 5607, SE-114 86
Stockholm, Sweden
Modern scanning probe instrumentations allow many surface properties besides
topography to be determined simultaneously. For instance with the PeakForce QNM mode
developed by Bruker images of surface topography, tip-sample adhesion, energy
dissipation, surface deformation and elastic modulus can be obtained simultaneously. With
some additional efforts also electrical conductivity maps can be created. This presentation
will describe how these properties are extracted from measured tip-surface force curves,
and some examples of surface property maps obtained for various layer structures will be
provided. Examples will include:
 Deposited nanoparticles that carries a grafted polymer layer. Here we will
demonstrate how the mechanical properties vary across the polymer-coated nanoparticle.
 Composite layers formed by mussel adhesive proteins and ceria nanoparticles
constitute a promising way to reduce corrosion. It will be discussed how the robustness of
such films are enhanced by the high level of DOPA groups in the mussel adhesive protein,
and an AFM-based robustness test will be described.
 Polymer layers containing low amounts of conducting polymer is another way to
combat corrosion, and we will show how scanning probe microscopy can be used for
distinguishing the conducting polymer additive from the matrix, and for demonstrating the
presence of a conducting network.
References
1. M. Sababi, F. Zhang, O. Krivosheeva, M. Forslund, J. Pan, P.M. Claesson, and A. Dedinaite. J.
Electrochem. Soc., C364-C371 (2012).
2. G. Dunér, E. Thormann, A. Dedinaite, P.M. Claesson, K. Matyjaszewski, and R.D. Tilton. Soft Matter,
8, 8312-8320 (2012).
3. M. Sababi, J. Kettle, H. Rautkoski, P.M. Claesson, and E. Thormann. ACS Appl. Mat. Interfaces, 4,
5534-5541 (2012).
25
AQUEOUS LUBRICATION BY ADSORBED POLYMER LAYERS
A. Dėdinaitė,1,2 X. Liu1, M. Rutland1,2,E. Thormann1, Č. Višnevskij3, R. Makuška3,
and P. M. Claesson1,2
1
KTH Royal Institute of Technology, School of Chemical Sciences and Engineering, Department of
Chemistry, Surface and Corrosion Science, Drottning Kristinas väg 51, SE-10044 Stockholm,
[email protected]
2
Materials and Surfaces, SP Technical Research Institute of Sweden, Box 5607, SE-114 86 Stockholm,
Sweden
3
Department of Polymer Chemistry, Vilnius University, Naugarduko 24, LT-03225 , Vilnius, Lithuania
Bottle-brush polymers are important constituents in naturally occurring biolubrication
systems, such as the synovial joints. We have made synthetic diblock bottle-brush
polymers that are designed to adsorb strongly to negatively charged surfaces, and
demonstrate how they can be used for forming an extended branched brush layer by
physisorption. Thediblock copolymer consists of a linear cationic blockthat anchors to the
surface and a non-ionic bottle-brush block with 45 units long poly(ethylene oxide) side
chains that form the extended bottle-brush structure. The adsorption properties of the
diblock copolymer, as well as of the two blocks separately, were studied on silica surfaces
using QCM-D, optical and neutron reflectometry. In agreement with theoretical
predictions,1 it was found that the surface excess was higher than for random copolymers
with the same type of segments. The water content of the adsorbed layer was found to be
high, above 90%. The kinetic adsorption data highlight that the diblock copolymers
initially adsorb preferentially parallel to the surface with both the cationic block and the
uncharged bottle-brush block in contact with the surface. However, as the adsorption
proceeds a structural change occurs within the layer and the PEO bottle-brush block
extends towards solution, forming a surface anchored branched brush layer.2
The forces acting between two such layers were determined with the AFM colloidal
probe technique and found to be dominated by a weak electrostatic repulsion at large
separations, and at shorter separations by a strong steric repulsion. The boundary
lubrication offered by the adsorbed layers was very favorable, combing a friction force
characterized by a friction coefficient of 0.03, a high load bearing capacity of at least 60
MPa in pure water, and a self-healing ability.3 The importance of the polymer structure and
the binding mechanism to the surface for these findings will be discussed.
References
1. 1. P. Linse, P.M. Claesson. Macromolecules, 42, 6310-6318 (2009).
2. 2. X. Liu, A. Dėdinaitė, M. Rutland, E. Thormann, E., Č. Višnevskij, R. Makuška, and P.M. Claesson.
Langmuir, 28, 15537-15547 (2012).
3. 3. X. Liu, E. Thormann, A. Dėdinaitė, M. Rutland, Č. Višnevskij, R. Makuška, and P.M. Claesson. Soft
Matter, 9, 5361-5371 (2013).
26
POLYANILINE: ITS BIRTH, LIFE, AND PASSING AS STUDIED BY
RAMAN SPECTROSCOPY
A. Malinauskas
Department of Organic Chemistry, Institute of Chemistry, Center for Physical Sciences and Technology,
Vilnius, Lithuania
Raman spectroscopy and its modifications like Resonant and Surface Enhanced
spectroscopy, as well as its combination with other methods like electrochemistry, are
useful tools in studying various aspects related to polymer chemistry and physics. During
the past decade, we paid much attention to new developments in time-resolved Raman
spectroscopy and spectroelectrochemistry, and their uses in kinetic studies related to
conducting polymers, and especially polyaniline.
One of our objectives are studies related to kinetics of aniline polymerization. Aniline
and many of its derivatives can be simply polymerized either by the chemical oxidation of
the corresponding monomers, or electrochemically by applying anodic oxidation
procedure. Both techniques generate active species like cation-radicals, which trigger the
polymerization process. As for chemical polymerization, many of reaction variables like as
concentration of reactants, the molar ratio of monomer to oxidant, the composition and
acidity of polymerization solution, are of primary interest in seeking of a good quality of a
resulting polyaniline. With the use of time-resolved Raman spectroscopy, we studied the
kinetics of chemical polymerization of aniline and N-methylaniline. The influence of
reaction variables on the kinetics have been studied, and some interesting phenomena like
as sigmoidal kinetics was demonstrated.
An another area of our studies presents investigation of redox transformations and
proton doping of polyaniline layers deposited at electrodes. It has been shown with Raman
spectroscopy that various polymer forms differing by the degree of proton doping level and
the redox state can exist at electrode depending on the electrochemical potential applied,
and acidity of surrounding electrolyte. Electrochemical redox transformations between
these forms have been studied, and the influence of reaction variables on these processes
was estimated.
Some electrochemical redox processes are accelerated at electrodes coated with
polyaniline and related polymers, enabling one to use them as sensors or biosensors for
assay of important biochemical substances. For the first time, we performed in situ studies
on electrocatalytic reactions of such substances like ascorbate, with the use of Raman
spectroscopy. The “redox catalysis” was found to be prevalent over “metal-like” catalysis
for many electrocatalytic reactions proceeding at polyaniline modified electrodes. It was
demonstrated that Raman spectroscopy, especially Surface Enhanced Raman spectroscopy,
presents a unique possibility to identify the depth of a reaction zone located within the
polyaniline layer. The location of this zone was shown to be dependent on many variables
like the concentration of solution species, the thickness of a modifier layer etc.
Time-resolved study on the decomposition of polyaniline and related materials in
electrochemical systems has been performed. It has been shown that the kinetics of this
process depends greatly on electrode potential, and the acidity of electrolyte solution. The
kinetic data obtained with Raman spectroscopy appear to be in a well accordance with the
corresponding data obtained by usual techniques.
27
SPECTROELECTROCHEMISTRY – A VERSATILE TECHNIQUE
FOR ANALYSIS OF CONJUGATED POLYMERS
M. Lapkowski, P. Data, and W. Domagala
Faculty of Chemistry, The Silesian University of Technology, Street M. Strzody 9, 44-100 Gliwice, Poland,
[email protected]
Since their discovery, applications of conductive polymers and conjugated
oligomers have progressed considerably, creating new areas of material sciences like
organic electronics and optoelectronics. Numerous conductive polymers applications
encompass electroluminescent diodes, field effect transistors, photovoltaic cells,
chemical sensors, and electrochromic devices. These applications stem from curious
properties of these materials like low work function, tuneable conductivity, intensive
colour complemented by solution processability. Owing to their favourable redox
properties, electrochemical methods proved a powerful, versatile and convenient tool
for both synthesis and property assay of these materials. When coupled together with
selected spectroscopic techniques details of redox processes taking place in these
polymers in the course of their doping process can be followed and elucidated.
The aim of the presentation is to demonstrate the broad applicability of the
electrochemical methods for the preparation of conjugated polymer insoluble films as
well as their subsequent characterisation. Features of electrochemical polymerisation
offering control of numerous important physicochemical properties of the polymer
films like its molecular mass, thickness or its morphology will be presented. The
application of various potential controlled techniques for the investigation of non stoichiometric redox reactions, underlying the doping phenomena observed in these
polymers, will also be presented.
Adapting and optimising the geometry of an electrochemical cell, one can prepare an
experimental set-up combining electrochemistry with a desired spectroscopic technique. In
this way, UV-Vis-NIR, EPR, IR and Raman spectroelectrochemical measurements and
combinations thereof can practically implemented. Taking advantage of each technique’s
field of focus, it is possible to investigate the electron transitions (UV-Vis-NIR), spin
generation and decay (EPR), heteroatomic bond (IR) and carbon skeletal (Raman)
rearrangements taking place in the investigated (macro)molecules upon change of the
doping level of their π-conjugated bond. Each spectroscopic method affords specific, yet
complimentary information, which pieced together, provide a comprehensive picture of the
investigated electroactive system. Specific examples of real experimental problems will be
demonstrated and the key concepts of their results interpretation shall be presented and
discussed.
28
ELECTROCHEMICAL REDUCTION OF ARYL DIAZONIUM SALTS
FOR ULTRATHIN POLYMERIC LAYERS ON AU AND SI SURFACES
X. Zhang1, V. Syritski2, J. Reut2, F. Rösicke1, G. Sun3, K. Hinrichs3, S. Janietz4 and
J. Rappich1
1
2
3
4
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut für Silizium-Photovoltaik,
Kekuléstr. 5, 12489 Berlin, Germany; [email protected]
Department of Materials Science, Tallinn University of Technology, Ehitajatetee5, Tallinn, 19086, Estonia
Leibniz - Institut für Analytische Wissenschaften - ISAS - e.V., Department Berlin, Albert-Einstein-Str. 9,
12489 Berlin, Germany
Fraunhofer Institute for Applied Polymer Research, Department Polymer Electronics, Geiselbergstr. 69,
D-14476 Potsdam, Germany
F B
polymer
from
4-BBDT
-
F
900 1000 1100 1200 1300 1400
Wavelength (nm)
2
F
0.2
0.0
F
+
N
N
4-BBDT
0
0
-1
-2
-3
-4
-5
1 x 10
-0.8
-0.6
-0.4
-0.2
Potential (Vvs Ag/AgCl)
0.0
-3
-1
-1
NH2
1510 cm
1624 cm
-1
20
0.3
0.1
40
F
F B
ring
0.4
60
1610 cm
Si:H reference
80
NH2 in plane
0.5
Current (µA/cm )
IPL (arb.u.)
Br
benzene ring
0.6
tan / tan Si(111)-H
2
m (ng/cm )
Electrochemistry on conducting or semi-conducting surfaces is a very promising
technique for deposition of ultrathin organic layers. The process can easily be controlled by
the electrochemical parameters such as potential or current and deposition time (i.e. by the
quantity of the passed electric charge) as well as the solution parameters like pH value,
concentration, solvent, electrolyte, and temperature. Additionally the substrate and the
surface influence the deposition by their morphology, charge distribution and orientation.
Substituted aryl diazonium compounds have been grafted covalently on metal, carbon and
semiconductor surfaces by electrochemical reduction from diazonium salts [1-5].
In particular ultrathin layers were deposited on Au and Si surfaces by electrochemical
reduction of e.g. 4-bromophenyldiazonium (4-BBDT). IR and Raman spectroscopy stated
the polyphenylene like chemical structure of deposited moelcules as also supported by
fluorescence spectroscopy data. Electron microscopy measurements (SEM / TEM) showed
the homogeneity of the ultrathin layers (about 4-6 nm thick) and found that e.g. bromine is
present only at the interface but not in the layer itself. Additionally, the deposited amount
was characterized by electrochemical quartz crystal microbalance techniques. The
electronic properties of the ultrathin polyphenylene layer / Si interfaces were studied by
photovoltage and photoluminescence techniques. The results show that the charge on the
Si surface changes and the defect concentration at the interface slightly increases compared
to a perfectly passivated (H-terminated) Si surface (see fig. 1).
(a)
(b) 100
(c)
0.7 exc. 743 nm
-
+
F N
N
F
4-ABDT
1700 1600 1500 1400
-1
Wavenumber (cm )
Fig. 1: (a) PL spectra of the H-terminated and polymeric layer modified Si surface (from 4-BBDT); (b)
current-voltage curve (bottom) and mass increase (top) of Au electrode during electrochemical treatment in
5 mM 4-BBDT in 0.1 M H2SO4 solution; (c) infrared spectrum of an amino functionalization of Si by a thin
layer grafted from a solution with p-aminobenzene diazonium salt.
References
1. J. M. Buriak; Chemical Reviews 102, 1272-1306 (2002).
2. P. Hartig, Th. Dittrich, J. Rappich; J. Electroanal. Chem. 120, 524–525 (2002).
3. J. Pinson, F. Podvorica; Chem. Soc. Rev. 34 433 (2005).
4. J. Rappich, K. Hinrichs; Electrochem. Commun. 11, 2316-2319 (2009).
5. M. M. Chehimi ed., Aryl Diazonium Salts: New Coupling Agents in Polymer and Surface Science
(Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2012).
29
LOW MOLECULAR GLASSES AS A PROMISING CLASS OF
MATERIALS FOR PHOTONIC APPLICATIONS
M. Rutkis1, V. Kokars2, V. Kampars2
1
2
Institute of Solid State Physics, University of Latvia, Riga, Latvia, [email protected]
Institute of Applied Chemistry, Riga Technical University, Latvia
Over the last two decades increased interest in the development of organic photonics
and optoelectronics is driven by demand for new cost effective high performance materials
which are easy to process. Most of attention is focused on such application areas as
photovoltaic, lighting and optical data processing. The key process in manufacturing
organic photonic device for above mentioned applications is preparation of uniform thin
films. In general there are two methods to prepare such films – thermal vacuum vapor
deposition and solution based methods like spin coating. For the first one high equipment
and processing cost is characteristic. Solution based thin film production processes are less
demanding therefore became more and more popular among researchers in field of organic
optoelectronics and photonics. Nowadays polymers and polymer composites are most
intensively employed in attempts to create devices via solution based technology. Among
them there has also been increasing interest in so called “organic molecular glasses” as
photonic thin film materials1, 2. Compared to polymeric systems, organic molecular glasses
do not need complicated chemical synthesis or purification processes and has a welldefined structure.
Within last decade our attention is paid to develop organic materials for nonlinear
optical (NLO) and organic electroluminescent (EL) applications. During our research it
came to our attention that the presence of triphenylmethyl and triphenylsilyl substitutes
noticeably enhances amorphous phase formation of low molecular weight molecules3.
Exploiting this molecular motif large amount of glass forming structures with different
active chromophores, are synthesized at RTU.
With scope of above mentioned applications thermal, optical, electrical and
electrooptical properties of these compounds are intensively investigated at ISSP UL. In
this contribution we would like to present our investigation results and discus possible
structure property relations within this new class of low molecular glasses.
Acknowledgements.This work has been supported by the Latvian National Research Program “Development
of Innovative Multifunctional Materials, Signal Processing and Information Technologies for Competitive
Science Intensive Products”
References
1. P. Strohriegl, J. V. Grazulevicius. Adv. Mater., 14, 1439 (2002).
2. S.-H. Jang and A. K.-Y. Jen. Chem. Asian J., 4, 20–31 (2009).
3. K. Traskovskis, I. Mihailovs, A. Tokmakovs, A.Jurgis, V. Kokars, M. Rutkis. J. Mater. Chem., 22 1126811276 (2012).
30
SUSTAINABLE, FUNCTIONAL NANOFIBRES BY
ELECTROSPINNING
A. Krumme
Department of Polymer Materials, Tallinn University of Technology, Tallinn, Estonia,
[email protected]
Electrospinning is a simple method for making thinner polymer fibres than with
mechanical fibre-spinning technologies. The biggest difference is the essence of the pulling
force. The use of electric charge to break up liquids into small particles has been well
known and extensively studied for over a century and electrospinning was first patented in
1934. The number of industrial applications is still small but the method is gaining more
attention nowadays due to development of nanotechnologies and novel materials.
In the electrospinning process, a polymer solution (or melt) held by its surface tension
at the end of a capillary tube is subjected to an electric field, thus inducing charge on the
liquid surface. When the electric field reaches a critical value at which the repulsive
electric force overcomes the surface tension force, a charged jet of the solution is ejected
from the tip of the capillary tube. Travelling in air, the jet thins as a result of both
elongation and solvent evaporation. Ultimately, solidification is carried out and fibres are
deposited on the surface of the collector, forming a randomly oriented non-woven mat or
as a novel trend, an aligned thread. Alternative, also novel route is to remove the solvent in
liquid environment.
When the diameter of a polymeric fibrous material is shrunk to submicron scale
outstanding properties – a very large surface area-to-volume ratio, light weight, also higher
flexibility in surface functionalities, and superior mechanical performance (e.g., stiffness
and tensile strength) appear, which make it optimal for many important applications. The
main fields are biomedical, electronics/energetics and finally functional materials.
Functional fibrous materials can be used for protective (smart) clothing, filters,
reinforcement in composites and sensing/actuating applications. The list can be probable
longer.
The aspect of sustainability is mostly related to environmental impact of the raw
materials and production/processing technologies. Key terms here are renewability and
recycling. Certainly, the most important renewable resource for producing polymeric
materials is cellulose. Its annual production in biosphere is estimated 90 gigatons. This is
approximately 300 times more than global plastics consumption and 16 000 times more
than consumption of biopolymers. Cellulose has several benefits in addition to availability
in huge amounts: it is not competing with food resources, has good mechanical properties,
heat stability and is resistant to several common solvents. Some of the benefits are also
drawbacks for processing: it is hard to dissolve cellulose. Fortunately, a relatively “green”
group of solvents for cellulose (compared to well-known Viscose, CarbaCell and LycoCell
processes), known as ionic liquids, has been invented during the last decade. Ionic liquids
are highly polar and therefore can break the hydrogen bonds between macromolecules of
cellulose. Besides, ionic liquids are not volatile, they can be easily regenerated and are
considered as nontoxic in most cases.
This review presentation summarises recent achievements in the field of functional
nanofibres and their production form cellulose or other polysaccharides by different
methods of electrospinning.
Acknowledgements.Archimedes Foundation in Estonia is acknowledged for support under ERF project no.
3.2.1101.12-0018.
31
ENGINEERING COMPLEX MACROMOLECULAR
ARCHITECTURES VIA PRECISION POLYMERIZATION
D. Gromadzki
Department of Chemical Engineering, McGill University, Montréal, Canada, [email protected]
Complex macromolecular architectures (CMA) with well-defined composition, shape
and functionalities such as block copolymers, molecular brushes, polymer stars have been
receiving increasing attention of a great number of scientists around the world. Selfassembly of CMA in solution and in bulk very often leads to a new interesting properties
and phenomena [1]. Ionic polymerization [2] and controlled radical polymerization [3]
along with orthogonal coupling strategies, e.g.click chemistry, can be effectively employed
to construct CMA. Taking advantage of unprecedented synthetic routes such as
combination of nitroxide-mediated polymerization (NMP) and photoiniferter controlled
polymerization we synthesize a comb-like architecture with polystyrene backbone and
methacrylate side chains [4]. Well-defined comb copolymers with varying backbone and
side chains are important model compounds for fundamental studies of their dilute
solutions [5]. Amphiphilic molecular brushes with temperature-responsive side chains can
be accessed by combining NMP with ionic polymerization [6]. Atom transfer radical
polymerization (ATRP) is a very robust technique for engineering CMA. We will show
how to prepare arborescent strong polyelectrolytes [7] and doubly-responsive
polyampholyte molecular brushes [8] using ATRP.
Poly(styrene-co-acrylonitrile), SAN, copolymers are well-known commercial materials
due to their excellent thermal and chemical resistance properties. Both NMP [9] and ATRP
techniques can be used to synthesize high-molecular weight SAN copolymers.
Commercially available second generation nitroxide BlocBuilder (Arkema) permits
synthesis of well-defined SAN copolymers with carboxylic acid residue. This feature can
be of advantage in reactive melt blending with functional polyethylenes. More importantly
BlocBuilder unimolecular initiator allows preparation of poly(methacrylates) which were
not possible with first generation nitroxides. Peculiarities and successes in the synthesis of
poly(methacrylates) based block copolymers and polyacrylonitrile by NMP will be
highlighted.
References
1. Y. Mai, A. Eisenberg. Chem. Soc. Rev., 41, 5969–5985 (2012).
2. M. Szwarc. Nature, 178, 1168–1169 (1956).
3. W.A. Braunecker, K. Matyjaszewski. Prog. Polym. Sci., 32, 93 (2007).
4. D. Gromadzki, R. Makuška, M. Netopilík, P. Holler, J. Lokaj. Eur. Polym. J., 44, 59–71 (2008).
5. D. Gromadzki, S. Filippov, M. Netopilík, R. Makuška, A. Jigounov, J. Pleštil. Eur. Polym. J., 45, 1748–
1758 (2009).
6. D. Gromadzki, A. Jigounov, P. Stepanek, R. Makuska. Eur. Polym. J., 46, 804–813 (2010).
7. D. Gromadzki, A. Tereshchenko, R. Makuska. Polymer, 51, 24, 5680–5687 (2010).
8. D. Gromadzki, P. Stepanek, R. Makuska. Mat. Chem. Phys., 137, 709–715 (2013).
9. D. Gromadzki, J. Lokaj, J. Slouf, P. Stepanek. Polymer, 50, 2451–2459 (2009).
32
TAILORING DENDRITIC STRUCTURES FOR THE USE IN EPOXY
THERMOSETS
A. Serra
Department of Analytical and Organic Chemistry, Rovira i Virgili University, Tarragona, Catalonia, Spain,
[email protected]
Dendritic polymers (among them, hyperbranched and star polymers) have attracted
much attention in the last years because of the characteristics that these structures possess,
such as large numbers of end groups, lower intrinsic viscosity values in comparison with
those of linear polymers of similar molecular weight, and very good solubilities.
Whereas dendrimers have a perfectly branched structure, HBPs have a defective and
less symmetrical structure, exhibiting properties that are intermediate between perfect
dendrimers and linear polymers and with a lower cost, which make them advisable for
technological applications.
Star-shaped polymers, comprising multiple arms radiating from a central branching
point or a core, represent one of the simplest branched topologies and present a very low
viscosity that depends on the arm length. They are quite easy to synthesize by different
methodologies.
Fig. 1. Idealized structures of dendrimer, hyperbranched polymer and multiarm star polymer
These dendritic polymers can be used as modifiers in epoxy thermosets, since it has
been observed that they give enhanced flexibilities and increased toughness to thermosets
without affecting other properties, such as hardness, modulus and Tg. Improved toughness
is due to local inhomogeneities in the crosslinked network caused by the covalent
incorporation of these polymers or to the formation of phase separated micro- or
nanoparticles with good interfacial adhesion between the separated phases.
It should be noted that functional groups at the end of the branches of these structures
can participate in the crosslinking reaction depending on the selected curing agent, and
therefore mechanical properties of the resin mainly depend on the shell chemistry of these
modifiers. However, it has been put into evidence that in some cases even the structure of
the repetitive units in the dendritic structure, used as additive in the epoxy formulations,
can play a role in the curing process and multifunctional initiators can be originated on
selecting the adequate curing process.
References
1. M. Morell, A. Lederer, X. Ramis, B. Voit, A. Serra. J. Polym. Sci. A: Polym. Chem., 49, 2395-2406
(2011).
2. D. Foix, X. Ramis, A. Serra, M. Sangermano. Polymer, 52, 3269-3276 (2011).
3. M. Flores, X. Fernández-Francos, F. Ferrando, X. Ramis, A. Serra. Polymer, 53, 5232-5241 (2012).
33
APPROACHES FOR FABRICATING HIGH-EFFICIENCY OLEDS
J. Jou
Department of Materials Science and Engineering, National Tsing-Hua University, Hsin-chu, Taiwan,
[email protected]
High efficiency is essential for OLED to be energy-saving and long lifetime for either
display or illumination applications. High-efficiency OLED devices can be obtained by
using electro-luminance (EL)-active emitters dispersed in properly matched hosting and/or
co-hosting materials with efficiency-effective device architectures and light extraction
structures.
We will brief in the presentation numerous architectural as well as material approaches
to obtaining high-efficiency OLED devices with monochromatic and polychromatic
emissions. They include (1) low carrier injection barriers, (2) high carrier mobility, (3)
effective carrier confinement, (4) a balance carrier injection, (5) exciton generation on host
or guest-and-host, rather than on guest only, (6) effective host-to-guest energy transfer, (7)
an EL effective dye, (8) a wide recombination zone, (9) the use of a co-host, and (10)
incorporation of a carrier modulation layer etc. OLEDs with record breaking power
efficiency will be revealed.
We will also demonstrate the employment of a tandem structure in fabricating a ultrabright candle-style OLED, hoping to meet the specification of a 30 lm/W efficacy with a
10,000 hours t50 lifetime at 3,000 cd/m2 for lighting application.
34
DECOMPOSITION OF THE TRIPLE-DETECTION SEC CURVES OF
LINEAR AND BRANCHED POLYMERS
M. Netopilík
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06
Prague 6, Czech Republic,[email protected]
Size-exclusion chromatography (SEC) with the triple concentration, light scattering
and viscosity detection is currently considered the best method for simultaneous
characterization of distribution of molar masses of linear and branched polymers, for the
latter of the average degree of branching and with optional UV detection of other details of
the polymer composition. One of the obstacles in complete characterization of complex
polymers with the multimodal molecular-weight distribution and therefore SEC elution
curves is the characterization of individual components forming the sample from the point
of view of finding parameters of their molecular-weight distribution and other
characteristics, e.g., of branching and grafting using the viscosity data.
Fig. 1. An example of light
scattering
elution
curves-detector
response in mV-of the light scattering
detector (DAWN-DSP-F, 90 degree)
from the analysis of a polystyrenestandard (Pressure Chemical) mixture of
molecular weights M of 400 a 900
thousands.
We present1 a new method of the separate evaluation of the individual non baselineresolved peaks and of the characterization of the individual polymer components
represented by the peaks. The method was tested on individual and mixed polystyrene
standards and further testing a grafted and branched samples is in progress. As an example
is presented in Fig. 1 the light scattering elution curve (90 degree) obtained for a mixture
of polystyrene standards obtained by the DAWN-DSP-F (Wyatt Ltd. Comp.), decomposed
in components f1 and f2 and yielding the fit of experimental data f.
Acknowledgements.The financial support of the Grant Agency of the Czech Republic (projects
P205/11/J043 and 13-02938S) is gratefully acknowledged. The author also expresses his gratitude to Wyatt
Technology Ltd for kindly providing the DAWN laser photometer.
References
1. M. Netopilík et al., prepared for publication.
35
ORGANOBORANE WONDERLAND: FROM THE VIEWPOINT OF A
UNIQUE INITIATOR OF RADICAL POLYMERIZATION
S. Kanno
Polymer Chemistry Laboratory, Tohoku Seikatsu Bunka University, Sendai, Japan, [email protected]
Since the method of radical polymerization has been studied systematically in the field of
synthetic polymer chemistry and its numerous ramifications, the radical polymerization is regarded
as the most convenient and applicable to a wide range for the industrial production of vinyl
polymers. In fact, it is said that more than 70 % amount of vinyl polymers is produced industrially
by the radical polymerization method. Additionally, present-day synthetic polymer chemistry is
directed toward the mass production of polymers having predetermined molecular structures.
Under these circumstances, living polymerization was extended to radical polymerization systems,
and various living radical polymerization systems are developed nowadays. In contrast to the
academic interest of various living radical polymerization systems, it is still difficult to industrialize
these living radical polymerization systems at present stage. Accordingly, it is very important for
the polymer chemists to develop practical living radical polymerization methods. Needless to say,
it should be realized that the system and the condition of a chemical reaction must be simple from
the standpoint of the the practical use in factories. In these meaning, the more simple reaction
conditions and the mild reaction temperature possesses great advantages over the syntheses of
industrial polymers. On the other hand, the chemistry of organoboron compounds is a special field
compared to the other fields of organic chemistry. This is due to the peculiar fact that the boron
atom has three valence electrons and four orbitals, of which three are occupied by electrons while
the fourth is empty. Especially, it was known about 60 years ago that the addition reaction of
diborane to alkenes and alkynes will occur easily in ether solvents, and was named hydroboration
reaction. This reaction made the organoboranes readily available. For instance, the bicyclic borane,
9-borabicyclo[3.3.1]nonane (9-BBN), can be synthesized by the reaction of 1,5-cyclooctadiene
with diborane in tetrahydrofuran (THF).
In this study, I have reported the recent achievement of the unique radical polymerization
systems of various vinyl monomers initiated with alkylborane and borane complex. The most
remarkable feature of these alkylborane- and borane complex-initiated polymerizations is the fact
that these polymerization reactions proceed under air at mild reaction temperature ranges, e.g., 0 ℃
- 70 ℃. Furthermore, the molecular weight of the obtained polymer increases with monomer
conversion in some of these polymerizations, suggesting the living properties of these
polymerizations. Consequently, compared with other living radical polymerization systems
reported, these novel living radical polymerization systems have the possibility to offer a more
general and efficient way toward the industrial production of various tailor-made polymers.1)-3) For
example, I have established a new facile living radical polymerization initiated with 9-BBN until
now, in which the polymerization proceeds easily under air at mild reaction temperatures. This
novel living radical polymerization process was named "hydroboration-autoxidation living radical
polymerization". The mechanism of the polymerization can be briefly explained as follows. Vinyl
monomer-9-BBN adduct is formed via hydroboration reaction, and the oxidation reaction rapidly
takes place at the C-B bond of the vinyl monomer-9-BBN adduct to form boron peroxide (C-O-OB) which can homolytically cleavage to generate an alkoxy radical (C-O・) and a borinate radical
(B-O・). After the homolytical cleavage of the boron peroxide, the alkoxy radical initiates the
polymerization and the borinate radical forms the dormant species of the propagating chain end.
References
1. S. Kanno, Japanese Patent No 3692934.
36
INITIATOR TYPE INFLUENCE ON PROPYLENE OXIDE
POLYMERS OF AND STAR-SHAPED DOPED POLYETHERS FOR
INDUSTRIAL APPLICATION
A.S. Swinarew1, S. Golba1, J. Gabor1, M. Łężniak1, T. Flak1, B. Swinarew2,
Z. Grobelny3
1
Institute of Materials Science, University of Silesia, Katowice, Poland
Institute for Engineering of Polymer Materials and Dies, Paint and Plastics Department, Gliwice, Poland
3
Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
2
Keywords: luminescence, carbazolyl, star-shaped polyethers, mechanical properties, anionic polymerization
Star-shaped polyethers were obtained by the anionic polymerization of propylene
oxide and carbazolyl monomers in the presence of cyclic oligo(potassium glicydoxide) as
the macroinitiator. Polymerization processes were investigated by the use of Size
Exclusion Chromatography (SEC). The end-products obtained were purified and
characterized with MALDI-TOF systems. The obtained polymers and co-polymers were
doped with nano silver colloid in ethylene glycol.
Silver particles having fine or ultrafine sizes have attracted scientific interest because
of their unusual properties compared to bulk metal. Colloidal particles because of their
quantum size effects and surface effects reveal excellent electrical conductivity, catalytical
activity, chemical stability and antimicrobial activity (1). These properties have led to
tremendous range of applications of silver nanoparticles, such as antibacterial textiles and
nanosilver-contained polymers used to make refrigerators, dish washers, rice cookers,
plastic film, chopping boards, vacuum bottles, plastic pails, and garbage containers.
In this work we investigate the synthesis and properties a star-shaped polyethers
containing silver nano particles for wide range of applications.
Fig 1. Structure and MALDI-TOF spectra of poly(9-(oxiran-2-ylmethyl)-9H-carbazole)
References
1. V. Pillai, P. Kumar, M. J. Hou, P. Ayyub and D. O. Shah,, Adv. Colloid Interface Sci. 55, 241-269 (1995).
37
SUPRAMOLECULAR HYDROGELS. SELF-ORGANIZATION
PROCESSES
S. Khizhnyak1, P. Pakhomov1, M. Ovchinnikov2, P. Komarov1
1
2
Department of Physical Chemistry, Tver State University, Tver, Russia, [email protected]
Department of Scientific Research, Tver StateMedical Academy, Tver, Russia
Low molecular weight supramolecular hydrogelators attract increased attention due to
variety of potential applications including tissue engineering, vehicles for controlled drug
release, pharmaceutical formulations and others. Sulfur containing amino acids are
interesting candidates for hydrogelation as they can be self-assembled using various noncovalent interactions in water including H-bonding, electrostatic, - and hydrophobic
interactions. A novel gel-forming supramolecular systems based on aqueous solutions of
amino acid L-cysteine, silver nitrate taken in excess and some electrolytes are discovered
by the authors. L-cysteine is a unique amino acid, it has three functional groups – thiol,
carboxyl and amino – not far separated from each other. Peculiarities of the systems are
gelation at a low concentrations of the initial low molecular weight components (~0,01%),
high antimicrobial activity, compatibility with the substances of another nature – polyvinyl
alcohol, polyvinyl pyrrolidone, dimethyl sulfoxide, liposome, that gives an opportunity to
create highly efficient pharmaceutical preparations.
On the base of experimental and theoretical data mechanism of gelation is suggested. It
is supposed that silver mercaptide, obtained on the first stage of reaction between cysteine
and silver nitrate, can form linear supramolecular chains [–Ag–S(Cys)–]n, where n~20,
with a relatively low interaction energy (~20 kcal/mol) due to non-covalent bonds. That is
so called ageing of cysteine–silver nitrate solution and in dependence on temperature (15–
400С) its duration is varied from some minutes to 16–20 hours. Characterization of
aggregation in the system by means of dynamic light scattering and transmission electron
microscopy (TEM) has shown that sizes of associates and clusters formed in the solution
are changeable over time. This self-organization process observed only in definite
concentration range of the initial components is required for gelation initiated by
introducing of some electrolytes (salts, acids or alkali).
Thus, the linear supramolecular chains can be considered as molecular precursors for
building up the network and their presence in the solution for gelation is required. Role of
“binders” for joining of the chains is performed by electrolyte anions. In dependence on
type of the electrolytes, structure and properties of the hydrogels are varied, that is
confirmed by means of viscometry and TEM.
But nevertheless, to clarify the gelation mechanism and a role of each amino acid
group in the processit is of great importance to reveal conditions of gelation in various
systems based on cysteine derivatives. It is found out that N-acetyl-L-cysteine (NAC) and
silver nitrate also are able to form supramolecular hydrogels at low concentrations. In NAC
molecule in contrast to L-cysteine a hydrogen atom of the amino group is substituted with
acetyl group that changes acidic-base properties of the molecule, charge distribution in the
functional groups and as a result conditions of gelation. As a result, gelation in the NAC
system is a one stage process occurring in a narrow ranges of pH and molar ratio of the
initial components 1:1. The NAC based gel is non-thixotropic, less stable over time and
weaker in comparison to the gels based on L-cysteine. TEM data showed that threedimensional network of NAC gel consists of nanofibers with high aspect ratio.
Investigations of the NAC-AgNO3 based gels by means of various techniques allowed to
suggest mechanism of gelation in this supramolecular system. The search of another gel
forming sulfur containing amino acids and cysteine derivatives is continued.
38
HIGHLY DURABLE DYE-SENSITIZED SOLAR CELLS UTILIZING
BIO-COMPATIBLE AND PHOTO-CROSSLINKABLE ACRYLICBASED HYDROGEL
L.-Y. Chen, S.-H. Huang
Department of Photonics, National Sun Yat-sen University, Kaohsiung, Taiwan, [email protected]
Dye-sensitized solar cells (DSSCs)1, benefiting from lower cost, more efficient light
harvesting, and easier fabricating process compared to silicon-based solar cells, have
attracted lots of attentions recently. Liquid electrolytes are generally used in DSSCs to
regenerating oxidized dye and transporting carriers towards electrodes efficiently2, but its
vaporization also makes DSSCs suffer from durability issues3. In this work, a biocompatible and photo-crosslinkable acrylic-based hydrogel, which has been widely
implemented in medical treatment, was successfully used as the support material for the
liquid electrolytes in the DSSCs to retard the vaporization of the liquid electrolytes. The
maximum power conversion efficiency (PCE) and the half lifetime (t1/2) of the device is
3.1% and 76 minutes, respectively. Compared to the standard DSSCs only utilizing liquid
electrolytes, the DSSCs adding hydrogels showed a lifetime enhancement up to 5 times
while sacrificed only 31% efficiency.
(b)
5
4
4
PCE (%)
PCE (%)
(a)
5
3
2
1
0
3
2
1
0
5
10
15
Operation Time (mins)
20
0
0
20
40
60
80
Operation Time (mins)
100
Fig. 1. Power conversion efficiency of DSSCs (a) utilizing only liquid electrolyte and (b) adding biocompatible and photo-crosslinkable acrylic-based hydrogel.
Acknowledgements.This work was supported by National Science Council under the Grants NSC 101-2221E-110-052.
References
1. A. Zengin, E. Yildirim, T. Caykara. J. Polym. Sci. A: Polym. Chem., 51, 954-962 (2013).
2. D. Randall, S. Lee. The Polyurethane Book, Wiley, New York (2002).
3. P. Wang, S.M. Zakeeruddin, P. Comte, I. Exnar, M. Grätzel. J. Am. Chem. Soc.125, 1166 (2003).
39
POLYMER MATERIALS FOR ADVANCED LITHIUM BATTERIES
V. Barsukov, V. Khomenko, I. Senyk, E. Senyn and V. Tverdokhleb
Department of Electrochemical Power Engineering & Chemistry, Kiev National University of Technologies
and Design (KNUTD), Kiev, Ukraine, [email protected]
Lithium-ion and lithium polymer batteries in the last decade "occupied" in full the
market of portable consumer electronics (mobile phones, small computers, camcorders,
digital cameras, etc.). An actual task of the present stage for such batteries is the
development and mass production of large size batteries for electric and hybrid vehicles,
aviation, marine and railway transport. This will increase dramatically the already huge
sales of batteries, which amounts to billions of Euros per year. For solving this problem, it
is necessary first to solve the problems of safety, reliable, cost effective and
environmentally-friendly materials and technologies. Optimal selection and modification
of polymeric materials which are commonly used in battery technology, can significantly
contribute to solving these problems.
PVDF and certain copolymers are most commonly used as effective binder additives
to the active materials of batteries, which must simultaneously provide a strong adhesion of
the active materials to the current collector. Therefore, one of the most important areas of
KNUTD research is a study of fracture mechanisms, rheological and adhesive properties of
the composites for different types of PVDF with graphite, carbon active materials and
metal current collectors of electrodes (copper, aluminum). According to our research, the
destruction of battery electrodes during intercalation-deintercalation of lithium ions is
usually not due to poor adhesion of the composite to metal current collector, but due to
cohesive failure of these composites. It is proved that the greater difference between a
surface energy of solid body and polymer, the greater intermolecular interaction between
these phases. Because graphite surface energy less than for metals, contact wetting
solutions of polymeric binder metal is better than with graphite and carbon materials.
PVDF based composites are also often used as ion-conductive solid electrolyte and
porous membranes, particularly for lithium polymer batteries. Research in this direction
KNUTD holds jointly with Energy Technology Institute-ITE, CEGASA International,
CSIC, ATOS (Spain); Institute of Chemistry Timisoara (Romania); Cleancarb
(Luxemburg); University of Liège, UMICORE (Belgium); VIF (Austria); Recupyl
(France); Accurec (Germany); Lithium Balance (Denmark). The main problem is to
develop a technology in which synthesis of polymer electrolyte would occur
simultaneously with an incorporation of active material particles (e.g., graphite) in order to
obtain an integrated electrode, in which pores are filled at once by polymer electrolyte.
For preparation of suspensions based on PVDF normally used quite toxic solvent
NMP. Therefore, a series of studies focused on explore the possibility of CMC as a
“green” binder additive, which use an aqueous solution as a solvent. It could allow in a
perspective develop some "green" technologies for production of batteries.
An important safety feature for a large size battery is using the two-layerporous
membranes with a quite different melting point of each layer. In case of a short circuit or
other causes sudden heating the battery a more fusible layer (e.g., polyethylene) melts and
floods pores of more refractory layer (e.g., polypropylene) disconnecting battery discharge.
For battery case is necessary to use light, durable polymers resistant to UV radiation.
Thus, an optimal choice of polymer materials and technologies has had a significant
impact on the operational and technological characteristics of lithium batteries.
Acknowledgements.The research leading to these results has received funding from the European
Community's Seventh Framework Programme (FP7/2007-2013) under Grant Agreement Nr. 266090
(SOMABAT).
40
MOLECULARLY IMPRINTED POLY(m-PHENYLENEDIAMINE)
FILMS AS A SENSING LAYER FOR ANTIBIOTIC DETECTION
A. Tretjakov1, V. Syritski1, J. Reut1, Y. Zhang1, A. Öpik1, K. Hinrichs2, J. Rappich3
1
Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn Estonia,
[email protected]
2
Leibniz - Institut für Analytische Wissenschaften - ISAS - e.V., Department Berlin, Albert-Einstein-Str. 9,
12489 Berlin, Germany
3
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut für Silizium-Photovoltaik, Kekuléstr.
5, 12489 Berlin, Germany
The excessive use of antibiotics to control infections in people and in domestic animals
has led to very serious problem in natural ecosystems. Antibiotics can alter the structure
and function of microbial communities in the environment and facilitate the development
and spread of antibiotic resistant strains of bacteria increasing the risk of pathogenic
bacterial infections. The greatest concern associated with the extensive occurrence of
antibiotics in aquatic environments is the potential for increased antibiotic resistance
among microbial populations continuously exposed to low levels of antibiotics [1].
Although a number of chromatography-based methods for detection and separation of
antibiotic contaminants is available, there is a great demand in the development of an
analytical method to detect antibiotics in low concentrations with high specificity in
relatively short time. Due to analytically useful properties, such as selectivity,
physical/chemical resistance and/or fast binding kinetics, MIPs have been proposed as
suitable molecular recognition elements for construction of a biosensor intended for
antibiotic detection in water [2]. The use of electropolymerisable monomers gives a
possibility to create MIP films by a highly-controllable electrodeposition technique directly
on the surface of transducers (e.g. gold electrode of quartz crystal microbalance (QCM) or
surface plasmon resonance sensors) providing thus feasibility for real-time label-free
detection of an analyte.
This study is aimed to develop a new and easy approach to prepare MIP thin films for
selective antibiotics recognition thus, giving a premise for construction of a sensor for
antibiotic real time detection.
Widely used antibiotics: Amoxicillin (Amox),
sulfamethizole (Smz) and doxycycline (Doxy), were selected as target molecules. The
probability of pre-polymerization complex formation between the monomer and selected
antibiotics was studied by UV-Vis spectroscopy. m-Phenylenediamine (mPD)
electropolymerization in the presence of the antibiotics was used for MIP thin film
formation directly on a QCM gold electrode. The antibiotic-imprinted PmPD films (AmoxMIP, Doxy-MIP, Smz-MIP) were studied in terms of their capability to selectively bind the
corresponding antibiotic from aqueous analyte solution by QCM technique combined with
flow injection analysis (FIA).
Acknowledgements. The financial supports of the Estonian Ministry of Education and Research (grant
PUT150) and the European Regional Development Fund (project 3.2.0801.11-0009) are gratefully
acknowledged.
References
1. F. Baquero. Drug Resistance Updates, 4 (2), 93–105 (2001).
2. A. Fernández-González, L. Guardia, R. Badía-Laíño, M.-E. Díaz-García. Trends Anal. Chem., 25 (10),
949-957 (2006).
41
CARBAZOLE BASED HOLE CONDUCTING MATERIAL FOR
EFFICIENT SOLID-STATE DSSC: AN ALTERNATIVE TO SPIROOMETAD
B. Schmaltz1, M. Degbia1,A. Tomkeviciene2, G. Puckyte2,A.
Michaleviciute2,E Gurskyte2, J. Grazulevicius2, J. Bouclé3, F. Tran Van1
1
Laboratoire PCM2E, Parc de Grandmont, Tours, France, [email protected]
3
Institut XLIM UMR 7252, Limoges, France
2
Dye-sensitized solar cells (DSSCs) are one of the most promising photovoltaic
technologies for production of renewable and low-cost energy. These cells are composed
of a nanocrystalline wide band gap semiconductor oxide (TiO2) deposited on a transparent
conducting oxide (FTO) glass substrate. A molecular sensitizer is linked via an anchoring
group to the oxide surface. Traditionally, a liquid electrolyte redox system is used to
regenerate the photo-excited dye. Liquid electrolyte-based DSSCs have reached conversion
efficiencies over 12%. However, these liquid-based DSSCs may suffer from potential
leakage and corrosion problems. Practical advantages have been gained by replacing the
liquid electrolyte with solid hole-transporting material (HTM). One of the most widely
used
organic
HTMs
is
2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’spirobifluorene (Spiro-OMeTAD). Nowadays solid state DSSC reached conversion
efficiency over 9%.
In this work, molecular glasses HTMs based on carbazole core and functionalized with
diphenylamine groups will be presented. In order to fine-tune the properties of the
molecules (energy levels, glass transition temperature, absorption in visible range, hole
mobilities,..), the design of the molecules have been studied. The effect of the methoxygroups, of the number of diphenylamine groups grafted onto the carbazole core, of the
structure dimension of the target molecules will be discussed. The synthesis of the HTMs
as well as their thermal, electrochemical, electronic and photovoltaic properties will be
developed. Our best photovoltaic results obtained with one of these new HTMs in solidstate DSSC device reach 3.4% [1-4]. In comparison, solid-state DSSC devices have been
built under the same conditions with the reference Spiro-OMeTAD as HTM and give
similar power conversion efficiency [5], which confirms the
O
relevance of our approach.
N
N
O
N
O
N
N
N
N
O
O
N
O
O
GP-12
N
O
O
GP-17
EG-5b
Fig. 1. Examples of structures of carbazole based HTM for DSSC applications.
References
1. A. Tomkeviciene et al. Synthetic Metals, 162, 1997– 2004 (2012).
2. G. Puckyte et al. Journal of Power Sources, 233, 86-92 (2013).
3. M. Degbia et al. Semiconductor Conference Dresden-Grenoble International, 24, 211-214 (2012).
4. A. Michaleviciute, Journal of Power Sources, submitted.
5. L. Schmidt-Mende et al. Adv. Mater, 17, 813-815 (2005).
42
ELECTROCHEMICAL AND SPECTROELECTROCHEMICAL
CHARACTERIZATION OF CHOSENBISAXIALLY COORDINATED
RUTHENIUM PHTHALOCYANINES AND THEIR LIGANDS
K. Lenartowicz1, P. Data1,2, M. Łapkowski1,2
1
[email protected]
2
Department Of Chemistry, Silesian University of Technology, Gliwice, Poland
Phthalocyanines (Pcs)have attracted considerable attention because of their impressive
and useful chemical and physical properties. They have strong delocalized 18 p-electronic
conjugated ring system, good thermal stability and interesting optical properties1.Pcs
physicochemical properties (solubility, electronic absorption, fluorescence, self-assembly
etc.) can be easy modified through synthetic manipulation, typically by modifications of
the benzene rings substituents, variation of the central metal ion and insertion of a
substituent as an axial ligand2,3.
Among metallophthalocyanines (MPcs), ruthenium phthalocyanines are especially
interesting because of efficient triplet state generation and photoinduced charge transfer, as
well as strong binding of axial ligands, which enable coupling to other functional
moieties4. Ruthenium phthalocyanine complexes have been investigated as photovoltaic
devices, catalysts, gas sensing thin films, organic conductors, sensitisers in photodynamic
therapy1. Non-ligated derivatives are hard to accessand the most attention has focused on
insertion of either single or double axial ligation. The most of the reported metal
complexes of phthalocyanine have N-donor axial ligands, e.g., pyridine, pyrazine and
quinoline derivatives and have the benzene ring substitutedat peripheral positions2,5.
The investigated MPcs are octa-substituted ruthenium phthalocyanines bisaxally
ligated with pyridine derivatives. Electrochemical and spectroelectrochemical investigation
have been provided to discuss the properties of ruthenium phthalocyanines as well as the
ligands.
Acknowledgements.This
2011/03/B/ST5/01475.
work
was
supported
by
National
Science
Centre,
Project
No.
References
1. C. Yağcı, A. Bilgin, Polyhedron, 51, 142–155, (2013)
2. N. Cammidge, G. Berber, I. Chambrier, P. W. Hough M. J. Cook, Tetrahedron, 61, 4067–4074, (2005).
3. M. Arıcı, D. Arıcan, A. L. Uğur, A. Erdoğmuş, A. Koca,Electrochimica Acta, 87, 554– 566, (2013).
4. T. Rawling, A. McDonagh, Coord. Chem. Rev. 251, 1128-1157, (2007).
5. T. Rawling, A. M. McDonagh , S. B. Colbran, Inorganica Chimica Acta, 361, 49–55, (2008).
43
THE INFLUENCE OF LINKING TOPOLOGIES ON THE
PROPERTIES OF THE DENDRIMERS WITH DIFFERENT CORES
AND FLUORENE SIDE ARMS
N. Kukhta, J. Simokaitiene, J. Grazulevicius, J. Ostrauskaite
Department of Organic Technology, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
Conjugated organic materials are the subject of intensive research for optoelectronic
applications. Organic glass-forming materials thin films of which can be obtained by spin
coating or casting are particularly attractive. Star-shaped molecules have several
advantages over the established polymer materials, such as well-defined structure and
increased solubility1. Moreover, molecules with star-burst architecture often possess
interesting optical and photophysical properties.
It is known, that optical, thermal and electrochemical properties of the molecules
depend on the linking topologies due to the differences in geometry and conjugation
between the constituting moieties.
:
R
R
1.
N
N
,R =
*
,R =
*
N
R R
2.
3.
,R =
*
N
:
R
R
In this work, we report on the synthesis and properties of three series of star-shaped
compounds, containing 2,4,6-triphenyl-1,3,5-triazine, triphenylamine and 2,4,6-triphenyl1,3,5-triphenylbenzene cores and peripheral fluorene moieties linked by the bridges
containing single, double and triple bonds. The influence of linking topologies on the
properties were studied by UV and fluorescence spectrometries. Thus, triazine- and
triphenylbenzene-based materials are strong blue emitters and their absorption maxima lay
in the range from 326 to 367 nm, while the emission maxima of the compounds with
triphenylamine core are red-shifted compared to those of the triazine and triphenylbenzene
derivatives. All the three series of compounds show solvatochromic effect, which strongly
depends on the linkage type. The star-shaped molecules possess high decomposition
temperatures (399-437oC) and relatively low glass transition temperatures (56-79oC). The
comparison of the experimental data with those obtained by the DFT calculations was
performed.
References
1. N. A. Montgomery et al, J. Phys. Chem. A115, 2913 (2011).
44
GLASS-FORMING DENDRITIC DERIVATIVES OF
TRIPHENYLAMINE
T. Matulaitis, V. Mimaitė, J. V. Gražulevičius
[email protected]
Since the first reports on dendrimers were published in 1985 [1], research in this field
increased exponentially because of their unique functional properties and potential
applications in such fields as light harvesting, light power limiting, electroluminescence,
medicine etc. Dendrimers and star-burst molecules represent a class of shape persistent
macromolecular materials, which possess a well-defined, and monodisperse molecular
structure, as well as superior chemical purity. The high electron density and the π stacking
tendency conveys the star-shaped systems interesting optical, electrical and optoelectronic
properties.
In this presentation we report on the synthesis and properties of new glass-forming
triphenylamine-based derivatives. The thermal properties of the synthesized compounds
were investigated by differential scanning calorimetry and thermo gravimetric analysis. All
the synthesized compounds form molecular glasses with high glass transitions
temperatures ranging in the interval 121-140 °C. The dilute solutions of the synthesized
compounds show fluorescence quantum yields ranging from 0.3 to 0.91 and high Stokes
shifts (82-135 nm). Some of the synthesized compunds exhibit positive solvatochromism.
Electrochemical studies were performed for all the synthesized compounds. All the studied
derivatives display reversible oxidation processes. Solid state ionization potentials and
electron affinities, estimated by cyclic voltammetry, are in the close range of 4.95-4.98 eV
and of 1.84-2.51 eV, respectively. The synthesized star-shaped molecules are characterized
by relatively small band gaps (2.47-3.12 eV). All the structures were optimized and
theoretical values of HOMO and LUMO energies were calculated and compared with
experimental data. The theoretical and experimental results were found to be in good
agreement.
References
1. D. A. Tomalia, H. Baker, J. R. Dewald, M. Hall, G. Kallos, S. Martin, J. Roeck, J. Ryder, P. Smith,
Polym. J. 17, 117 (1985).
45
AN ELECTROCHEMICAL AND SPECTROELECTROCHEMICAL
INVESTIGATION OF CARBAZOLE AND TRIPHENYLAMINE
DERIVATIVES CONTAINING SELENOPHENE UNITS
P. Pander1, P. Data1,2
1
Silesian University of Technology, Faculty of Chemistry, Strzody 9, 44-100 Gliwice, Poland;
[email protected]
2
Carbazole and its derivatives have been known for many years mainly due to their high
hole transporting capabilities and strong fluorescence, as components of opto- and electroactive materials. There are two types of carbazole derivatives, N-substituted-2,7-carbazole
and N-substituted-3,6-carbazole. Both types were characterized: (1) 9-nonyl-2,7bis(selenophen-2-yl)-9H-carbazole
and
(2)
9-nonyl-3,6-bis(selenophen-2-yl)-9Hcarbazole.
Triphenylamine derivatives such as tris[4-(thiophen-2-yl)phenyl]amine are
trifunctional monomers for electropolymerization of films having high conductivity1.
(3) Tris[4-(selenophen-2-yl)phenyl]amine differs from the compound above only in the
type of heteroatom.
The presence of selenium atoms in investigated compounds lead to conclusion that
they are possible monomers for electro-conductive polymers for optoelectronics.
Monomers shown in Fig. 1 and deposited on Pt electrode polymer films were
examined using cyclic voltammetry (CV) measurements. Films obtained by
electropolymerization was also analyzed by UV-VIS-NIR spectrophotometry and EPR
spectroscopy coupled with cyclic voltammetry and chronoamperometry techniques.
C9H19
N
Se
Se
Se
Se
(1)
N
C9H19
(3)
N
Se
Se
Se
(2)
Fig. 1. Investigated compounds.
2011/03/N/ST5/04362.
work
was
supported
by
National
Science
Centre,
Project
No.
References
1. K. Yamamoto, M. Higuchi, K. Uchida, Y. Kojima. Macromolecules, 35, 5782-8 (2002).
46
SPECTROELECTROCHEMICAL INVESTIGATION OF NOVEL
POLYTELLUROPHENE DERIVATIVES
P. Data1,2, P. Pander1, A. Swist3
1
Silesian University of Technology, Faculty of Chemistry, Strzody 9, 44-100 Gliwice, Poland,
[email protected]
2
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34, 41-819
Zabrze, Poland
3
Wroclaw University of Technology, Faculty of Chemistry, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw,
Poland
The study of new organic materials with potential photoluminescent properties, such as
conjugated molecules and polymers featuring photo- and electroluminescent properties,
has attracted exceptional interest in terms of molecular optoelectronics applications, e.g. as
potential elements of electroluminescent diodes, displays and photovoltaic cells. The
demand for this type of material is growing intensively in connection with the development
of organic electronics, otherwise known as "flexible" electronics or "transparent"
electronics. At present linear macromolecules are mainly used in the investigation of
optically active organic materials. A new trend in research laboratories worldwide is the
shift from linear conjugated macromolecules to dendritic forms, branched and
hyperbranched systems or molecules featuring a star-shaped architecture. Tellurophene
derivatives have lower oxidation potential in compare to its selenophene, sulfur or oxygen
analogs. In our work we will present a spectroelectrochemical characteristic of novel
monomers (Fig.1) and their electrodeposited polymer.
Fig. 1. Investigated monomers
Acknowledgements. This
2011/03/N/ST5/04362.
work
was
supported
by
National
Science
Centre,
Project
No.
47
INFLUENCE OF REDUCING AGENT AND TEMPERATURE ON
SILVER NANOPARTICLES SYNTHESIS IN BRANCHED DEXTRANPOLYACRYLAMIDE MATRICES
N. Kutsevol1, M. Bezuglyi1, 2, T. Bezugla1, O. Korichenska1
1
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv,Ukraine,
[email protected]
2
There is great interest in silver nanomaterials due to their unique physicochemical
properties and wide range of potential application in research area. Perspective route of
aqueous Ag sol production is in situ synthesis of silver nanoparticles (Ag NPs) in
polymeric matrices. Reductant, pH, temperature and polymer matrix (its chemical nature,
modification type and grade, internal structure in solution, etc.) strongly affect the
morphology and dimension of nanoparticles.
In this work we studied the effect of internal structure of polymeric matrices and type
of reductant on formation and properties of silver sols. Anionic derivatives of star-like
copolymer dextran-polyacrylamide with dextran core (Mw=7×105) and 5 grafted
polyacrylamide chains (D70-PAA5) as well as linear polyacrylamide (PAA) were used as
polimeric matrices. Hydrogen, glucose, sodium citrate, ascorbic acid, sodium borohydride,
hydrazine were applied as reductants. UV-Vis spectroscopy, TEM microscopy, electron
diffraction were used for Ag-NPs characterization. The influence of pH was studied for the
systems obtained using hydrogen, glucose and ascorbic acid. Also the influence of
synthesis temperature was investigated for some systems.
The Plasmon absorption is observed in range 350÷500nm, depending on synthesis
conditions (Figure). This fact indicates the formation of Ag NPs with size from 8 to 50nm.
There are two maxima in spectrum of sol obtained using hydrazine (375 та 475nm). This
may be due to the presence of two fractions or non-spherical shape of NPs.
1,0
1,0
0,5
Absorbance
Absorbance
3
3
0,5
2
2
1
0,0
200
400
600
Wavelength, nm
a
1
800
0,0
200
400
600
Wavelength, nm
800
b
Figure. Spectra of silver sols obtained in polymer matrices: anionic derivative of D70-PAA5 (Mw=2,2×106)
(a) and anionic derivative of PAA (Mw=1,4×106) (b). Reductant: hydrogen (1), glucose (2), hydrazine (3).
It was revealed the shift of absorption peak from 300 to 450 nm when pH changed
from 2 to 12 for sols obtained by hydrogen reduction of silver ions.
Thus, both the type of reductant and internal structure of polymeric matrix in solution
affect the process of Ag NPs formation and properties of silver sol.
Acknowledgements.This investigation was funded by NATO Grant CB.NUKR.CLG 98424 .
48
SYNTHESIS AND PROPERTIES OF NOVEL STAR-SHAPED
MOLECULES BASED ON CARBAZOLE
A. Brzęczek1, P. Data1,2, K. Walczak1, M. Łapkowski1,2
1
2
Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland, [email protected]
In order to meet commercial application, materials used in organic compounds based
devices should exhibit high thermal stability, high efficiency and solution processability
[1]. These requirements can be fulfilled by star-shaped molecules that lack the planarity
and thus do not tend to aggregate [2]. The phenomena, caused mostly by π-π stacking
interactions, is a problem of linear π-conjugated polymers. Moreover, star-shaped
architectures are characterized by high glass-transition temperature which results in
amorphous morphology that can ensure the device reproducibility and good stability [3].
Both optical and electronic properties of these compounds can be tuned via introduction of
different cores.
Carbazole unit is widely employed in the design of optoelectronic materials because it
reveals interesting optical and electronic properties [4]. Its derivatives are among the most
studied materials for organic light emitting diodes (OLEDs) since they show blue photoand electroluminescence and good hole transporting properties.
Herein we report the incorporation of 3,6-substituted carbazole into the novel starshaped derivatives. All monomers were synthesized via Suzuki coupling reaction. The
functionalization of the carbazole nitrogen atom with alkyl chains provides excellent
solubility of the high molecular weight monomers in common organic solvents. Obtained
monomers were characterized using spectroscopic and spectroelectrochemical methods.
2012/05/B/ST5/00745.
work
was
supported
by
National
Science
Centre,
Project
No.
References
1. J. Yang, X. Tao, C. Yuan, Y. X. Yan, L. Wang, Z. Liu, Y. Ren, M. H. Jiang. J. Am. Chem. Soc., 127,
3278-327 (2005).
2. M. Liang, J.Chen. J. Chen. Chem. Soc. Rev., 42, 3453-3488 (2013).
3. Y. Zou, T. Ye, D. Ma, J. Qin, C. Yang. J. Mater. Chem., 22, 23485–23491 (2012).
4. R. R. Reghu, J. V. Grazulevicius, J. Simokaitiene, T. Matulaitis, A. Miasojedovas, K. Kazlauskas, S.
Jursenas, P. Data, M. Lapkowski, P. Zassowski. Dyes and Pigments, 97, 412-422 (2013).
49
PECULIARITIES OF ACID DOPING OF POLYANILINE
OLIGOMERS WITH LOW-MOLECULAR WEIGHT AND
POLYMERIC ACIDS
O. E. Bogomolova, A. A. Savelyeva, V. G. Sergeyev
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia, [email protected]
The acid doping of linear tetraaniline and mixture of polyaniline oligomers with lowmolecular weight and polymeric acids was studied. Linear tetraaniline was obtained by
dimerization of N-phenyl-p-phenylenediamine; the fraction of polyaniline soluble in
dimethyl sulfoxide (DMSO) was used as polyaniline oligomers mixture. Camphorsulfonic
acid was used as low-molecular weight dopant, poly(4-styrenesulfonic acid) and poly(2acrylamido-2-methyl-1-propane-sulfonic acid) were used as polymeric ones.
It was found that during acid doping of both tetraaniline and polyaniline oligomers
with polyacids in DMSO the new absorption band appears in UV-vis-NIR spectra. This
band is intensive, quite sharp in case of tetraaniline, broader in case of oligoaniline mixture
and characterizes by the maximum at the wavelength of more than 1000 nm. The result is
nearly the same for both polyacids.
The similar spectra appeared to be achievable by addition of huge excess (orders of
magnitude) of camphorsulfonic acid to the system only in case of tetraaniline.
Appearance of such a long wavelength absorption band in UV-vis-NIR spectra of
polyaniline oligomers is fascinating since it looks similar to free-radical tail observed in
highly conductive polyaniline.
Acknowledgements.This work was partially supported with RFBR project № 11-03-01151а
50
CATIONIC POLYMERIZATION OF VINYL MONOMERS USING
COMPLEXES OF AlCl3 WITH ETHERS: FROM FUNCTIONAL
OLIGOMERS TO SUSTAINABLE PLASTICS
S. V. Kostjuk1, I. V. Vasilenko1, D. I. Shiman1, Y. A. Veraksa1, A. N. Frolov1,
N. A. Kukhta1,2
1
Research Institute for Physical Chemical Problems of the Belarusian State University, Minsk, Belarus,
[email protected] or [email protected]
2
Aluminum trichloride (AlCl3) is one of the most widely used in industry Lewis acids.
Particularly, such important polymers as isobutylene-based elastomers, polyisobutylenes,
terpene resins etc. are industrially manufactured by the AlCl3-coinitiated cationic
polymerization.1 However, two main disadvantages of AlCl3, i.e. high Lewis acidity and
poor solubility in common organic solvents restrict the use of this Lewis acid in the
synthesis of well-defined polymers. To overcome these limitations of AlCl3-based catalytic
systems we used in our investigations the complexes of AlCl3 with ethers. The use of such
complexes allows to solubilize the Lewis acid in polymerization media and decrease its
instantaneous concentration that leads to totally different behavior of these complexes in
the polymerization processes in comparison with neat AlCl3.2–5 In this study, the
application of AlCl3 complexes with ethers for the synthesis of exo-olefin-terminated
polyisobutylenes as well as the first synthesis of high molecular weight poly( -pinene)
will be discussed.
The complexes of AlCl3 with ethers of moderate basicity (Hex2O, Bu2O, iPr2O)
induced fast cationic polymerization of isobutylene in CH2Cl2 to afford so-called highly
reactive polyisobutylenes congaing predominantly exo-olefin terminal groups (>90%).3,4
On the contrary, complexes of AlCl3 with weak electron donors such as Ph2O and anisole
led to ill-defined polyisobutylenes containing mainly tri- and tetra-substituted double
bonds. These results indicate that the basicity of electron donors used for the preparation of
complexes with AlCl3 plays a key role in the selectivity of -H abstraction. Importantly,
well-defined polyisobutylenes with high content of desired exo-olefin end groups were also
synthesized in such non-polar and non-toxic solvents as toluene (exo content >90%) and nhexane (exo content > 80%).4 Finally, AlCl3 etherates showed good activity and selectivity
towards -H abstraction even at room temperature and at high monomer concentration
([M]5.1 M) indicating high industrial relevance of proposed catalytic system.
AlCl3 etherates (AlCl3OPh2, AlCl30.8EtOAc) showed also high activity toward
cationic polymerization of -pinene and trans-anethole affording relatively high
molecular weight polymers (Mn up to 20,000 g mol–1) having good thermal properties for
practical use under industrially attractive experimental conditions (room temperature, low
catalyst content, use non-toxic solvents). 5
Acknowledgements. The authors thank BASF SE and State Committee on Science and Technology of the
Republic of Belarus for financial support of this research.
References
1. J.E. Puskas, G. Kaszas. Carbocationic Polymerization. Encyclopedia of Polymer Science and
Technology, V.5, Wiley-InterScience (2003).
2. A.N. Frolov, S.V. Kostjuk, I.V. Vasilenko, F.N. Kaputsky. J. Polym. Sci. Part A.: Polym. Chem., 48,
3736-3743 (2010).
3. I.V. Vasilenko, A.N. Frolov, S.V. Kostjuk. Macromolecules, 43, 5503-5507 (2010).
4. D.I. Shiman, I.V. Vasilenko, S.V. Kostjuk. Polymer, 54, 2235-2242 (2013).
5. N.A. Kukhta, I.V. Vasilenko, S.V. Kostjuk. Green Chem., 13, 2362-2364 (2011).
51
EFFECT OF MOLECULE STRUCTURE AND PACKING ON
PHOTO- AND ELECTROPHYSICAL PROPERTIES OF ORGANIC
THIN FILMS
A. Kukhta, P. Kuzhir
Institute for Nuclear Physics, Belarusian State University, Minsk, Belarus, [email protected]
Thin film nanostructures based on -conjugated organic compounds attract wide
attention of researchers owing to the unique properties and the possibility of manifold
practical applications. In such nanostructures the optical and electrophysical properties
depend essentially on molecular structure and organization of the molecules in the solid
state.
In this talk a short review on our latest studies of some optical and electrophysical
properties of organic thin films based on the set of linear -conjugated molecules with
close structures are presented.
The effect of the substrate nature, the molecule structure, and the deposition rate on
optical and luminescent properties, morphology and photostability, is shown using
dibenzoxazolylbiphenyl derivatives as typical example. It was revealed the reversible
molecular reorganization resulting to the formation of partially ordered structures with
luminescence polarization and radiating ability depending on the film temperature below
the glass transition. The unusual behaviour of photostability at appropriate molecule
packing has been revealed. The presence of oxygen was found to cause the essential
luminescence quenching. The effect of adsorbed oxygen on electrophysical properties of
some organic thin film nanostructures was found. The interesting gas phase photophysical
experiments are also presented.
52
THE EFFECT OF ANISOMERIC CARBONACEOUS NANOFILLERS
ON THE RELAXATIONAL BEHAVIOUR OF THERMOPLASTIC
POLYMERS
T. Ivanova1, J. Zicans1, J. Bitenieks1, R. Merijs Meri1, S. Maksimenko2, P. Kuzhir2
1
2
Institute of Polymer Materials, Riga TechnicalUniversity, Riga, Latvia
Institute for Nuclear Problems, Belarus State University, Minsk, Belarus
Carbonaceous nanofillers (CNTs, graphene, onion like carbon and others) novadays
are recognized as potential fillers for modification of polymer materials due to their
specific electrical properties. Incorporated in polymer matrix these nanofillers have ability
to form conductive network, which allows manufacturing of polymer nanocomposites with
improved electrostatic discharge dissipation (ESD), electromagnetic interference (EMI)
shielding and microwave absorption.
In this study the effects of carbonaceous nanofillers, in particular carbon nanotubes
(CNTs), on elastic and dielectical relaxation and microwave scattering parameters of two
thermoplastic polymers - polypropylene (PP) and styrene acrylate copolymer (SAC) - are
investigated. PP nanocomposites have been prepared by melt mixing with twin screw
extruder. SAC nanocomposites have been prepared by ultrasound assisted mixing of SAC
and nanofiller suspensions in aqueous media, followed by film casting. Carbonanceous
nanofiller concentration in the studied polymer nanocomposites is varied
from 0 to 5 wt. %.
The study shows that in the case of PP based nanocomposites permittivity ’,
measured in frequency range from 10-2 – 107 Hz, for neat PP is independent from
frequency and is within 1.9. This behavior is characteristic for typical insulating materials.
However by adding CNTs a noticeable linear increase in ’ is observed, especially at
lower frequency range. The percolation threshold is observed at 1 wt. % of CNT, testifying
that conducting CNT filler network is formed through the polymer matrix. The change in
’ by several orders of magnitude is noticed at CNT concentrations of 2 and 5 wt. %.
Microwave scattering measurements have been performed at frequency range from 26
– 36 GHz. By analyzing the CNT impact on PP matrix, it can be concluded that increasing
the concentration of CNTs leads to an increase in the reflection and absorption parameters,
and consequently, to a decrease in transmission. Thus adding 2.0 wt. % CNTs weakens the
power of the electromagnetic radiation by 80%. These results indicate that investigated
polymer nanocomposites may be used as lightweight, effective EMI shielding materials.
53
INFLUENCE OF THE SILVER NANOPARTICLES
CONCENTRATION ON POLYMER/SILVER NANOCOMPOSITE
PROPERTIES
J. Pudlauskaitė1, V. Jankauskaitė1, P. Narmontas2, I. Prosyčevas 2
1
Faculty of Design and Technologies, Kaunas University of Technology, Studentų g. 56, Kaunas LT-51424,
Lithuania, e-mail: [email protected]
2
Institute of Materials Science, Kaunas University of Technology, Savanorių pr. 271, Kaunas LT-50131,
Lithuania
Nowadays technologies continuously require new knowledge-based nanostructured
polymers.
In modern times, there is an increasing need of knowledge-based nanostructured
polymers with special properties being used in the latest technologies.
The future progress in the field of science, technology, engineering and medicine is
largely dependent on new knowledge-based nanostructured materials with special
combinations of exclusive properties. The incorporation of nanoparticles into polymer
matrixes will create a new class of materials – nanocomposites in which the dimension of
dispersed particles occurs at the nanometer scale [1]. These materials are of current interest
because of their multi-functionality, ease process ability, potential for large-scale
manufacturing and lightness compared to metals.
The aim of this work was to investigate the influence of silver (Ag) nanoparticles
deposited from colloidal solution in photopolymer composition on the morphology of
grating. Light sensitive phenol formaldehyde resin with naftochinon diazid (positive
photorezist) was used for the investigations. Ag colloid was produced in distilled water,
dioxane, chloroform and alcohol-polyvinylpyrrolidone solvents by chemical reduction of
silver nitrate, and incorporated into polymer composition by mixing. The content of Ag
colloid concentration in polymer varied from 0 wt% up to 30 wt%. The film of modified
polymer was obtained by spin coating on optical quartz substrate and dried at 100° C for
20 min. The gratings were formed by lithography.
Analysis performed with FT-IR, AFM and SEM with X-ray microanalysis showed that
Ag nanoparticles from different colloidal solutions change the grating chemical structure
and geometry – the ridges of grating splits into two parts, supposing due to the Ag
nanoparticles light diffusion. Therefore, the ridge surface becomes soluble to etching
solvents, while exposure areas are removed.
According to the study results the best surface quality was obtained by using Ag
nanoparticles prepared in chloroform and distilled water. These colloid solutions were
selected for further investigations in order to determine the Ag nanoparticles content
influence on the periodic structures geometry. Obtained results confirm that variation in
the Ag nanoparticles content permit of the controlling geometrical parameters of periodic
structures.
References
1. O. M. Folarin, E. R. Sadiku, A. Maity. J. Phys. Sci., 24, 4869-4882 (2011).
2. P. R. Reddy, K. M. Raju, N. S. Reddy. Chem. Sci. Rew. Lett. 4, 228-235 (2013).
54
SOME FEATURES OF STARCH GELATINIZATION
J. Galkin1, E. Mažonienė1,2, J. Liesienė1
1
2
Department of Organic Chemistry, Kaunas University of technology, Radvilėnų pl. 19 Kaunas, Lithuania
AB Amilina, J.Janonio 12, Panevėžys, Lithuania
Starch is a natural material obtained from renewable resources. As a biomaterial,
starch from different botanical sources has considerably different properties. Starch
properties are strongly influenced by the formation of amylose-lipid complexes which are
present in case of cereal starches [1].
The main aim of the study was to analyze the influence of lipids on the starch
gelatinization process and how in consequence this influence is connected to rheological
properties of starch pastes.
In order to achieve these goals methods, such as differential scanning calorimetry, a
rheological analysis (including the oscillatory rheology), a particle size analysis (based on
a light scattering principle) were applied on starch suspensions and pastes. For deeper
understanding the starches from a different botanical origin were compared: potato, wheat
and corn (those are the main commercial sources of starch in EU [2]). Moreover, the
samples with additional quantities of surface active compounds (SAC) were included into
the
study;
chosen
additives
were
sodium
dodecyl
sulfate
(SDS),
alkylbenzyldimethylamonium chlorides (ABDMC) and sodium oleate (SOL).
The study revealed that SAC had an effect on the starch gelatinization profile,
gelatinization enthalpy and distribution of particle sizes in a starch paste after
gelatinization. Gained results showed that the effect of SAC was starch botanical source
dependent, which is an indication of the existing competition between SAC and lipids in
starch itself. Basically, the effect of SAC has been similar for wheat and corn starch that
are the cereal starches and contain noticeable amounts of lipids, however potato starch
(where the amount of lipids is minor) has exhibited a different behavior.
The gelatinization profile was affected significantly; maximum of viscosity was
changed, as well as the temperature of the onset point in viscosity development during
gelatinization. A general trend was observed; additives decreased the peak viscosity for
potato starch (applied changes were up to 50% based on values without additives),
meanwhile they increased it in the case of cereal starches with ABDMC and SDS (applied
changes were more than 50% based on values without additives) and kept it similar in the
case of SOL additive.
Distribution of the particle size was affected by SAC, but interestingly that if the
additives were promoting higher peak viscosity, the mean particle size was shifted towards
the range of smaller particles, and also if additives reduced the peak viscosity, the mean
particle size was shifted towards bigger particles. This might not be the evidence of
swelling degree, since the pastes were kept at 90oC for 20 min prior the analysis, but it
could be connected to the degree of solubilization of starch granules. This hypothesis was
confirmed indirectly, via measuring the storage and loss modulus of starch pastes during
and after gelatinization. General trend has been observed that if the peak viscosity
increases, the storage modulus decreases, indicating the loss of the solid like material
response in the sample.
Acknowledgements. We would like to thank AB “Amilina” company for making this study possible.
References
1. N. Singh, J. Singh, L. Kaur, N. S. Sodhi, B. S. Gill. Food Chemistry, 81 (2003).
2. By- products from the EU starch industry: Valuable and safe ingredients for animal feeding, aAf, 2000.
55
IMPROVED PHYSICAL-MECHANICAL PROPERTIES OF
BIODEGRADABLE PAPER BY ADDING NANOPARTICLES FROM
LIGNOCELLULOSE
L. Vikele, I. Birska, A. Treimanis, M. Laka, S. Chernyavskaya
Latvian State Institute of Wood Chemistry, 27 Dzerbenes Street, Riga, Latvia. [email protected]
The traditional way to improve the properties of paper after refining is a special
addition of synthetic organic and inorganic additives. A part of these additives creates the
problems in recycling process as well as they are resistant in the biodegradation process.
The objective of this study is to develop the various paper additives that are 100%
biodegradable.
This study is focused on the application of the biodegradable nanosize fillers from
cellulose and lignocellulose (wood residues – sawdust and bark). These nanoparticles were
used for paper to improve the strength indices, surface characteristics and barrier
properties. The cellulose nanoparticles are a promising new material constituent that can
provide the reinforcement of polymer composites due to the high stiffness of the cellulose
crystallites and the network formation.
The nanoparticles were prepared from kraft pulp and woodworking residues by
thermocatalytic method and following mechanical treatment in the water dispersion at a
high shear stress, TEMPO oxidation as well as by modification of nanoparticles by
cationisation.
The size and charge of particles were examined using AFM microscopy, “Nanosizer”
and zeta potential measurements.
The particles were added to the furnish consisting of bleached kraft pulp in different
amount. The composition was evaluated by mechanical and barrier properties testing.
Particles from cellulose (kraft pulp) and wood residues in the amount of 10-20% by
weight lead to the increase of the paper handsheets tensile and burst strength indices by up
to 30%. Also the wet-strength indices of the paper have been improved by 40%. The
retention of the nanocellulose particles was improved substantially by cationisation of the
particles as well as by TEMPO-oxidation. Paper surface was improved significantly when
modified with 20% charge of nanocellulose. The samples exhibited also improved barrier
properties by about 25% related to the water penetration and contact angle measurement.
56
HEMICELLULOSES FROM DIFFERENT RESOURCES –
COMPARISON OF PROPERTIES
J. Zoldners, J. Kuncēvičs, T. Kiseļeva, L. Stiebra
Latvian State Institute of Wood Chemistry Riga, Latvia, [email protected],
Hemicelluloses (HC) are the second abundant polysaccharides in different plant
material, representing 20-35% of the material mass and arise interest for different practical
application – as food additives, thickeners, stabilizers and emulsifiers. The properties of
isolated from plant material HC depend on isolation conditions and plant resource. In this
work properties of HC isolated from some popular in Latvia hardwoods – grey alder (Alnus
incana), birch (Betula verrucosa) , aspen (Populus tremula) as well ashemp shives were
compared. The HC were isolated by extraction the plant material with 7% KOH 3 h at
20oC and were divided in water-soluble (WSHC) and water-insoluble (WIHC) fractions
after neutralization of HC solution with acetic acid till pH5.2. At the mentioned isolation
conditions the highest HC total yield and lowest WSHC proportion was from birch wood
(12% from total yield of HC), the highest – for hemp HC (84% from total yield). For aspen
and grey alder wood WSHC fraction yield was approximately similar (34-39% from HC).
Sugar composition, determined by using Liquid chromatography and sugar standards for
all preparations was comparatively similar – 97-98% was xylan. The others were
rhamnose, glucose, galactose and mannose. Al HC preparations contained 0.2-0.3 % free
0.5-0.8% esterified COOH groups and 1-3% lignin. Specific viscosities in DMSO for
separate HC and their fractions did not differ essentially and were in boundary 0.37- 0.55
dl/g. For the evaluation of possibility of practical application of HC, their emulsifying and
thickening properties were compared. Emulsions contained 70% by volume olive oil and
30% HC solution or dispersion in water. HC concentration in the water phase was 7%.
Experiments demonstrated that all HC preparations can be used as emulsifying agents. The
emulsions with higher viscosity and stability were formed at using grey alder HC; with
lowest viscosity – at using aspen HC. Evaluation of the thickening properties of HC
demonstrated, that WSHC preparations formed solutions with very low viscosity and are
not useful as thickeners. For the WIHC the highest viscosity at the same concentration was
observed for birch HC; the lowest – for alder WIHC. We found that additionally HC
dispersions viscosity can be regulated at introduction in the solutions some organic acids.
Further experiments demonstrated that WSHC preparations in the presence of glycerin as
softener, formed transparent films with comparatively high strength properties but very
low (1-2%) elongation at break and non - resistant to water. The worse film-forming
properties were observed for hemp HC.
Acknowledgement . The investigations were sponsored by the Latvian State Research Program.
57
ADVANCES IN LIGHT SCATTERING FOR POLYMER
CHARACTERISATION
S. Olivier,P. Clarke, M. Pothecary, M. Nicholls, S. Ball
Malvern Instruments, Grovewood Road, Malvern, WR14 1XZ, United Kingdom
[email protected]
Gel-permeation chromatography has been around for many years and is a wellestablished technique for the measurement of polymer molecular weight and molecular
weight distribution. Historically, the molecular weight was determined using standards of
a known molecular weight and by comparing the retention volume of the sample to the
standards. This worked well for simple polymers such as polystyrene or polymethyl
methacrylate where molecular weight standards are readily available, but is inaccurate
when the sample and standard polymers are different as each has its own relationship
between size (which define retention volume) and molecular weight. This relationship is,
of course, structure-based and related to intrinsic viscosity (IV).
With novel polymers becoming more and more common and the lack of availability of
molecular weight standards for anything but simple polymers, light scattering offers a
compelling alternative route to determine molecular weight independent of sample
retention volume. Since light scattering detectors were introduced, they have seen several
different development iterations. Modern systems are now either based on the
RALS/LALS (Right Angle/ Low Angle) single angle approach or the MALS (MultiAngle) approach. The former is often combined with a viscometer detector and hence also
leads to choice between Rg and IV for determining structural differences in polymers.
This presentation will compare and contrast different methods for making light
scattering measurements of molecular weight and also compare the resulting size data with
size from intrinsic viscosity. The results from each will be examined to determine whether
the full range of measurements can further increase the potential of light scattering and
multi-detector GPC to gain further insights into the mass, size and structure of novel
polymers.
58
AUTOMATED 2-DIMENSIONAL CHROMATOGRAPHY FOR THE
CHARACTERIZATION AND DEFORMULATION OF COMPLEX
POLYMERS AND BLENDS
A. Williams
PSS Polymer Standards Service, D-55120 Mainz, Germany, [email protected]
Today polymers are fine-tuned to optimize their properties, e.g. higher temperature
stability and improved mechanical characteristics. However, in order to achieve these
engineering aims, polymer formulations are getting more and more complex. This makes
polymer characterization especially demanding.
Gel Permeation Chromatography (GPC, SEC) has been used widely to analyze
polymers for more than half a century. Since GPC/SEC separation is not governed by
molar mass but by hydrodynamic volume, copolymers, polymer blends and complex
polymer formulations cannot be characterized easily using GPC/SEC techniques alone. On
the other hand, gradient HPLC can be used to separate copolymers by
chemical composition.
A 2-dimensional chromatography system is presented, which is able to acquire and
process samples automatically in two dimensions (e.g. HPLC combined with GPC, TREFGPC, GPC-SFC, GPC-CE).
The superior resolution of 2-dimensional chromatography is demonstrated using
several samples including a 16-component mixture of styrene/butadiene block copolymers
having 4 different molecular weights and 4 different compositions each.
Using a 2-dimensional experiment, such complex mixtures can easily be resolved. The
2D contour map representation can be used for quantitation, whereas the surface plot
illustrates the 3D data array.
A GPC chromatogram of such complex mixture often only shows a broad peak with
little structure. The gradient HPLC alone may show additional peaks, but often with poor
resolution and no further indication of the complexity of the sample mixture.
Combining both separation techniques allows the separation of the multi-component
mixture, giving accurate molar mass and composition information for each single
component in only one run.
References
1. P. Kilz, H. Pasch. In: Encyclopedia of Analytical Chemistry (R.A. Meyers, ed.), Vol. 9, 7495-7543,
Wiley, Chichester (2000).
2. P. Kilz. In: Encyclopedia of Chromatography (J. Cazes, ed.), Dekker, New York, 195-200 (2001).
3. P. Kilz, F. Gores. In: Chromatography of Polymers (T. Provder, ed.); ACS Symposium Series 521, ACS,
Washington, Chapter 10 (1993).
4. P. Kilz, R.P. Kruger, H. Much, G. Schulz. In: Chromatographic Characterization of Polymers (T.
Provder, ed.); Advances in Chemistry 247, 223, ACS, Washington (1995).
59
PROJECT EVOLUTION: ELECTRIC VHEICLE CONCEPT
THROUGH BIO-SUSTAINABLE MATERIALS
M. Kirpluks, U. Cabulis
Polymer Laboratory, Latvian State Institute of Wood Chemistry, Riga, Latvia, [email protected]
The solution of the world’s diminishing petroleum reserves could be seen in different
types of electric vehicles (EVs). All of them have one common trait, they are energy
efficient. This is achieved through different lightweight materials and clever engineering
solutions. Polyurethane (PU) foams are bio-inspired structures with immense potential and
extraordinary properties. They are light-weight cellular materials with a very high specific
stiffness, very good vibration and sound damping, energy absorption capability, moisturesealing properties and thermal insulation. Due to these multifunctional characteristics these
materials show great potential for use in the new generation of EVs [1].
Latvian State Institute of Wood Chemistry (IWC) has started research of PU foams for
automotive application in frame of EUs 7th FP project EVOLUTION. For this project six
different environment friendly polyols were investigated as possible raw material for
production of PU core of sandwich structure panels. These panels will be used in
construction of vehicle NIDO EV under body. Their main goal is to reduce weight also
there is possibility of adding additional beneficial properties like sound proofing and
thermal insulation. °
Polyols used in this project are derived from renewable resources like tall oil and
rapeseed oil; also they are synthesized from industrial waste of PET production. Tal oil is
byproduct of cellulose production and rapeseed oil is an agricultural product. Form these
natural oils polyols were synthesized using ester and carboxyl group reaction with
polyfunctional alcohols like diethanolamine and triethanolamine. Also, polyols were
obtained using epoxydation of fatty acid double bonds and epoxy ring opening with
diethyleneglycol (DEG) [2]. Lithuanian company “Neo Group” in Klaipeda district
supplied IWC with three different aromatic polyester based polyols synthesised from
industrial PET waste [3]. For development of PU formulations polyols with hydroxyl value
of 240-400 mgKOH/g and average functionality of 2.0-3.1 have been chosen.
Rigid PU foam samples were obtained in free rise mould and stainless steel mould.
Also, the sandwich panel production was modeled by foaming PU foam between two
aluminum sheets. Free rise density of obtained rigid PU foams was 110-160 kg/m3. Closed
cell content for PU samples obtained in free rise mould was 90-99%. The density of
moulded PU foams was 220-230 kg/m3. The physical-mechanical properties of PU were
following: the compression strength: 2.96-3.95 MPa (Emod: 75-107 MPa) and the tensile
strength: 2.63-3.76 MPa (Emod: 118-161 MPa). The morphology of obtained rigid PU
foams was determinate using SEM imagining
This study will help to determinate which of polyol type is better for chosen EV part
production. The aromatic structure of PET polyols results in increase of physicalmechanical properties of PU foams when compared to natural oil polyols. Further work on
optimization of PU foam formulation and reinforcing their structure with different fillers
will continue.
Acknowledgements.The research leading to these results has received funding from the EC 7th FP project
EVOLUTION under grant agreement n° KBBE-314744.
References
1. E. Schwartz. Polymotive, 9, 14-18 (2011)
2. M. Kirpluks, U. Cabulis, M. Kuranska, A. Prociak. Key Eng. Mat., 559, 69-75 (2013).
3. Vitkauskiene, R. Makuska. Chemija, 19, 29-34 (2008).
60
RECYCLED POLYETHYLENE TEREPHTHALATE BASED HYBRID
NANOCOMPOSITES: STRUCTURE AND PROPERTIES
G. Japins1, R. Berzina1, J. Zicans1, R. Merijs Meri1, V. Kalkis2, I. Reinholds2
1
2
Institute of Polymer Materials, Riga Technical University, Riga, Latvia, [email protected]
In last decades it is approved that post-consumer polyethylene terephthalate can be
purified to a very high level and used as high class engineering material for broad range of
applications. It is an important prerequisite for using recycled polyethylene terephthalate
(RPET) as a perspective matrix for development of nanocomposites. Use of RPET for
development of polymer nanocomposites is governed also by ecological reasons – the
amount of waste, going to the landfill as well the use of fossil raw materials can be
considerably reduced. Besides it, manufacturing of RPET based nanocomposites is
promoted by broad availability of recycled polymer, due to well-developed recycling
strategy of this polymer.
It is economically favorable to melt mix RPET with nanostructured montmorillonite
clay (MMT) by using twin screw extruder. Due to its platelike shape and nanodimensions
MMT is well known as perspective modifier of elastic, thermal and barrier properties of
polymers. The addition of nanostructured modifiers in most case adversely affects
deformability and processability of the materials. Consequently, in the current research
liquid crystal polymer (LCP) is used as processability modifier of RPET/MMT
nanocomposites. Due to its rigid rod structure LCP should be regarded also as reinforcing
additive in respects to mechanical and barrier properties of polymer.
Consequently in this research structure and selected exploitation properties of RPET
hybrid nanocomposite with MMT and LCP, obtained by twin screw extrusion, are
investigated. In the study main attention is paid to the evaluation of the effect of the
simultaneous addition of LCP and MMT on the structural, mechanical and barrier
properties of RPET based composite by using following methods of investigation:
differential scanning calorimetry, water vapour sorption test, dynamic thermal mechanical
analysis, tensile stress-strain analysis, instrumented impact strength test.
It is shown that at certain LCP and MMT concentrations considerable synergetic effect
is observed especially in respect to Young’s modulus.
Acknowledgements.The research is carried out within the framework of the ERDF project Nr.
2010/0209/2DP/2.1.1.1.0/10APIA/VIAA/028
61
INVESTIGATION OF DISPERSE DYES APPLICATION FOR
COTTON BLENDED FABRIC COLOURATION
A. Borisova, S.Reihmane
Several interrelated factors contributing to the justification of replace homogeneous
textile materials by blends, such as economy, physical properties, appearance and
durability have been stated in recent decades. Blends of ester fibers with cotton are
produced in great quantity worldwide. Aspects contributing to this situation have been the
relative ease of processing, effective clearing and versatility of application, leading to a
wide range of dyes and finished effects [1]. Without question the exploitation of
cotton/polyester blends represents the most successful compromise between the contrasting
physical properties of natural and synthetic fibers.
The dyeing process of textile materials and its successful outcome results the quality
estimation in general of ready-made garments and provides outlet possibilities according to
customer demands and fashion tendencies. There are few types of coloured effect achieved
by dyeing a blend of two fibers, for instance shadow, contrast etc., but the most difficult
task is to create a solid colouring effect (sometimes called a union-dye effect) when both
fibers are dyed as closely as possible to the same hue, depth and brightness. This challenge
has been solved on an industrial scale by application of two dye classes, for example the
combination of reactive and disperse dyes, via two-bath or one-bath two-step dyeing
method employing suitable dyes and chemicals for each fiber [2], also raising a strict
preparation and process control necessity and making it cost-expense. Investigation in the
field of optimization of cotton blended fabric dyeing technology is of current importance.
The present study covers the twill weave 50% cotton/ 50% polyester blended fabric
one-step one-bath dyeing technology elaboration using a single dye class, namely disperse
dyes. The thermal dyeing approach (also called a thermosol) was applied. For better
examination of concomitant processes and action mechanism during the dyeing, models of
100% cotton and 100% polyester fabric were used. The content of dyeing bath as well as
amounts of all applied chemicals were obtained experimentally and examined practically.
Continuing research study on fabric’s modification in alkaline medium [3], the exhaust
sodium hydroxide treatment with vary of different technological parameters was executed
prior to dyeing as a pretreatment operation. Weight loss, water absorbency, dye exhaustion,
colour measurements, stiffness, tensile strength and elongation at break values were
determined according to national and international standards. Results of colour fastness to
rubbing, washing, ironing and artificial light were also attained. Achieved results are
promising as an alternative cost-effective dyeing technology for cotton blended fabric
colouration.
References
1. J.Mokhtari et al. Color Technol, 124, 295-300 (2008).
2. J.A.Bone et al. Color Technol, 123, 152-162 (2007).
3. A.Borisova, S.Reihmane. Key Eng Mat, 556, 13-18 (2013).
62
HYDROGEN-BONDING OF METHOXY GROUPS VERSUS
CHARGE-TRANSPORTING PROPERTIES: EXPERIMENTAL AND
THEORETICAL APPROACH
G. Sini1, J.V. Grazulevicius2,J. Keruckas2, D. Gudeika2, V. Mimaite2, V. Jankauskas3
1
Laboratoire de Physicochimie des Polymères et des Interfaces (LPPI), Université de Cergy-Pontoise, 5 mail
Gay-Lussac, F-95031 Cergy-Pontoise Cedex, France, [email protected]
2
Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas,
Lithuania
3
Department of Solid State Electronics, Vilnius University, Saulėtekio alėja 9, LT-10222 Vilnius
Methoxy groups (OMe) are known to influence the properties of charge-transporting
materials. The reduction of the ionization potential of low molar-weight glassy-materials
and red-shifting of the absorption spectra are among the most frequently evocated effects.
However, different studies have shown that OMe containing materials show better chargetransporting performances as compared to the non containing OMe groups1-2. In this
presentation we show how the (-OMe…., N, O) hydrogen bonds established in the holetransporting materials may contribute to the enhancement of the hole mobility in these
materials. A quantitative and qualitative theoretical analysis in the frame of Marcus theory
allows for a better understanding of the experimental results2. Recent results, comparing
OMe- versus methyl substituted compounds, are also discussed.
References
1. J. Keruckas et al, J. Mater. Chem. 22, 3015 (2012)
2. D. Gudeika, et al, submitted.
63
PATTERING IN POLYMERIC NANOCOMPOSITES BY PULSE
LASER
R. Bakanas1,2, S. Zacharovas2, P. Narmontas3, V. Jankauskaitė1
1
Faculty of Design and Technologies Kaunas University of Technology, Studentu st., 56, LT-51424 Kaunas,
Lithuania, [email protected]
2
JSC “Geola Digital”, Naugarduko st. 41, LT-03227 Vilnius, [email protected]
3
Institute of Materials Science Kaunas University of Technology, Savanorių st. 271, LT-313432 Kaunas,
Lithuania
Over last decades “Geola” group has made significant progress in realizing RGB
pulsed laser solutions for holography for the needs of imaging [1]. The pulsed 440 nm laser
wavelength lies in a useful range for many photosensitive materials such as photoresists,
silver halides, and photopolymers. At present time authors initiated the research
concerning pulsed radiation interaction with photoresist for commercial application. It was
obtained that in order to record transmission holograms with pulsed laser significantly less
energy is needed than in the case of continuous wave (CW) laser. The holograms were
recorded on 10 m positive photoresist Shipley S1813 layer with only 8 mJ/cm2 of pulsed
energy at 440 nm and duration of 50 ns. It is related to the photoresist sensitivity that is
greatly affected by low intensity reciprocity failure [2]. AFM investigations showed that
profiles with grating height of more than 100 nm can be achieved. Such holograms suitable
for the manufacturing of a shim matrix for high quality embossed holograms.
The aim of present study is the investigation of possibility to record holograms with
pulsed laser in the polymeric nanocomposite layer. For this purpose positive photoresist
Shipley S1813 was used. To obtain the nanocomposite silver (Ag) nanoparticles were
deposited in photoresist bulk from colloidal solution, produced by chemical reduction of
silver nitrate. The photoresist and Ag nanocomposite layer was obtained by spin coating on
optical quartz substrate and dried at 100° C for 20 min. The grating with period of 100 nm
was formed by pulsed laser.
The influence of Ag nanoparticles concentration on the composition morphology and
holograms optical properties has been studied. Synthesized Ag nanoparticles were
characterized by various methods (UV-Vis spectrometry, SEM-EDS, etc.). Analysis of the
holograms performed with AFM and SEM showed that the Ag nanoparticles increase the
surface roughness and changes diffraction efficiency of holograms.
References
1. S. Zacharovas, A. Nikolskij, R. Bakanas, D. Brotherton-Ratcliffe. Proc. SPIE 8644, Practical
Holography XXVII: Materials and Applications, 864407 (2013).
2. H. Bjelkhagen, D. Brotherton-Ratcliffe. Ultra-realistic Imaging – Advanced Techniques an Analogue
and Digital Colour Holography, Taylor & Francis, 2013.
64
THE CREATING ORDERED OFNANOSTRUCTURE: CONTROL OF
SELF-ORGANISATION IN BOTTOM-UP APPROACH
M.Yu. Barabash, D.A.Grynko, G.G. Vlaykov
Technical Center of NAS of Ukraine, Kyiv; 04070, Ukraine, [email protected]
size distribution, a.u.
Template is a tool which allows fabricating nanostructures, fig. 1,2, in nonlithographic process [1-5]. For the electrostatic template preparation authors suggest to
apply photothermoplastic electrophotographic process with a free surface of the specific
nanocomposite organic photoconductors [1-5].
The spatial resolution of template is determined by the larger of two factors: the
diffusion length of components (molecules, nanoclusters, nanocrystals, etc., which
essentially depends on the mass of nanoparticles and interaction with the surface topology)
and the period of the field distribution.
Template-organized 2D optical
nanostructures
maked
with
organic dye and gold nanoclusters.
Their optical resonances and
template preparation technique
presented in publications [4].
Nanocomposite Au-polymer
(poly-N-vinyle-carbazole),
codeposited
in
vacuum
on
the
Fig.1.
Gold
nanoclusters
Fig.2. Nanostructure
organized by strong electric
assembly
on
the
surface of template, selforganised
field of the template, AFM.
template.
efficiently
also.
TEM
Period 2 mkm, height 120 nm.
Nanostructure
investigation of nanocomposite
topology controlled by
gold clusters permit to find out
topology of light field.
nanoclusters size distribution and
critical nuclear size [4]. Shift of critical nuclear size, fig.3, in the electric field of template
show the dramatic impact of local electric field on nucleation and critical nuclear size.
Au-PVC nanocomposites
Nucleation
modeling
in
the
thermodynamics approach yield estimation of
nucleation in the common conditions
local electric field. Estimated fields are: electric
nucleation in electric field
mean field 108V/m and local field up to
of the template
1010V/m.
Conclusions. Manipulation with electric field
of template allows controlling basic processes
of condensed phase formation: adsorption,
diffusion and nucleation and to assemble some
nanocluster size, nm
nanostructures
for
nanophotonics
and
critical nuclear size
nanoplasmonics via guided selforganisation
Fig.3. Size distributions comparison for gold
processes in bottom-up approach. Nucleation in
nanoclusters in the Au-PVC nanocomposites
the electric field of the template is the way to
deposited in the electrical field of template and
new phases formation.
without field.
1,0
0,8
0,6
0,4
0,2
0,0
0
1
2
3
4
5
References
1. Patent of Ukraine №55127 (2010).
2. Patent of Ukraine №58732 (2011).
3. M.Yu. Barabash, D.A. Grynko. Nanosystems, Nanomaterials, Nanotechnologies, 11 (3), 595-608
(2012).
4. D.A. Grynko, Yu.M. Barabash, I.E.Matyash, B.K.Serdega, Physics of the Solid State,54 (11), 146153 (2012).
5. M.A. Zabolotny, N.P. Kulish, Yu.M. Barabash, Physics of the Solid State, 52 (4), 826-830 (2010).
65
ARYLETHYNYL-SUBSTITUTED FLUORENES AS EFECTIVE
HOLE-TRANSPORTING MATERIALS
M. Baronaitė, J. Simokaitienė, J. V. Gražulevičius, D. Volyniuk
Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50245, Kaunas,
Search for new materials with advanced properties is one of the major tasks of the
rapidly developing field of organic optoelectronics. Fluorene-based materials exhibit high
emission quantum yields, good charge-transporting properties, and good processibility due
to their good solubility in common organic solvents [1].Incorporation of an acetylene
segment is an interesting approach to increase the π-conjugationin materials that provide
enhanced photovoltaic propertiesand ensure an efficient intramolecular charge separation
with highphotocurrent generation and slow recombination [2].
In this presentation we report on the synthesis and properties of arylethynyl-substituted
derivatives of fluorene.
5
1
O
O
O
2
6
3
7
O
4
O
O
8
Compounds 1-8 were sinthesyzed by one step procedure from appropriate mono- or dibromofluorene by Sonogashira coupling with various terminal alkynes. Compounds were
purified by colum chromatography. They were indentified by 1H and 13C NMR, IR and
mass spectrometries. The thermal, optical and photoelectrical properties of the synthesized
compounds were studied. Their initial decomposition temperatures were recorded above
318 oC. Their dilute solutions feature fluorescence emission in the blue spectral range with
the quantum efficiency ranging from 40 % to 60 %.
The ionization potencials of the synthesized compounds estimated by cyclic
voltammetry range from 5.17 to 5.61 eV. Hole drift mobilities of the molacular mixtures of
the synthesized compounds with bisphenol Z polycarbonate reach10-3 cm2/Vs at high
electric fields.
Acknowledgments. This research was funded by the European Social Fund under the Global Grant measure.
References
1. B.K. Yap, R.D. Xia, M. Campoy-Quiles, P.N. Stavrinou, D.D.C. Bradley. Nature Mater 7, 80-84 (2008).
2. P. Singh, A. Baheti, K.R.J. Thomas, C.P. Lee, K.C. Ho, Dyes and Pigments, 95, 523-533 (2012).
66
FORMATION OF SILVER NANOPARTICLES: INFLUENCE OF THE
STRUCTURE OF THE POLYMER MATRIX AND THE SYNTHESIS
TEMPERATURE
N. Kutsevol1, T. Bezugla1, M. Bezuglyi1,2, V. Chumachenko1
1
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv,Ukraine,
[email protected]
2
Noble metal nanoparticles (NPs) are becoming increasingly important due to their
potential applications in catalysis, photographic processes, cosmetics, medicine,
biotechnology, etc. Properties of nanosystems strongly depend on the morphology, crystal
structure, and dimension of nanoparticles. Polymer matrices have attached considerable
attention as a promising approach for in situ synthesis of metal NPs of controlled size and
morphology.
In this study Ag NPs were generated in polymer matrices with different internal
structure in solution: linear polyacrilamide (PAA) and star-like copolymers dextran-graftpolyacrilamide (D-g-PAA) as well as their anionic derivatives [1]. Sodium borohydride
was used for reduction of silver nitrate in aqueous medium. Syntheses were carried out at
different temperatures.
The nanosystems were characterized by UV-Vis spectroscopy, TEM microscopy,
small-angle X-Ray, dynamic light scattering (DLS). The formation of Ag NPs was
observed by the appearance of brownish-red color of the solution and intensive surface
Plasmon absorption band in the range of 390 – 410 nm. Obtained diffraction data confirm
the face-centered cubic (fcc) form of Ag NPs.
TEM images of Ag NPs showed spherical or roughly spherical particle shape. Analysis
of TEM and DLS data revealed the average size of Ag NPs of 5-20 nm. Size distribution
functions for all colloid samples have the binodal character with maxima located in the
range of 5-8 and 12-16 nm and are depended on the type of polymer matrix and the
synthesis conditions.
Stable silver colloids were obtained in temperature range of 0 – 80 ºC in nonionic and
anionic D-g-PAA matrices. The increase in temperature leads to increased intensity of the
Plasmon maxima indicating higher concentration of Ag NPs created in nonionic star-like
D-g-PAA matrix. On contrary, for Ag NPs synthesized at 80 ºC in nonionic linear PAA
matrix active oxidation and aggregation process were observed.
Silver colloids fabricated in the anionic linear PAA matrix were unstable even at room
temperature, while Ag NPs in anionic derivatives of star-like D-g-PAA were stable for a
long time after preparation.
The internal structure of macromolecules affects both the process of NPs formation
and metal colloid stability. The host macromolecular chains improve the dispersion of
nanoparticles inside the polymer matrix, and also partially prevent the formation of
aggregates. It was found that branched macromolecules D-g-PAA are more efficient
matrices for Ag NPs creation in comparison with linear PAA having coil conformation in
solution. Star-like structure of polymer matrix provides obtaining of stable silver colloids
with a narrow size distribution and roughly spherical shape of particles.
Acknowledgements.This investigation was funded by NATO Grant CB.NUKR.CLG 98424.
References
1. N. Kutsevol, T. Bezugla, M. Bezuglyi, M. Rawiso. Macromol. Symp. 317-318 (1), 82-95 (2012).
67
SYNTHESIS AND CHARACTERIZATION OF NOVEL
POLY(AMIDOAMINE)
A. Bočkuvienė, I. Vinkevičiūtė, A. Vareikis
Department of Polymer Chemistry, Vilnius University, Vilnius, Lithuania, [email protected]
Poly(amidoamines) (PAA) is unique family of water-soluble, biodegradable,
biocompatible and non-cytotoxic polymers. They are widely developed for use as
biomedical materials, as drug and gene delivery vehicles [1, 2].
PAA can be easily synthesized by Michael-type polyaddition of primary or secondary
amines to bis(acrylamides). Chemical constitution of the backbone and side chains of PAA
can be easily tailored. As usually this is done via selection of amine-type monomer(s)
because of their great diversity and accessibility [2].
This work represents investigation of addition of 1,3-diamino-2-propanol (DAP) to
N,N'-methylenebisacrylamide (MBAA) (Scheme 1) which leads to a novel type of
hydroxyl-containing poly(amidoamines) (HPAA) where hydroxyl group is directly
attached to the main chain (Scheme 1).
Using equimolar amounts of MBAA and DAP, addition reaction was carried out in
N,N-dimethylformamide, N,N-dimethylacetamide, methanol, water as well as in waterorganic solvent mixtures (10 and 50 vol% of water). Total concentration of monomers was
10 or 30%, reaction temperature was set to 35 and 60°C and duration for 7 days. Reaction
products were purified by dialysis through 3,5 kDa membranes.
Scheme 1. Synthesis of HPAA
It was found that yields of purified HPAA were solvent-dependent and they were in
the range of 5-50%. Highest yields were obtained when pure organic solvents were used
and lowest, when 50 vol% of particular solvent was replaced by water. Hence it may be
concluded that water itself may add to MBAA, thus act as a chain-terminating agent and
prevent formation of high molecular weight HPAA.
FT-IR and 1H NMR spectra of HPAA synthesized are consistent with the structure
drawn in the Scheme 1. However, 13C NMR spectra revealed that some polymers are partly
branched through imine groups of DAP unit.
The number average molecular weights of HPAA measured by SEC are in the range of
3000-8000 Da and they are in fair correlation with intrinsic viscosities and hydrodynamic
radii of polymers. Generally, higher molecular weight products were obtained when lower
reaction temperature and higher concentration of monomers were used, but such tendency
was clear only for some reaction solvents. The polydispersity index of polymers is ranging
from 2 to 6. Both these trends are typical for polycondensation or polyaddition processes.
The acid-base titration showed that imine groups of HPAA, like imine groups of linear
or branched polyethyleneimines, only partly protonated at physiological pH. Therefore
HPAA may be very promising as gene delivery vehicle.
References
1. G. Coué, J.F.J. Engbersen. J. Control. Release, 152, 90-98 (2011).
2. P. Ferruti, M.A. Marchisio, R. Duncan. Macromol. Rapid Comm., 23, 332-355 (2002).
68
GLASS-FORMING PHENANTHROIMIDAZOLE-BASED
DERIVATIVES AS POTENTIAL CHARGE TRANSPORTING
MATERIALS FOR ORGANIC ELECTRONICS
R. Butkutė, R. Lygaitis, J.V. Gražulevičius
Faculty of Chemical Technology, Kaunas University of Technology, Kaunas, LT 50254, Lithuania
Phenanthroimidazole derivatives are recognized as efficient emissive or charge
transporting materials for various organic electronics applications [1,2]. Here we report on
the synthesis and properties of new 2,7- and 3,6-substituted phenanthroimidazole-based
derivatives (9-16) (Scheme 1). The phenanthroimidazole core was modified attaching
carbazole and diphenylamine moieties using Cu and Pd-catalysed chemistry.
N
R=
N
*
*
*
R
R
N
N
N
N
X
X
X
X
10, 12, 14, 16
9, 11, 13, 15
X=
N
N
*
*
N
*
N
*
Scheme 1. 2,7- and 3,6-substituted phenanthroimidazole-based derivatives
All the synthesized derivatives were characterized by 1H BMR, IR spectroscopy and
mass spectrometry. The thermal, optical, photophysical, electrochemical and
photoelectrical properties were investigated. The glass transition temperature of
synthesized compounds are observed in the region from 81 to 239 oC. The hole mobility
of 0.001 cm2/Vs was determined by time-of-light technique in the layer of one of the
compounds. The ionisation potential was determined by means of cyclic voltammetry and
it ranges from 4.96 eV to 5.52 eV. The investigation showed that the synthesised
compounds are potential semiconducting materials which could be used in various fields of
organic electronics.
References
1. Shaoqing Zhuang, Ronggang Shangguan et. al., Organic Electronics (2012)
2. Ying Zhang, Shiu-Lun Lai et. al., Chem. Mater. (2012)
69
ARYLFLUORENYL SUBSTITUTED METOXYTRIPHENYLAMINE
MOLECULAR GLASSES FOR OPTOELECTRONIC APPLICATIONS
M. Čekavičiūtė, J. Simokaitienė, J. V. Gražulevičius, D. Volyniuk
[email protected]
Derivatives of triphenylamine represent one of the largest and one of the most widely
studied class of organic electroactive materials [1]. In most of the applications the ability to
transport positive charges of the derivatives of triphenylamine is exploited. They are
widely used in electrophotographic photoreceptors, organic light emitting diodes, solar
cells. In this presentation we reported on the synthesis and investigation of the properties
of new glass-forming methoxy-substituted triphenylamine derivatives.
O
O
O
O
N
O
O
O
N
O
O
Compounds were synthesized by one step procedure by acid promoted Friedel-Craftstype substitution reaction [2]. They were identified by IR-, 1H NMR-, 13C NMR
spectroscopies and mass spectrometry. The synthesized compounds were found to
constitute glass-forming materials with glass transition temperatures in the range of 148165 ºC as characterized by differential scanning calorimetry. Absorption spectra of the
dilute solutions of the compounds in tetrahydrofuran are similar. The absorption maxima
are observed at 269 nm and 310 nm. The wavelengths of fluorescence intensity maxima
depend on the position of methoxy groups in the triphenylamine moiety. The synthesized
compounds are electrochemically stable. Hole drift mobilities of the glassy layers of the
synthesized compounds were measured by CELIV method and were found to exceed 10-4
cm2/Vs at an electric field of 9∙104 V/cm.
Acknowledgement. This research is funded by the European Social Fund under the Global Grant measure.
References:
1. A. Iwan, D. Sek. Prog.Polym. Sci., 36, 1277–1325 (2011).
2. P.-I. Shih, C.-H. Chien, F.-I. Wu, C.-F.Shu. Adv. Funct. Mater., 17, 3514–3520 (2007).
70
THERMAL BEHAVIOR OF ACRYLONITRILE COPOLYMERS
WITH LOW CONTENT OF VINYL MONOMER PREPARED VIA A
RAFT TECHNIQUE
E. Chernikova1, A. Baskakov2, S. Kishilov1, A. Plutalova1, Yu. Kostina2
1
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia,
[email protected]
2
Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
In this research we present the results of the synthesis of compositionally
homogeneous binary copolymers of acrylonitrile (AN) containing low amount (2 – 10
mol.%) of vinyl monomers, such as methyl acrylate, tert-butyl acrylate, n-butyl acrylate,
styrene, and acrylamide by means of reversible addition – fragmentation chain transfer
(RAFT) polymerization. The copolymerization was carried out in DMSO solution
(DMSO :AN = 6 : 4 v/v) at 80°C using AIBN as an initiator and various trithiocarbonates
as RAFT agents. In all the investigated systems the linear increase of Mn with progress in
monomer conversion as well as the formation of narrow dispersed copolymers has been
observed.
The thermal behavior of the synthesized copolymers has been studied by means of
DSC and IR-spectroscopy combined with IR-pyrolysis.
It was shown that the addition of low amount of vinyl monomer allows to keep the
ability of PAN to form polyconjugated system (PSS):
CN
N
N
CN
CN
CN
N
N
N
CN
CN
N
The formation of PSS both in inert and air atmosphere in AN copolymers starts at
higher temperatures and is characterized by higher exothermic effect corresponding to
cyclization reaction comparing to homopolymer.
The chemical nature of the monomer, its content in the macromolecule and the
monomer chain distribution influence strongly on the PSS structure and the observed
thermal effects.
The PSS formation can take place only if the macromolecule contains enough long
sequences of acrylonitrile units. On the contrary, the alternation of AN units with another
monomer impede the PSS formation.
Acknowledgements. The work is financially supported by Russian Foundation for basic research (project
11-03-00640).
71
SYNTHESIS OF BRUSH COPOLYMERS CONTAINING ANIONIC
SIDE CHAINS VIA ISARA ATRP
G. Ciuta, M. Savickaite, S. Ketleriute, C.Visnevskij, R. Makuska
Polymer brushes are attractive to scientific community due to their specific properties.
Polymer brushes have been used for the synthesis of polymer-coated metal-based
nanoparticles, as templates for biomimetic silicification, or as biolubricants [1]. Atom
transfer radical polymerization (ATRP) is an extremely versatile and robust technique to
build brush copolymer structures [2]. However, polymerization of acidic monomers under
conditions of ATRP is complicated, because of complexation of the acidic monomer with
Cu ions and deactivation of the catalyst.
The backbone of the brush copolymers consisted of polyhydroxyethylmethacrylate
(pHEMA) which was synthesized by ISARA ATRP. ISARA ATRP is developed in our
laboratory for polymerization of hydrophilic monomers in aqueous solutions and is based
on simultaneous use of CuCl2, ligand Me6TREN, reducing metals copper or iron and
supplemental redox intermediates (SRI) like iron (III) chloride, ascorbic acid (AscA) or
hydroquinone (HQ) in their oxidized form [3].Several synthesized pHEMA (Mn 17 000,
53 000 and 80 000, Mw/Mn1.21, 1.28 and 1.66, respectively) were modified by αbromoisobutyryl bromide (degree of modification 95-98%, 1H-NMR) yielding
macroinitiator pBIEM. Anionic brush copolymers were synthesized by graftcopolymerization of methacrylic acid (MAA) from the macroinitiator pBIEM. To find
optimal conditions for the attachment of anionic side chains by ISARA ATRP, different
SRI and two reducing agents, zerovalent copper or iron,were used. Before polymerization,
MAA was neutralized by several amines making it soluble in organic solvents solubilizing
macroinitiator pBIEM. Molecular weight, size and polydispersity of the copolymers were
determined by SEC with triple detection.
A series of anionic brush copolymers pBIEM-graft-pMAA with molecular weight
from 60 000 to 330 000, polydispersity index Mw/Mn from 1.3 to 1.6, and length of the side
chains from 5 to 30 monomeric units of MAA was synthesized. Though triethyl amine was
the best neutralizing agent for MAA enabling to control polymerization of this monomer
by ISARA ATRP and get Mw/Mnof 1.3–1.4, diethyl amine and ethyl amine were also
acceptable giving similar but slightly higher polydispersity. Brush copolymers with the
lowest polydispersity were synthesized using Cu as a reducing agent and FeCl3 as SRI. The
use of organic SRI AscA or HQ facilitated to synthesize anionic brush copolymers with
very high molecular weight (over one million) but they were rather polydisperse (Mw/Mn
about 2.5).Thus ISARA ATRP of MAA neutralized by triethyl amine is a proper choice for
the attachment of negatively charged side chains to a selected backbone giving anionic
brush copolymers.
Acknowledgements.Financial support from the Research Council of Lithuania under the project MIP51/2012 is gratefully acknowledged.
References
1. S. Tugulu, R. Barbey, M. Harms, et al.,Macromolecules,40, 168–177 (2007).
2. R. Barbey, L. Lavanant, D. Paripovic,et al., Chem. Rev., 109, 5437–5527 (2009).
3. C. Visnevskij, R. Makuska, Macromolecules, Doi 10.1021/ma400536j (2013).
72
SYNTHESIS AND PROPERTIES OF DIFFERENTLY SUBSTITUTED
DERIVATIVES OF CYANURIC ACID
A. Dainyte1, D. Gudeika1, J.V.Grazulevicius1
1
Kaunas University of Technology Department of Organic Technology, Radvilenu 19, LT-50254 Kaunas,
Tri-substituted 1,3,5-triazines are one of the oldest classes of organic compounds.
These compounds have been used as subunits in the formation of supramolecular structures
since they possess interesting optical and electronic properties and are able to form
multiple hydrogen bonds [1]. Each chloride atom of cyanuric chloride can be substituted
by various nucleophiles.
The molecules chosen for this study consist of a central acceptor triazine ring with
different groups symmetrically substituted in 1,3,5 positions (Scheme 1); The compunds
obtained are cyanuric acid derivatives with phenyl as well as p-substituted (methyl, nitro,
ciano, methoxy and tert-amyl) phenyl groups. The structures of the synthesized
compounds were confirmed by 1H NMR, IR and mass spectrometries.The optical and
electrochemical properties of the synthesized compounds were studied. Dilute solutions of
1,3,5-triazines derivatives in acetonitrile absorb electromagnetic radiation in the region of
200-375 nm with the band gaps of 3.96-4.81 eV. Cyclic voltammetry studies revealed
solid state ionization potentials (Ipechem) ranging from 7.20 eV to 8.35 eV.
2
NO2
CH 3
O
O2N
O
N
4
N
O
N
O
N
O
CH 3
O
N
O
N
O
OH
OH
O
1
NO2
NO 2
CH 3
O
H 3C
O
N
OH
OH
Cl
N
Cl
N
N
O
N
N
O
Cl
NC
OH
CN
O
N
N
3
O
CN
N
O
O
N
O
N
N
NC
O
5
Scheme 1. Compounds1-5.
References
1. H. Zhong, E. Xu, D. Zeng, J. Du, J. Sun, S. Ren, B. Jiang, Q. Fang, Org. Lett., 10, 709-712 (2008).
73
INFORMATION MEDIA BASED ON ELECTRONS DONOR
OLIGOMERS
N.A. Davidenko, Yu.P. Getmanchuk, E.V. Mokrinskaya, L.R. Kunitskaya,
I.I. Davidenko, V.A.Pavlov, S.L. StudzinskyS.L., N.G.Chuprina
Department of Chemistry, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine, [email protected]
Development of new materials possessing photoconductivity within the visible and
near IR ranges of spectrum seems to be very important problem for their practical
application in photoelectric converters of solar energy, in light emitters, in modulators and
switches of light beams, in devices for optical information recording and processing. For
optical holographic recording by photothermoplastic technique reversible holographic
media based on oligomers with hole type of conductivity are used. New carbazole
containing radial tetra substituted silans and germans are described in the present work.
Si ( O CH2 CH O
CH2
N
n
C2H5 )
CH3
4
Ge ( O CH2 CH O
CH2
Si
n
C6H5
OH )
4
N
One can conclude from the results of carried out investigations that information
characteristics of the recording media depend not only on the ratio between ionization
potential of donor and electron affinity of acceptor but on the shape of molecule for which
donor-acceptor interaction of oligomer-sensitizer becomes easier and rheological
properties of the film become better. Besides, in the media based on radial oligomers
“memory” effect was observed under preliminary illumination with light. This effect can
be employed for holographic recording with several expositions. “Memory” effect can be
attributed to presence of energetic traps which ones are formed by end carbazole groups.
Results of the investigations are practically used for development of new information
media. In particular, the new media were tested in small-sized holographic interferometer
designed for detection and determination of residual stresses in units of metallic
construction. The same media were tested in small-sized holographic device [1].
References
1. http://photonics.kiev.ua
74
EFFECT OF LIPID MOLECULE GEOMETRY ON STRUCTURE
AND PROPERTIES OF LIPOSOME–POLYCATION COMPLEXES
A.A.Efimova, D.A. Pyatnikova, A.A.Yaroslavov
Polymer Department, M.V.Lomonosov Moscow State University, Moscow, Russia,
[email protected]
Spherical bilayer lipid vesicles (liposomes) are extensively used as containers for the
targeted delivery of biologically active compounds. However, it should be noted that over
time the lipids of which the containers are constructed may undergo a number of changes.
For example, during storage the processes of lipid oxidation can take place. It is well
known that in this case the geometry of lipid is changed. Preferably the oxidation of lipids
produces surfactants containing one alkyl chain. Such surfactants are in the form of turned
cone and differ from the majority of lipids having a cylindrical shape. This can lead to
defect formation in the liposomal container and premature leakage of its content. The
contact of polycation with the container may become irreversible. Changes in structure
and properties of the containers from the polycation-liposome complexes remain
practically unknown at the present time. Therefore the aim of this study was to investigate
the stability of polycation complexes with oxidized liposomes using model system:
liposome membrane with built-in surfactant containing one alkyl chain.
Interaction of cationic polyelectrolyte, poly(N-ethyl-4-vinylpyridinium bromide)
(PEVP) with small unilamellar anionic liposomes has been analyzed. We used mixed
liposomes composed of neutral and negatively charged lipids of different geometry. We
used phosphatidylcholine (PC) and n-hexadecylphosphocholine (HDP) as neutral
component. The charged component was represented by: cardiolipin (CL), palmitic and
heptanoic acids (PA, HA). HDP, PA and HA were used as sructural models of lipid
oxidation products. PC is in cylindriform. The form of HDP, PA and HA molecule is
turned cone. The influence of form of anionic lipids on the stability of polycationliposome complexes in water-salt media was investigated.
The stability of the resulting complexes in water salt media and the integrity of the
liposomal membrane in contact with the adsorbed polycation were found to be strongly
dependent on the lipid form. The incorporation of neutral and negatively charged
surfactants containing one alkyl chain into the liposomal membrane leads to the formation
of defects and irreversible interaction with the polycation.
Acknowledgements.This work was supported by Russian Foundation of Basic Researches (project № 11-0300936)
75
SYNTHESIS AND PROPERTIES OF TRIS(CYCLOPENTADIENYL)ZIRCONIUMTETRAKIS(PENTAFLUOROPHENYL)BORATE
D.P. Fedorov1, 2, V.Ya. Churkina1, E.I. Knerelman1, V.D. Makhaev1,
Yu.I. Zlobinskiy1, I.V. Sedov1, 2
1
Institute of Problems of Chemical Physics of the Russian Academy of Sciences, Russia
Departmentof Fundamental Physics and Chemical Engineering, Moscow State University,
Russia,[email protected]
2
1. Metallocene-based systems consisting of IV group transition metal (Ti, Zr, Hf)
derivatives and an organoaluminum compound are of the most active catalytic systems for
the production of various grades of polyethylene. A wide range of PE grades with
possibility of flexible control on their properties can be obtained with these catalysts. A
serious problem in their application is a large excess of an activator (in most cases
methylaluminoxane) required. Perfluoroarylborates are used as alternative activators for
these systems.We have proposed a novel ethylene polymerization catalyst
[Cp3Zr][B(C6F5)4] (1) and developed a three stage route to its synthesis. The synthesis
scheme includes the steps of CpK and Cp4Zr separation and interaction of Cp4Zr with
[Ph3C][B(C6F5)4]:
Compound (1) has been characterized by IR, NMR, and UV-visible spectroscopy.
These data allow for suggestions onthe composition and structure of compound (1).1HNMR spectrum of compound (1) is a singlet with δ = 5,87 ppm due to the equivalence of
the three cyclopentadienyl rings in the NMR time scale. In the time scale of the IR
spectroscopy technique the cyclopentadienyl rings are also equivalent in contrast to Cp4Zr
having three π-bound and one σ-bound cyclopentadienyl ring (ν = 745 cm-1) [1].
Compound (1) is active in the ethylene polymerization in the absence of
aluminoxanes. It can be activated by triisobutilaluminum (TIBA). Linear polyethylene has
been obtained in mild conditions (at 60°C and a 6 bar ethylene pressure). The productivity
of the system [Cp3Zr][B (C6F5)4] – TIBA makes 644 g/(g Zr × h) ([Cp3Zr][B(C6F5)4] = 4.7
× 10-4 mol/L, Al/Zr molar ratio = 107). The system based on Cp4Zr is more active when it
is activated by methylaluminoxane in such conditions. Drastic reduction in the activity of
complex (1) can be attributed to its rapid deactivation.
References
1. B. V. Lokshin, E. M. Brainina. J. Struct. Chem., 12 (6), 923-927 (1971).
76
SYNTHESIS OF N-VINYL SUCCINIMIDE POLYMERS FOR
BIOMEDICAL APPLICATIONS VIA RAFT POLYMERIZATIONIN
BULK
A. Gostev1, E. Sivtsov1, E. Parilova2, E. Chernikova3
1
Plastics Technology Department, Saint-Petersburg State Institute of Technology, Russia, [email protected]
Institute of Macromolecular Compounds of the RAS, Saint-Petersburg, Russia
3
2
(Co)polymers based on N-vinylsuccinimide (VSI) cause intense interest due to
possibility of application as hydrophilic non-toxic materials in medicine. Such copolymers
can be easily modified by alkaline hydrolysis resulting in conversion of VSI units to the Nvinylsuccinimidic acid (VSA) units with carboxylic groups attached to the main chain via
–NH–C(O)–CH2–CH2– spacer permit to bind low molecular compounds including
medicinal products to the polymers, leading to various advantages of such polymeric drug
conjugates, for instance, their prolonged action in vivo.
The main aim of this study was to obtain soluble VSI polymers and copolymers with
high composition homogeneity by polymerization in bulk. This task cannot be achieved
using conventional free-radical polymerization because of (a) the chain transfer reaction to
VSI cycle methylen protons leading to cross-linked product and (b) a great difference of
VSI and other vinyl monomers reactivity ratios. To overcome these problems we have
applied RAFT technique to the homopolymerization and copolymerization of VSI using
dibenzyl trithiocarbonate (BTC) as a RAFT agent and azobisisobutyronitrile (AIBN) as an
initiator.
The (co)polymerization of VSI in the presence of BTC was carried out under the
following conditions: [BTC]=10-2 ÷10-1 mole/l, [AIBN]=10-3 mole/l. The polymers remain
soluble, not cross-linked, with high composition homogeneity (in the case of
copolymerization) up to the limited monomer conversions. Monitoring of monomer
concentrations, copolymer composition, calculation of polymers molecular mass and
conversions were carried out by NMR 1H spectroscopy. It was shown that with increase of
the polymerization time the molecular masses of the polymers formed successively grow.
Molecular masses calculated from NMR data (using the fact that both end groups are
known) and found by GPC analysis correspond with the theoretical values well enough. It
is important to mark that polydispersity index is extremely low (1.13–1.15). This result
allows concluding that polymerization proceeds in a controlled mode.
In a supplementary experiment a copolymer (1.3×10-4 mole/l) was heated in inert
solvent (benzene) with excess of AIBN (3×10-1 mole/l) at 80°C during 24 h to determine
the location of CS3-group in macromolecules. If trithiocarbonate group (SC(=S)S)
is located in the middle of the polymeric chain, but not on its tail, after heating with the
initiator in the absence of monomer the molecular mass of the polymer should decrease in
half. If it is located on the tail, molecular mass should remain practically the same.
Using RAFT technique compositionally homogeneous copolymers of VSI were
synthesized in bulk: water-unsoluble copolymers of VSI and butyl acrylate forming
polymeric films for medicinal covering on skin wounds; water-soluble copolymers of VSA
and vinyl alcohol (obtained by alkaline hydrolysis of VSI and vinyl acetate copolymers)
and their remantadine complexes with antiviral activity "Polyrem". The advantage of
RAFT polymerization over conventional radical polymerization is the precise control of
molecular mass characteristics of (co)polymers obtained and the possibility of solvent-free
synthesis of non cross-linked polymers in bulk.
77
NEW ELECTRO-ACTIVE MATERIALS FOR ORGANIC LIGHT
EMITTING DIODES
D. Tavgeniene1, G. Krucaite1, R. Griniene1, D. Rasymaite1,
S. Grigalevicius1*, J.H. Jou2
1
Department of Organic Technology, KaunasUniversity of Technology, Kaunas, Lithuania,
[email protected]
2
Department of Materials Science and Engineering, National Tsing-Hua University, Taiwan
Twin derivatives with two 9-alkylcarbazol-3-yl fragments will be presented. The
electro-active materials were synthesized by the multi-step synthetic rout. The materials
were characterized by differential scanning calorimetry and electron photoemission
technique. Some of the derivatives were tested as solution processed hole transporting
layers in OLEDs with Alq3 as the emitter. The devices exhibited promising overall
performance with a maximal photometric efficiency of about 2.9 cd/A and maximum
brightness of 6000 cd/m2.
Polyether containing electronically isolated carbazolyl fragments and its model
compound will be presented. The electro-active materials were synthesized and
characterized. Weight- average molecular weight of the polymer was about 31500 with
polydispersity index of 2.4. Both the compounds represent amorphous materials of high
thermal stability with glass transition temperatures of 137 °C for polymer and of 41 °C for
model compound. The derivatives were tested as host materials in green as well as blue
phosphorescent OLEDs. The green device with polymeric host exhibited turn-on voltage of
3.3 V, a maximal current efficiency of 11.5 cd/A and maximum brightness of 1312 cd/m 2.
An efficient blue OLED using the model compound as host demonstrated a turn-on voltage
of ca. 4.3 V, a maximum brightness of 6225 cd/m2, and maximum current efficiency of
23.3 cd/A at 100 cd/m2.
Acknowledgements.Some of the OLED materials were developed in the frame of project MIP 024/13
financed by the Research Council of Lithuania.
78
ELECTRO-ACTIVE POLYMERS CONTAINING
FRAGMENTS
E. Zaleckas1, R. Zostautiene1, L. Liu2, B. Zhang2, Z. Xie2, S. Grigalevicius1
1
Department of Organic Technology, Kaunas University of Technology, Radvilenu plentas 19, LT50254,
Kaunas, Lithuania, [email protected]
2
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, China
Aromatic amine-containing polymers and low molecular weight derivatives are among
the most studied materials for optoelectronic and electronic applications due to their high
hole mobility and photoconductive properties. Some of the materials have been
commercialized in a number of devices and processes (photocopying machines, laser
printers, etc.) [1]. N-Phenyl-N-naphtylamine moiety is also interesting for the design and
synthesis of organic semiconductors. It is aromatic unit providing a high thermal,
morphological, chemical and environmental stability. A wide variety of functional groups
can be attached to its nitrogen atom [2]. Usually N-phenyl-N-naphtylamine -based
materials exhibit lower ionization potentials and demonstrate better hole injection and
transport properties as compared to other aromatic amines [3].
We will report the synthesis and properties of new polymers (1 and 2) containing
pendent and electronically isolated N-phenyl-N-naphtylamine fragments. The application
of the materials for hole transporting layers in OLEDs was demonstrated.
2
1
The polymers represent amorphous materials with glass transition temperatures of 71–78
°C and thermal decomposition starting at temperatures > 320 °C. The synthesized materials
have been tested as hole transporting layers in simple OLED devices with Alq3 as the
emitter/electron transporting layer. The green devices containing hole transporting film of
polymer 1 exhibited the best overall performance with a driving voltage of 4.5 V,
maximum photometric efficiency of 3.6 cd/A and maximum brightness of 2850 cd/m2.
Acknowledgements. Postdoctoral fellowship (Ernestas Zaleckas) is being funded by European Union
Structural Funds project ”Postdoctoral Fellowship Implementation in Lithuania“.
References
1. P. Strohriegl, J. V. Grazulevicius, J. Pielichowski, K. Pielichowski, Prog. Polym. Sci. 28, 1297 (2003).
2. A Balionyte, E. Lideikis, S. Grigalevicius, J. Ostrauskaite, E. Burbulis, V. Jankauskas, E. Montrimas, J.V.
Grazulevicius, J. Photochem. Photobiol. A: Chem., 162, 187 (2004).
3. V. Vaitkeviciene, S. Grigalevicius, J.V. Grazulevicius, V. Jankauskas, V.G. Syromyatnikov, Eur. Polym.
J., 42, 2254 (2006).
79
VISUALIZATION OF STRUCTURAL REARRANGEMENTS
DURING ANNEALING OF SOLVENT-CRAZED ISOTACTIC
POLYPROPYLENE
T. E. Grokhovskaya, A.L. Volynskii, A.I. Kulebyakina, A.A. Efimova, A.V.
Bol’shakova, and N.F. Bakeev
Polymer Department, M.V.Lomonosov Moscow State University, Moscow, Russia, [email protected]
In our recent works, we have used new microscopic procedure to study structural
rearrangements in the course of deformation and annealing of amorphous glassy polymers
after solvent crazing or, in other words, after their tensile drawing in the presence of
adsorptionally active liquids environments. Deformation and shrinkage of the oriented
amorphous polymers were accompanied by features unknown earlier. Therefore, one can
reasonably expect that the proposed direct microscopic procedure can also be efficiently
used for the visualization and characterization of structural rearrangements during the
deformation and shrinkage of semi-crystalline polymers. The objective of this work is the
use of the proposed microscopic procedure for the visualization of structural
rearrangements in solvent-crazed isotactic PP upon its annealing.
Structural rearrangements taking place upon the annealing of solvent crazed isotactic
polypropylene (PP) are studied by means of the direct microscopic method. Independently
of the type of its crystalline structure, solvent- crazed PP undergoes shrinkage in a wide
temperature interval, starting even from room temperature and up to its melting
temperature. This shrinkage is a result of the structural processes in crazes and proceeds
via shutting down of the walls of individual crazes. This low temperature shrinkage of
solvent crazed PP is assumed to have an entropy nature. This process involves the
contraction of extended polymer chains and their transition into thermodynamically
favorable conformations. This contraction is allowed because, upon annealing, the entropy
contracting force increases. As a result, the crystalline framework of oriented PP melts
down (amorphization), extended chains appear contracted, stored stresses relax, and
subsequent recrystallization in the unstressed state takes place.
80
SYNTHESIS AND PROPERTIES OF GLASS-FORMING
NAPHTHALIMIDE COMPOUNDS CONTAINING CARBAZOLE
MOIETIES
D. Gudeika1, J.V. Grazulevicius1, A. Miasojedovas2, S. Jursenas2
1
Department of OrganicTechnology, Kaunas University of Technology,Radvilenu pl. 19, LT-50254, Kaunas,
2
Institute of Applied Research, Vilnius University, Sauletekio al. 9, LT-10222, Vilnius, Lithuania
Carbazole is perhaps ideal electron donor with high charge carrier mobility, high
thermal and photochemical stabilities. These properties are commonly exploited when
carbazole derivatrives are used as hole-transporting materials in optoelectronic devices
[1].The combination of 1,8-naphthlimide with carbazole is expected to give materials
withexcellent photophysical properties and capabilityof forming amorphous layers and
transporting charges.
In this study, we synthesized a new series of donor-acceptor derivatives containing
accepting N-alkyl-1,8-naphthalimide species and electron-donating carbazole moieties
with the different linking topologies. Compounds 1-4 were synthesised by Suzuki coupling
reaction [2]. Compounds 5 and 6 were synthesized by Ullmann type condensation of imide
with 9H-carbazole or 3,6-di(tert-butyl)carbazole, respectivelyin o-dichlorobenzene in the
presence of copper powder as catalyst and potassium carbonate as a base. The structures of
1-6 are shownbellow.
O N O
N
O N O
O
O
N
O
1
N
O
N
N
2
3
N
O
O
N
N
O
O N O
O N O
O
4
N
N
5
6
The structures of the synthesized compounds were proved by 1H and 13C NMR, IR and
mass spectrometries. Thermal, optical, electrochemical and photophysical properties of the
synthesized compounds were investigated. The compounds were found to be capable of
glass formation.
References
1. T. K. R. Justin, J. T. Lin, Y. T. Tao, C. W. Ko. J. Am. Chem. Soc., 123, 9401-11 (2001).
2. S. Y. Tang, Q. X. Guo, Y. Fu. Chem. Euro. J., 17, 13866-76 (2011).
81
THE EFFECT OF ADDITION OF IONIC LIQUID ON THE
ELECTROSPINNING CONDITIONS OF SAN SOLUTIONS AND THE
MORPHOLOGY OF OBTAINED NANOFIBERS
V. Gudkova1, M. Viirsalu1, M.Rikko2, E.Tarassova2, T.Märtson2, A. Krumme2
1
Department of Polymer Materials, Tallinn University of Technology, Tallinn, Estonia,
[email protected]
2
Electrospinning is a fast and simple process to produce nano-scaled or micro-scaled
polymer filaments, which is driven by an external electric field on the surface of applied
polymeric fluids in a melt state or a solution state. For processing of any polymer therefore
requires either chemical derivatization or physical dissolution in a suitable solvent. [1, 2]
The solvent have to provide the stability of electrospinning process and therefore have to
be chargeable. The volatilization of convenient organic solvents may contaminate the
environment and at the same time may be difficult to recycle. [3] For years ionic liquids
have been considered the potential green solvent. Generally, ionic liquids consist entirely
of ions, and exist as liquids at relatively low temperatures (less than 100 °C). [4] These are
the main reasons to find out the appropriate way for utilization of ionic liquids in
electrospinning process.
The aim of this research was to investigate how addition of ionic liquid 1-butyl-3methylinmidazolium chloride [Bmim]Cl into styrene – acrylonitrile copolymer SAN
solution will influence electrospinning conditions, stability of process and morphology of
obtained nanofibers.
First the solutions of SAN in DCE with different concentrations 10-20 % were spinned
at different conditions 10-20 cm and 10-20 kV to obtain appropriate electrospinning
conditions and solution concentration for electrospinning of continuous fibers with uniform
diameter. After that different amount of [Bmim]Cl ionic liquid was added into SAN
polymer solution of certain concentration. Mixed solutions were electrospun at the same
conditions and results were compared to previously electrospun pure SAN in DCE
solutions. All results were investigated by optical and SEM microscopy.
References
1. D.H. Reneker, A.L. Yarin. E. Zussman, H. Xu. Adv. Appl. Mechan., 41, 43-195; 345-346 (2007);
[Online] ScienceDirect (10.04.2013).
2. S. Ramakrishna, K. Fujihara, W-E. Teo, Z. Ma. An Introduction to Electrospinning and Nanofibers.
Singapore: World Scientific Publishing Co. Pte. Ltd, 358 (2005) (08.12.2012).
3. G. Wypych. Handbook of Solvents: Ionic Liquids. ChemTec Publishing, 2001. [Online] Knovel.
(10.04.2013)
4. Kokorin A. Ionic Liquids: Applications and Perspectives: Advanced Applications of Ionic Liquids in
Polymer Science. InTech, 674 (2011). [WWW] http://www.intechopen.com/books/ionic-liquidsapplications-and-perspectives (10.04.2013)
82
SYNTHESIS AND PROPERTIES OF NEW
PHENANTHROIMIDAZOLE-BASED MONOMER AND POLYMER
A. Ivanauskaitė, R. Lygaitis and J. V. Gražulevičius
Efficient solid-state emissions of organic materials are essential for optoelectronic
devices, such as organic light-emitting diodes, organic field-effect light emitting
transistors, organic solid-state lasers or organic luminescence sensors. Nowadays the
molecular design and development of new chromophores that emit visible light in the solid
state with high efficiency are strongly desired for the realization, modification, and
advanced applications of such devices with a superior performance. Phenanthroimidazole
derivatives are recognized as efficient emissive or charge transporting materials for organic
light emitting diodes [1] as well as for various sensory applications [2]. However there are
no any data on their solid state emission properties. Here we report on the synthesis of new
phenanthroimidazole-based monomer and polymer (Scheme 1).
O
OH
F
F
NH 2
O
+
F
F F
+
F
F
F
CH3COOH, CH3COONH4, N2
O
120oC, 6h.
OH
CHO
F
F
N
N
F
F
Cl
F
F
N
dry toluene, KOH, dry Na2SO4
120oC, 6h.
N
F
F
F
F
1
Scheme 1. Synthesis of phenanthroimidazole-based monomer
The structures of the synthesized compounds were confirmed by 1H NMR, 13C NMR,
IR spectroscopy and mass spectrometry. Thermal properties were investigated by the
differential scanning calorimetry and thermogravimetry. Optical and photophysical
properties were studied by UV and fluorescence spectroscopies. The polymer was obtained
by conventional radical polymerization using AIBN as initiator as well as by selfpolymerization at elevated temperatures. The kinetics of polymerization of the synthesized
monomer was investigated by real time FT-IR technique. The average molecular weights
were estimated by GPC technique.
References:
1. J. Mater. Chem., 21, 5451 (2011).
2. J. Mater. Chem., 21, 8206 (2011).
83
THE MODIFICATION THE POLYAMIDE FILMS BY LAYERS OF
METAL SELENIDE
R. Ivanauskas, I. Ancutienė, L. Samardokas, A. Ivanauskas
Department of Inorganic Chemistry, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
In modern technology composition materials which are made of a combination of
various components play an important role. Polymers with the layers of binary metal
chalcogenide on the surface are also described as composites. The study of these
composites has received considerable interest in recent years because of their novel
properties, which are combinations of those of the original inorganic and polymer
materials. Polymers with the layers of binary metal chalcogenide are characterized by
important physical properties such as semiconductor or metallic conductivity, ability of
absorbing radio waves, to act as polarizers of infrared radiation, as solar radiation controls
and sensitive elements of gas sensors.
Hydrophilic and semi-hydrophilic polymers are capable of absorbing ions of various
electrolytes from aqueous solutions [1]. Polyamide as semi-hydrophilic polymer is capable
to absorb ions of various electrolytes from aqueous solutions. This fact enabled us to
introduce the anions of selenotrithionate, SeS2O62 [2], containing divalent selenium atom
of low oxidation state into films of PA. Further treatment of seleniumized polyamide films
with metal salts water solution leads to formation of metal selenide layers on the surface
and matrix of polymer.
The goal of the present work was to study the formation of the layers of metal selenide
on polyamide PA 6 films when the solution of potassium selenotrithyonate as precursor of
seleniumization was used. To the experiment the pieces of the PA film 1570 mm in size
and the 70 m thickness were used. In the first stage, polymer was seleniumized in a 0.05
mol/dm3 concentration solution of potassium selenotrithyonate, (K2SeS2O6), in HCl (c=0.1
mol/dm3) at 60 oC up to 4 h. In the second stage, seleniumized films of PA 10 min were
treated with an aqueous solution of different metal salt at 80 oC. The layers of copper
selenide, thallium selenide and silver selenide by sorption-diffusion method on polyamide
films were formed. The phase composition of the obtained layers was investigated using a
DRON-6 diffractometer. Four phases of copper selenide, namely, tetragonal Cu3Se2 (721421) umangite, cubic berzellianite Cu2-xSe (6-680), tetragonal bellidoite Cu2Se (29-575)
and monoclinic copper selenide Cu2Se (27-1131), four tetragonal phasesof thallium
selenide Tl2Se2 (75–880), Tl2Se1.2 (75–1007), Tl5Se3 (41–1295),Tl2Se (47–1299) and the
phase of the orthorhombic naumannite – Ag2Se (24–1041) have been identified in the
layers by X-ray diffraction.
Acknowledgements. All the Authors are kindly thanked for the financial support of the Lithuanian State
Science and Studies Foundation.
References
1. G. E. Zaikov, A. L. Yordanskiy, V. S. Markin. Diffusion of Electrolytes Into the Polymers, Khimiya,
Moscow, (1984) (in Russian).
2. R. Ivanauskas, Mater. Sci. (Medžiagotyra), 15, 243–249 (2009).
84
SYNTHESIS OF MULTIBLOCK COPOLYMERS BY RAFT USING
LINEAR MULTIFUNCTIONAL CHAIN TRANSFER AGENTS
J. Jonikaitė-Švėgždienė, T. Krivorotova, T. Joskaudas, R. Makuška
Multiblock copolymers consist of alternating homogeneous segments of two different
monomers which are attached to each other. Due to the increased number of chain
junctions, multiblock copolymers exhibit unique elastic material properties and can selfassemble into ordered microstructures [1]. Multiblock copolymers can be synthesized via
RAFT process using linear multifunctional chain transfer agents (CTA) [1, 2].
For the synthesis of multiblock copolymers, three linear multifunctional RAFT CTA
with different structure synthesized in our laboratory were employed. Synthesis of multiCTA1 is based on the SN2 reaction between di(trithiocarbonate) anions and α,α´dibromidoesters; synthesis of multi-CTA2 is based on Huisgen 1,3-dipolar cycloaddition
between dialkyne-terminated trithiocarbonate and diazide; and synthesis of multi-CTA3 is
based on carbodiimide-mediated esterification between diacid-terminated trithiocarbonate
and 1,6-diaminohexane (Scheme 1). Molecular weight and polydispersity (Mw/Mn) of
multifunctionalCTAs were determined by SEC with triple detection. Mn of multi-CTA
varied from 700 to several thousands, and Mw/Mn from 1.1 to 1.7. Thus, multi-CTA with
optimal structure were suitable for the synthesis of tetrablock or hexablock copolymers.
Scheme 1. Synthesis of multiblock copolymers by RAFT using linear multifunctional chain transfer agents
RAFT polymerizations of styrene (St) and hydroxyethyl acrylate (HEA) were carried
out in bulk and in DMF at 70oC in the presence of multi-CTA1 and multi-CTA2. The best
control of styrene polymerization was achieved using multi-CTA1 with molecular weight
not exceeding 2300. Molecular weight of the products determinedby SEC with triple
detection was far from the calculated valuesbased on the monomer conversion and
concentrationof trithiogroups. Polydispersity indices Mw/Mn of the most samples were over
3.0, much higher compared to those of polymers synthesized using monofuncional
trithiocarbonates. Nevertheless, the proposed method opens new possibilities for the
synthesis of multiblock copolymers.
Acknowledgement. Financial support from the Research Council of Lithuania under the project MIP51/2012 is gratefully acknowledged.
References
1. B. Ebeling, P. Vana. Polymers, 3, 719-739 (2011).
2. Y. Liu, K. A. Cavicchi. Macromol. Chem. Phys., 210, 1647-1653 (2009).
85
UNIQUE PROPERTIES OF IONIC LIQUIDS AS A NOVEL
INITIATOR OF RADICAL POLYMERIZATION
S. Kanno
Polymer Chemistry Laboratory, Tohoku Seikatsu Bunka University, Sendai, Japan, [email protected]
Monomer C onversion (%)
Monomer Conversion (%)
CH 3
The application of ionic liquids is at an
+ Br
H 3C N
incredibly exciting stage in its spread of a wide
N
CH 3
range of ramifications. On the other hand, it has
been widely realized that the research and Scheme 1. 1-Ethyl-2, 3-dimethylimidazolium
bromide ([edmim]Br ).
development of new class of radical initiators
CH 3
40
contributes further development in the field of
+ Br
H3C N
N
radical polymerization. Until recently we reported
CH 3
the application of ionic liquids as an initiator of
30 1. 1-Ethyl-2, 3-dimethylimidazolium
radical polymerization.1)-4) The object of this Schme
bromide ([edmim]Br ).
investigation is to explore the possibility for some
20
kinds of ionic liquids as a novel initiator of radical
polymerization.
Vinyl monomer, solvent, and ionic liquid were
10
placed in a brown glass ampoule, which was
sealed with a rubber septum. The polymerization
was carried out under air or under argon. The
0
0
1
2
3
4
5
conversion was determined gravimetrically.Molar
Time (hr)
1. Effect of atmosphere on the Polymeriza of
mass (Mn) and polydispersity index (Mw/Mn) were Figure
MMA initiated with [edmim]Br.. MMA 4.7 mmol,
DMF 1.0 ml, [edmim]Br 0.024 mmol, 80
℃,
determined by GPC.
( ) under air, ( ) under argon.
For example, I have shown for the first time
40
that imidazolium ionic liquid such as 1-ethyl-2,3dimethylimidazolium bromide ([edmim]Br, see
30
Scheme 1) has the ability to initiate the radical
polymerization.As shown in Figure 1, the
20
polymerization of methyl methacrylate (MMA)
initiated with[edmim]Br in N,N-dimethylformamide
(DMF) proceeded smoothly under air at 80 ℃.
10
However, the corresponding polymerization under
argon scarcely proceeded. On the other hand, Figure
0
0
1
2
3
4
5
2 reports the effects ofhydroquinone (HQ) and 2,6Time (hr)
di-tert-butyl-p-cresol (BHT) as radical inhibitors, Figure 2. Effect of additives on the polymerization of
initiated with [edmim]Br.MMA 4.7 mmol,
and 1-dodecanethiol (1-DT) as a radical chain MMA
[edmim]Br 0.024 mmol, DMF 1.0 ml, under air, 80 ℃,
:(
) nil, (
) HQ 1.41 mml, (
) BHT
transfer agent on the polymerization of MMA Additives
1.41 mml, ( + ) 1-DT 1.41 mml.
initiated with [edmim]Br in DMF at 80 ℃ under air.
As seen in Figure 2, the polymerization was perfectly inhibited in the presence of these
additives. From the data obtained here, it is immediately clear that the [edmim]Br-initiated
polymerization of MMA proceeds via a radical pathway that is different from that of
conventional radical polymerization.
References
1. S. Kanno. Mol. Cryst. Liq. Cryst., 556 (1), 61-73 (2012).
2. S. Kanno. J. Mat. Sci. Eng. In press.
3. S. Kanno. Japanese Patent No 4719076.
4. S. Kanno. Japanese Patent No 4719080.
86
ENHANCING THE SURFACE CHARGE OF BCTMP OF ASPEN
WITH SUPERCRITICAL CO2 TREATMENT
K. Kärner1, R. Talviste1, K. Viipsi2, U. Kallavus1
1
2
Centre for Materials Research, Tallinn University of Technology, Tallinn, Estonia, [email protected]
Laboratory of Inorganic Materials, Tallinn University of Technology, Tallinn, Estonia
Surface charge of cellulosic fibres is important as it influences the interactions between
fibres and between other additives in pulping process as well as in other applications. The
most common surface charge measurement method is a polyelectrolyte titration technique
[1].
The method is regarded as an ion-exchange process such that a 1:1 charge stoichiometry
takes place, as one polyelectrolyte charge adsorbs for every available fibre surface charge.
The aim of this work was to analyse the effect on supercritical CO2 (sc CO2) and
mechanical treatment on surface charge of aspen bleached chemi-thermo mechanical pulp
(BCTMP). The new experimental method was practiced to measure surface charge: pDADMAC (poly-diallyldimethylammoniumchloride) solution was added to pulp and then
titrated with KOH solution. Dried, grinded BCTMP of aspen was dispersed in water,
treated with Bag Mixer with nylon separator, treated with sc CO2 with and without
ethanol-water co-solvent, influenced with 1% NaOH. The processes were carried out in
various times and order of succession.
Figure 1.SEM image of Sample with high surface charge (75.12 mmol/kg): treated in Bag Mixer and with
supercritical CO2.
This experimental technique suited for surface charge measurements and to evaluate the
effect of different thermo-mechanical treatments. The work also raised several
fundamental questions about the nature of surface charge, methods of development and
measurement.
References
1. E. Horvath, T. Lindström, Nordic Pulp and Paper Research J., 22, 87-92, (2007).
87
LIGHT EMMITING DENDRONIZED OLIGOPHENYLENES WITH
ACETYLENE GROUPS
I. A. Khotina1, M. A. Babushkina1, N. S.Kushakova1, A. I.Kovalev1
1
A.N.Nesmeyanov Institute of organoelement compounds RAS, Moscow, Russia [email protected]
The branched oligophenylenes with phenyleneethynylene fluorestent groups
synthesized via Sonogashira reaction. Trihalo-derivatives of 1,3,5-triphenylbenzene and
diethynyl compounds were taken as the starting compound as sketched in the scheme:
Hal
Hal
Ar
Ar
Ar
Hal
+ HC C
C CH
Pd(PPh3)4 ,
n
NEt3
CuI ,
THF
n = 1, 2
Hal = Br, I
Hal
Ar
Ar
Ar
Ar =
O-1 (n=1)
O-2 (n=2)
C C
C C Ar
n
Ar
Ar
Hal
Ar =
O
O-3 (n=2)
Fluorescence intensity, a.u.
The molecular weight was controlled by the comonomers molar ratio (4:3,
respectively). The end halogen groups were substituted with phenylethynyl groups. Figure
1 shows the absorption spectra of the oligophenylenes in methylene chloride solutions. The
absorption maxima of the oligomers peaked at 325-340 nm and photoluminescence
maxima are at 360 - 400 nm.
1,0
O-2
O-3
0,8
0,6
0,4
O-1
0,2
0,0
350
400
450
500
550
Wavelength [nm]
Fig. 1. Photoluminescence spectra of oligophenylenes O-1; O-2 and O-3
The photoluminescence quantum yields of the oligophenylenes were measured with
respect to quinine sulfate water solution and amounted 76-78%.
88
RAFT COPOLYMERIZATION OF PEO MACROMONOMERS IN
THE PRESENCE OF TRITHIOCOMPOUNDS
V. Klimkevičius, R. Makuška
There is an increasing demand to develop novel cationic comb and brush copolymers
for stabilization of aqueous and non-aqueous silica and titania colloidal suspensions. These
copolymers can also be used for modification of oppositely charged surfaces, building
multilayer structures, complexation, etc. The use of RAFT for the synthesis of cationic
comb copolymers is essential avoiding crosslinking and preparing comb copolymers with
relatively narrow MWD (Mw/Mn< 1.5) and, possibly, more even distribution of PEO side
chains along backbone.
Comb copolymers were synthesized by random copolymerization of [2(methacryloyloxy)ethyl] trimethyl ammonium chloride (METAC) as a cationic monomer
and poly(ethylene oxide) methyl ether methacrylate (PEOMEMA) as a macromonomer.
Six different trithio- RAFT chain transfer agents (CTA) (Figure 1) were synthesized and
used for the synthesis of the comb copolymers. Cationic comb copolymers with various
charge densities and densities of the side PEO chains as well as length of the side chains
were synthesized by altering the ratio of METAC and PEOMEMA and using the
macromonomer with longer or shorter PEO chain.
Fig. 1. RAFT CTA used to control random copolymerization of METAC and PEOMEMA
Trithiocompounds were found to be more efficient as RAFT CTA in copolymerization
of PEO macromonomers compared to dithiocompounds used earlier. Comb copolymers
with narrow MWD and low PDI 1.3-1.6 were synthesized using RAFT CTA 3-6. The
optimal control of random copolymerization of PEOMEMA and METAC up to high
conversion was realized at the molar ratio of a CTA and an initiator equal to 2/1 (mol/mol).
Control of copolymerization of the macromonomer with shorter PEO chain
(PEO25MEMA) was more efficient.
Acknowledgement. Financial support from the Research Council of Lithuania under the project MIP51/2012 is gratefully acknowledged.
89
THERMAL OXIDATION AND INVESTIGATION OF COMMERCIAL
POLYPROPYLENE
R. Alaburdaitė1, V. Krylova2
1
2
Department of General Chemistry, KaunasUniversity of Technology, Kaunas, Lithuania,
Department of Inorganic Chemistry, KaunasUniversity of Technology, Kaunas, Lithuania, [email protected]
Semiconductor/polymer composite materials are very important for practical
application due to their numerous advantages. In contrast to inorganic matrices, the use of
organic polymers as a matrix has the advantages of processability and easy handling of the
composite materials. The polymer matrices can be moulded at lower temperatures, are
generally flexible, and show higher toughness than inorganic matrices. Among these
polymers, isotactic polypropylene (iPP) plays an important role due to its low cost,
flexibility, easy processing, and resistance to many solvents and chemicals [1].
Furthermore, for chemical Ag2S [2] and CuxS [3] semiconductor deposition commercial
iPP films are suitable only under thermal oxidation.
The aim of this work was the investigation of commercial iPP and thermally oxidized
iPP films by the means of UV-Vis, ATR-FTIR and DSC measurements.
80
Mass, %
5
Exo
3
Endo
163,1
60
1
-1
164,4 oC
-3
-5
40
-7
commercial iPP
oxidized iPP
20
0
30
119
208
297
386
-9
Heat Flux, mW/mg
100
-11
-13
475
Temperature, oC
Fig. 1. TG and DSC curves for commercial and oxidized iPP
Polypropylene used in this study is commercial, supplied by KWH Plast (Finland).
When iPP was treated with oxidizing solutions [2, 3],a chemical reaction took place; there
was a change in the chemical structure of the polymer what often causes a change in a loss
in physical properties. In the UV-Vis absorption spectrum of commercial iPP the following
three absorption peaks are observed: a peak at 200 nm. The intensity of absorption
peak in the spectrum of the oxidized iPP decreases; it shifts to the side of lower
values, i.e. 195 nm, what indicates the existence of polar group in the polymer matrix.
ATR-FTIR spectrum of oxidized iPP has shown that characteristic peaks of
commercial iPP sharply diminish and a new signal appears at 1719 cm–1. This signal is
characteristic of carbonylic stretching vibrations.
The endotherms obtained at the heating rate 10o/min (Fig. 1) have shown that melting
temperature Tm of commercial iPP was 163.1 oC and melting enthalpy was 68.84 J/g. For
oxidized iPP Tm was 164.4 oC and melting enthalpy was 54.14 J/g. DSC results have
shown that presence of polar group in oxidized iPP influences melting temperature Tm and
melting enthalpy; they are unambiguously lower compared to the ones of commercial iPP.
Melting enthalpy change showed the change in surface energy and adhesion.
References
1. T. Zeiler, S. Kellermann, H. Münstedt, J. Adhesion Sci. and Technol. 14 (5), 619-634 (2000).
2. V. Krylova, R. Alaburdaitė, A. Guobienė, Chemija, 24, 30-38 (2013).
3. R. Alaburdaitė, S. Grevys, E. Paluckienė, Materials science, 17, 399-401 (2011).
90
ELECTROACTIVE THIOPHENE- AND PHENOTHIAZINE-BASED
HYDRAZONE MONOMERS
R. Laurinavičiūtė, J. Ostrauskaitė, J. V. Gražulevičius
Department of Organic Technology, KaunasUniversity of Technology, Kaunas, Lithuania,
[email protected]
Organic charge-transporting materials are used in optoelectronic devices such as
electrophotographic photoreceptors, light emitting diodes, solar cells [1, 2].Aromatic
hydrazones that can form morphologically stable polymeric layers are not widely described
in the literature yet [3, 4].
Thiophene- and phenothiazine-based hydrazone monomers (1-8) have been
synthesized and investigated in this study.
S
S
S
N
N N
N N
S
N
3
5
1
S
S
S
N N
N
N N
N
N
S
N
N
N N
N
6
2
4
N
N
S
7
N
N
N
N
S
N
N
8
Fig.1. Thiophene- and phenothiazine based hydrazones with reactive functional groups
The glass transition temperatures of the monomers are in the range of (15-100) oC, the
exothermal polymerization signals observed in the differential scanning calorimetry curves
are at (160-314) oC, and the glass transition temperatures of the polymerization products
are at (73-190) oC. Cyclic voltammetry measurements showed that the synthesized
compounds are electrochemically stable. They exhibited one step reversible oxidation. All
the synthesized compounds absorb electromagnetic radiation in the range of (200–500) nm
and emit in the range of (375–550) nm in purple and blue colours.Hole-drift mobilities in
the layers of neat thiophene–based dihydrazones and phenothiazine-based mono- and
dihydrazones are in the range of (10-5-10-7) cm2/Vs at the electric
field of 1·106 V/cm, at 25 °C.
References
1. R. Lygaitis, V. Getautis, J.V. Grazulevicius. Chemical Society Review. 37, 770-788 (2008).
2. S. Juršėnas. Organiniai puslaidininkiai. Vilniaus universitetas, Vilnius (2008).
3. V. Mimaitė, J.V. Gražulevičius, J. Ostrauskaitė, V. Jankauskas. Dyes and Pigments. 95, 47-52 (2012).
4. V. Getautis, M. Daškevičienė, T. Malinauskas, V. Gaidelis, V. Jankauskas, Z. Tokarski. Synthetic
Metals. 155, 599-605 (2005).
91
THE INFLUENCE OF CHAIN MICROSTRUCTURE ON SELFORGANIZATION OF COPOLYMERS IN SEMIDILUTE SOLUTIONS
E. Litmanovich
Polymer Chair, Chemical Faculty, Moscow State University, Moscow, Russia, [email protected]
Semidilute solutions of two samples of vinyl alcogol (VA) – vinyl acetate (VAc)
copolymers were studied by means of dynamic light scattering technique. The copolymers
series were the same in polymerization degree and by the composition (50% VAc), but of
different chain microstructure. The samples were synthesized from poly (vinyl acetate).
Sample 1 was obtained by alkaline hydrolysis of PVAc in water-acetone mixture. The
reaction occurs with accelerating neighboring group effect, so sample 1 has multiblock
structure (average block lengths was 5 units). Sample 2 was obtained in two stages. On the
first stage the exhaustive hydrolysis of PVAc was performed. On the second stage poly
(vinyl alcohol) obtained was esterified by acetaldehyde to 50% of conversion. The reaction
of esterification occurs without neighboring group effect, so in sample 2 the distribution of
comonomer units was random (average sequence length was 2 units). DMFA was used as a
solvent in light scattering experiments.
The distributions by relaxation times, restored from correlation functions, were found
to be trimodal in case of multiblock-copolymer, and bimodal in case of random copolymer.
The dependence of relaxation rate on squared wave vector was found to be linear for all
modes observed. This fact indicates that all modes comply with diffusive processes. The
diffusion coefficients and then hydrodynamic radii were calculated. The fast mode in case
of random copolymer corresponds to radius about 5 nm, in case of multiblock-copolymer –
about 130 nm. Therefore, the fast mode in random copolymer solution is the diffusion of
blobs, or chain sections between entanglements. On the contrary, in multiblock-copolymer
solutions the radius, corresponding to the fast mode, is much larger that macromolecule
coil radius. This data indicate that the associates of macromolecules, or may be microgels
exist in semidilute solutions of multiblock-copolymer. The interchain hydrogen bonds
between VA and VAc blocks are the reason of association.
The existence of large associates in multiblock-copolymer solutions was proved by
means of static light scattering data. The intensity of scattered light decreases sharply with
increase of scattering angle. In case of random copolymer the scattering indicatrix was
found to be symmetrical.
Acknowledgements.This work was supported by Russian Foundation for Basic Researches (project No 1103-00232).
92
RADICAL POLYMERIZATION OF ACRYLIC MONOMERS IN THE
PRESENCE OF COPPER (II) IONS IN AQUEOUS SOLUTIONS
E. Sivtsov, A. Logunova, A. Gostev
Free-radical polymerization is the main method of polymer synthesis. Unfortunately
there are not enough tools to regulate parameters of the reaction. So much the more
required any technique allowing to control the properties, especially molecular mass
characteristics, of polymers obtained. It is known that copper (II) is an effective regulator
of poly(acrylic acid) molecular mass in the case of acrylic acid (AA) radical
polymerization initiated by hydrogen peroxide thermal decomposition at 90°C in aqueous
solutions. Molecular mass of the polymer decreases with increasing Cu2+ concentration.
The interesting fact is that molecular mass distribution becomes more narrow. From the
point of view of kinetics there are not any retardation or inhibition of polymerization:
conversion of the monomer over 90% is achieved for several minutes.
In the present study we investigated the possibility of using this simple molecular mass
regulation method for polymerization and copolymerization of some other vinyl monomers
It was successful applied in homopolymerization of acrylamide (AAM). Using 1% of
AAM mass Cu2+ (in the form of sulphate) allows to obtain of 20% poly(acrylamide)
aqueous solutions with low viscosity. In the absence of copper ions even 1% solution
hardly flows. We proposed the mechanism of Cu2+ effect in such systems shown in the
scheme below:
O
R
O
C
CH
C
R
C
O
Cu+HSO4-
R
+
H2O2
CH2
R
O
C
CH
R
O
C
+
Cu2+ SO42-
CH
C
O
R
Cu2+ SO42-
+
HO
+
+
H2O
CH2
CH
etc.
C
O
R
C
R
CH
CH
+
Cu+HSO4-
O
R = OH, NH2, O(CH2CH2O)nOCH3
C
R
O
The chain termination occurs due to redox interaction between the propagating
macroradical and Cu2+, copper is reduced to Cu1+, which is oxidized by hydrogen peroxide
with formation of OH• radical capable to reinitiating of polymerization.
This effect was used in copolymerization of AA with methoxy polyethylene glycol
methacrylates (MPEGMA) with PEG radicals of various length and with vinylene
carbonate (VC). In both cases molecular mass of copolymer decreases with increasing of
[Cu2+]. On the base of copolymers AA–MPEGMA hyper-plasticizers for concrete was
obtained which can find extensive application in construction industry, especially for
preparation of ready concrete mixtures with extreme fluidity – ideal materials forming bulk
constructions with complex configuration. The copolymers are used in comparatively low
dosage (0.15-0.3% of cement mass) and extremely low water-cement relations. They have
optimal properties at the very narrow diapason of molecular masses because in the
mechanism of action of such hydrophilic polymers the role of ζ-potential is very low and
the mutual repulsion of cement particles and stabilization of suspension are made because
of prevalent steric effect of the long PEG radicals.
93
MIXED POLYMER MICELLES WITH SEGREGATING
AMPHIPHILIC CORONA
E. A. Lysenko1, A.M. Rumyantsev2, E.Yu. Kramarenko2, A.B. Zezin1
1
2
Chemical Department, Moscow State University, Moscow, Russia, [email protected]
Physical Department, Moscow State University, Moscow, Russia
Polymer micelles from AB-diblock copolymers (A is hydrophobic block, B is water
soluble block) with homogeneous A-core and homogeneous B-corona were the subject of
intensive study. A challenging task is a creation of hierarchically organized polymer
micelles with the core or corona further subdivided onto structural domains with different
properties and composition [1]. To solve this task we have prepared mixed polymer
micelles from AB and AC diblock copolymers (A and C are hydrophobic blocks, B is ionic
block). In aqueous media these block copolymers spontaneously self-assemble into joint
micelles with hydrophobic A-core and segregating amphiphilic BC-corona. The structure
and properties of micelles were studied as a function of corona composition
 = [B]/([C]+[B]), both theoretically and experimentally.
Mixed micelles demonstrated a remarkable inflection in structure near  ~ 0.5. Above
this point aggregation number (m) and micelle dimensions coincided with those of
individual AB-micelles. When  decreased below 0.5, dramatic growth of aggregation
number was observed, accompanied by growth in micelle size and stretching B-chains.
Scaling relationships between micelle characteristics and  were obtained from threelayered model of mixed micelles (A-core; shell from collapsed C-blocks, wrapping the
core; the outer B-corona) via minimization of micelle free energy, taking into account
electrostatic, osmotic, volume and surface contributions. Theoretical estimations predicted
dramatic influence of  on aggregation number, m ~ -3. This result is in general
agreement with experimental data and confirms the correctness of the core–shell–corona
model (Fig. 1). The inflection in micelle structure entails drastic changes in micelle ability
to form soluble complexes with oppositely charged polymeric or amphiphilic
complexing agents [2].
m
1200
900
600
300
0

0.2
0.4
0.6
0.8
1.0
Fig. 1. The dependence of micelle aggregation number (m) vs. . Dashed line is theoretical.
References
1. M. Motornov, Yu. Roiter, I. Tokarev, S. Minko. Prog. Polym. Sci., 35, 174–211 (2010).
2. E. Lysenko, A. Kulebyakina, P. Chelushkin, A. Rumyantsev, E. Kramarenko, A. Zezin. Langmuir, 28,
12663–12670 (2012).
94
GLASS-FORMING TRIPHENYLAMINE DERIVATIVES AS HOLE
TRANSPORTING MATERIALS
V. Mimaite1, J.V. Grazulevicius1, V. Jankauskas2
1
[email protected]
2
Department of Solid State Electronics, Vilnius University, Vilnius, Lithuania
Small organic molecules that readily form glasses above room temperature are referred
as molecular glasses or amorphous molecular materials. Such compounds may form
amorphous films without generation of structure defects by different techniques. They
constitute a class of functional organic materials for electronic and optoelectronic
devices [1].
The aim of this work was to compare the optical, thermal, electrochemical and
photoelectrical properties of synthesized triphenylamine derivatives 1-5 shown in Fig.1.
Compounds were synthesized by simple two-step synthetic route. The chemical structures
of the synthesized triphenylamine derivativeswere confirmed by IR, 1H NMR and mass
spectrometries.
R
R1
1
H
H
2
H
OCH3
3
OCH3
OCH3
4
H
CH3
5
CH3
CH3
Fig. 1. Chemical structures of glass-forming triphenylamine derivatives.
The obtained materials are capable of glass formation, their glass transition
temperatures are in the range of 73-77 ºC. The ionization potential values of the amorphous
layers of the compounds range from 5.23 eV to 5.56 eV. The introduction of methoxy and
methyl groups into the structure of thriphenylamine-based derivatives 2-5 enables to
decrease their ionization potentials. Time-of-flight hole drift mobilities in the amorphous
layers of compounds 1-4 well exceed 10−3 cm2/Vs at high electric fields. The
triphenylamine derivative 5 exhibited superior charge transporting properties with hole
drift mobility of 1.4·10-2cm2/Vs at an electric field of 106 cm2/Vs.
Acknowledgment. This research was funded by the European Social Fund under the Global Grant measure.
References
1. Y. Shirota and H. Kageyama. Chem. Rev.,107, 953-1010 (2007).
95
COPPER NANOPARTICLE EFFECT ON THE PROPERTIES OF
PERIODICAL STRUCTURE FORMED ON PHOTORESIST
P. Narmontas1, J. Pudlauskaitė2, V. Jankauskaitė2, E. Giškonis3, I. Prosyčevas1
1
Institute of Materials Science, Kaunas University of Technology, Savanorių pr. 271, Kaunas LT-50131,
Lithuania, e-mail:[email protected]
2
Faculty of Design and Technologies, Kaunas University of Technology, Studentų g. 56, Kaunas LT-51424,
Lithuania
3
Department of General Chemistry, Kaunas University of Technology, Radvilnų pl. 19, Kaunas LT-50254,
Lithuania
Metal nanoparticles have received tremendous scientific and practical interest due to
their unique and novel properties [1]. Nanoparticles like Ag, Au, Cu draw scientists
attention due to their chemical and physical properties. Particles of these metals display
surface plasmon resonance in the visible spectrum region and exhibit enhanced nonlinear
optical properties which can be used in many applications in optical devices and nonlinear
optical materials, such as optical switches or photochromic glasses, applications. Among
various metal particles, copper nanoparticles attracted more interest due to its excellent
electrical conductivity, low cost preparation and many potential applications in catalysis,
cooling fluid or conductive inks.
The aim of this work was to investigate the influence of copper (Cu) nanoparticles
deposited from colloidal solution in positive tone photoresist composition on the
morphology and optical properties of grating. In the photoresist Cu nanoparticles (Cu NPs)
were deposited from colloidal solution produced by chemical reduction method using
copper sulfate pentahydrate salt CuSO4·5H2O and hydrazine hidrate N2H4·H2O as reducing
agent [2]. Synthesized Cu NPs were spherical or roughly spherical with diameter varied
from 40 nm up to 130 nm. The content of nanoparticles in the photoresist matrix was
varied by increasing Cu colloidal solution concentration. The grating was formed by
contact lithography. The quantification of Cu NPs and chemical analysis of Cu/NPs were
performed using energy dispersive X-ray analyser SEM/EDS technique. Analysis
performed with atomic force microscope and scanning electron microscope showed that
Cu nanoparticles change the grating geometry – the ridges of grating become concave
(Fig. 1). The optical properties (absorbance) of modified nanostructure were evaluated by
ultraviolet-visible light spectrometry and diffraction efficiency measurements.
Fig. 1. The schematic view of Cu nanoparticles influence on the morphology of periodical structure
formed in photoresist composition
References
1. S. Wang, X. Huang, Y. He, H.Huang, Y. Wu, L. Hou, X. Liu, T. Yang, J. Zou, B. Huang. Carbon. 21192125 (2012).
2. S. Hass, A. Shanmugam, A. Gedanken. J. Phys. Chem. 110, 16947-16952 (2006).
96
THE COMPETITIVE INTERACTIONS OF POLYANIONIC
HYDROGELS WITH WATER-SOLUBLE
INTERPOLYELECTROLYTE COMPLEXES RICH IN THE LINEAR
POLYCATIONS
O.A. Novoskoltseva, V.B. Rogacheva, A.B. Zezin
Department of Polymer Science, Faculty of Chemistry, Lomonosov Moscow State University, Russia,
Moscow, [email protected]
Complex gels have become an active research field nowadays. This work presents the
investigation of the competitive interactions between polyanionic hydrogels and watersoluble non-stoichiometric interpolyelectrolyte complexes (NIPECs) formed by the
lyophilizing poly(N,N`-diallyl-N,N`-dimethylammonium chloride) (PDADMACl; Mw 
500,000) and the blocking sodium poly(acrylate) (PANa; Mw 30,000).
The slightly cross-linked highly water-swollen polyanionic hydrogels of sodium
poly(2-acrylamido-2-methylpropansulphonate) and sodium poly(acrylate) covalently
cross-linked by 1.5 and, correspondingly, 1 wt.% N,N'-methylenebis(acrylamide) were
used.
The conditions under which water-soluble NIPECs are formed and the behavior of
PDADMA-PA complexes in water-salt solutions of NaCl were examined in advance. It
was found that soluble positively charged NIPECs are formed in the presence of more than
a two-fold molar excess of PDADMACl in the reaction mixture, i.e. at the molar ratios
=[PANa]/[PDADMACl]<0.5, in the region of NaCl concentrations from 0 M to 0.4 M.
It was established that the polyanionic network (as sulfocontaining, as
carboxylcontaining) is the effective competitor to linear PANa for binding with
PDADMACl. The hydrogels effectively sorb PDADMA-cations from the solutions of
NIPECs (=0.20.4) to form the cross-linked interpolyelectrolyte complexes that is
accompanied by a strong collapse of the polyanionic networks. It is important, that the
hydrogels do not uptake the second component of NIPEC, and linear PA-anions substituted
by the similarly charged network segments redistribute between the particles of
NIPECpresenting in the solutions. As far as the sorption degree of PDADMA-cations by
the hydrogel increases, the progressive increase in the composition of NIPEC in the
equilibrium solutions is observed, and at ≥0.5 the insoluble particles of stoichiometric
PDADMA-PA (1:1) complex are formed. The results obtained demonstrate that the
hydrogels can undergo the substitution reaction with the soluble positively charged NIPEC
and induce phase separation in the solutions of NIPEC.
Acknowledgements. This work was supported by the Russian Foundation for Basic Research, project № 1203-00705-a.
97
COMPETITIVE REACTIONS IN THE TRIPLE SYSTEM,
CONTAINIG POLY(ACRYLIC ACID) STAR, LINEAR, AND CROSSLINKED POLYELECTROLYTES
T. V. Panova and A. B. Zezin
Polymer Department, Faculty of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory,
119991, Moscow, Russia, [email protected]
Lightly cross-linked polyelectrolyte networks are very attractive objects of
investigations. Polycomplex gels formed as a result of interactions between polyelectrolyte
networks and different oppositely charged species, such as linear polyelectrolytes,
surfactants, proteins have been studied thoroughly. Different features determined by the
cross-linked nature of a complex component were revealed.
In this work, interactions between anionic network and water soluble nonstoichiometric interpolyelectrolyte complexes (NIPCs) formed by star-like poly(acrylic
acid) and linear polycation were studied. Lightly cross-linked sodium poly(acrylate) or
sodium poly(2-acrylamido-2-methylpropanesulfonate) were used as a polyelectrolyte
network. NIPCs contain star-like poly(acrylic acid) and (poly(N-ethyl-4-vinylpiridinium
bromide) or poly(2,5-ionen bromide) as a polycation. The composition of NIPC, φ, i.e. the
ratio of mole amounts of positively charged amino groups to negatively charged carboxylic
groups was φ = 0.2-0.3. Such complexes are water soluble due to the excess of charged
groups of star-like polyelectrolyte.
In the triple systems studied, the star-like polyelectrolyte competes with a network for
the binding with a linear polycation. It was found that sulfo-containing polyelectrolyte gel
can sorb linear polycations from NIPC aqueous solutions with the formation of a new
polycomplex (network-polycation). This process is accompanied with a gel collapse. Starlike poly(acrylic acid) previously bound with a linear polycation is released from NIPC
and remained in a solution. In contrast to sulfo-containing network, in the case of
carboxylic gel, the substitution reaction does not proceed. Thus, in the systems described,
the chemical nature of polyanionic network determines the direction of the substitution
reaction.
Acknowledgements. This work was supported by Russian Foundation for Basic Research (project no. 12-0300705)
98
POLYTHIONIC COMPOUNDS AS PRECURSORS FOR THE
FORMATION OF SOME METAL CHALCOGENIDE LAYERS ON
POLYAMIDE 6 SURFACE
V. Janickis, R. Stokienė, N. Petrašauskienė, S. Žalenkienė
Department of Inorganic Chemistry, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
The binary transition-metal chalcogenides (MxQy) exhibit wide range of structures and
physical properties, which include metallic, semiconducting and insulating materials,
materials with magnetic ordering, refractoriness, intractable and others.
A new sorption-diffusion way of formation of metals chalcogenide layers on dielectric
surfaces was found and developed [1, 2].
This way was attractive from technological point of view because only two solutions
have to be used.
The method consists of 2 stages. Since a PA as semi hydrophilic polymer is capable of
adsorbing ions of various electrolytes from aqueous solutions, in the first stage – chalcogenization of the polymer  PA films were treated with the solution of polythionates, the
anions of which contain chains of divalent sulfur atoms, O3S–Sn–SO3, selenotrithionate,

O3S–Se–SO3, selenopentathionate, O3S–S–Se–S–SO3, or telluropentathionate,

O3S–S–Te–S–SO3. In the second stage, the chalcogenized in polythionates solutions
PA was treated with a solution of Cu(II/I) salts, Tl(I) salt or Co(II) salt and thin layers of
copper sulfides, CuxS, thallium sulfides, TlxS, and cobalt sulfides, CoxS, respectively, were
formed in the surface of a PA. If the solution of selenotrithionate has been used for PA
initial chalcogenization, the layers of copper and cadmium selenides, CuxS and CdxSe,
respectively, in the surface of a polymer were formed. In the cases of selenopentathionate
and telluropentathionates use for PA chalcogenization, the layers of mixed copper
selenides-sulfides, CuxS–CuySe, and mixed copper tellurides-sulfides, CuxS–CuyTe, have
been formed in the surface of PA.
The concentration of chalcogens adsorbed-diffused into PA film depends on the
temperature of a solution and the period of a polymer treatment The conditions of initial
PA chalcogenization determined the concentrations of metals in chalcogenide layer: the
latter increased with the increase of the concentration and the temperature of PA
chalcogenization precursor’s solution.
The layers on PA films surface, formed by sorption – diffusion method using solutions
of polythionic compounds, were characterized by atomic absorption spectrometry, X-ray
diffraction, X-ray photoelectron spectroscopy, atomic force microscopy and scanning
electron microscopy methods.
Concluding we may state, that the layers of metals chalcogenidesforms in the surface
of PA film when the polymer is chalcogenized in polythionic compound solution and later
treated with a solution of Cu(II/I), Co(II), Tl(I), Cd(II): the anionic particles of polythionic
compounds,containing chalcogen atoms of low oxidation state react with the listed metal
ions.The conditions of a polymer chalcogenization determine the concentration of metal
and the composition of chalcogenide layer.
References
1. V. Janickis. Polythionates. Monography, Technologija, Kaunas (2006).
2. V. Janickis. Seleno- and Telluro Polythionates. Monography, Technologija, Kaunas (2007).
99
ALUMINUM COMPLEXES WITH PHENOXY-IMINE AND SALEN
LIGANDS AS CATALYSTS FOR RING-OPENING
POLYMERIZATION OF -CAPROLACTONE AND D,L-LACTIDE
Yu.A. Piskun1, I.V. Vasilenko1, S.V. Kostjuk1, K.V. Zaitsev2
1
Research Institute for Physical Chemical Problems of the Belarusian State University, Leningradskaya st.
14, 220030, Minsk, Belarus, [email protected]
2
Moscow State University, Department of Chemistry. Vorob’evy gory, 119899,Moskow, Russia
Poly(D,L-lactide) and poly(-caprolactone) are biodegradable and biocompatible
(co)polyesters which extensively studied and widely used in medicine (implants, orthopedic
fixing devices), pharmacology (drug delivery systems) and in the production of environment
friendly polymer materials. Today a particular attention is paid to the synthesis of
functionalized polyesters due to the possibility to use them as building blocks,
macromonomers or macroinitiators for obtaining more complex macromolecular
architectures (star-shape, graft copolymers and etc.) This work is devoted to the investigation
of -caprolactone and D,L-lactide polymerization in bulk in the presence of new aluminum
complexes with phenoxy-imine(1a, 1b, Fig. 1) and SALEN (2a, 2b, 2c Fig. 1) ligands
modified by unsaturated alcohol.
Scheme 1. Structures of catalysts used in this work
The polyesters with acceptable content of vinyl end groups (Fn75%), controlled
molecular mass (Mn up to 50000 g/mol) and narrow MWD (Mw/Mn<1.7) have been
obtained in the presence of functional complexes with phenoxy-imine ligands at 80-130ºC.
It was found that 1a induced considerably faster polymerization of D,L-lactide than 1b (the
polymerization time is 1 and 24 h, respectively). But in the case of -caprolactone
polymerization the inverse dependence is observed (the polymerization time is 2 and 1 h,
respectively).
The Al complexes with SALEN-ligands demonstrated quite high activity at
temperatures 80-130ºC affording polyesters with Mn up to 20000 g/mol and relatively
narrow MWD (Mw/Mn<1.8), but rather low functionality (Fn<50%). 1H NMR studies of the
obtained polyesters revealed the presence of a vinyl group at the chain end indicating that
the polymerization takes place exclusively at the Al–OR bond of the catalyst through a
“coordination-insertion” mechanism.
100
THE COMPOSITE MATERIALS OF POLYANIONS AND MULTIWALLED CARBON NANOTUBES: SYNTHESIS AND PROPERTIES
O. Pyshkina, N. Volosova, V. Sergeyev
Department of Polymer Science, Faculty of Chemistry, Lomonosov Moscow State University, Russia,
Moscow, [email protected]
The composite materials based on multi-walled carbon nanotubes (MWCNT) are an
active research field nowadays due to their unique properties such as high mechanic
strength and electroconductivity. However MWCNT are not dispersible in all known
solvents, so they are usually modified covalently or non-covalently in order to disperse
them in polar or non-polar solvents. This work presents the investigation of the noncovalent modification of MWCNT by polycarbonic acids with different molecular masses
(polyacrylic acids with Mw  2000 and 250000 and polymethacrylic acid with Mw 
100000) and the study of the chemical properties of obtained composite materials.
It was shown, that multi-walled carbon nanotubes dispersing in polycarbonic acids
aqueous solutions leads to their aggregates destruction and formation of their stable
dispersions. For all studied polyacids MWCNT concentration in the dispersion increase
monotonous with the increase of the MWCNT concentration added into polyacid solution.
The dispersed MWCNT concentration is almost the same as added MWCNT concentration
up to some added MWCNT concentration, i.e. its complete dispersion was observed. The
addition of MWCNT at the concentration higher than mentioned above induces the
considerable decrease of their amount in the dispersion (in several times) and MWCNT
precipitation from the solution. This phenomenon can be explained as follows: after the
addition of excess MWCNT amount they are soluilized by polyacid macromolecules
already contained MWCNT, and such system loses the sedimentative stability (sheme
below).
The increase of polycarbonic acid molecular mass causes the increase (by module) of
electrophoretic mobility and ζ-potential of MWCNT-polyacid system, which can be the
reason of the increase of dispersed multi-walled carbon nanotubes amount with the
increase of polycarbonic acid molecular mass.
By means of IR-spectroscopy the interactions between MWCNT and polycarbonic
acids were established, which indicate to the formation of MWCNT-polyacid composite
materials.
Acknowledgements. This work was supported by the Russian Foundation for Basic Research, project № 1303-00605-a.
101
SYNTHESIS OF GLASS-FORMING CARBAZOLE DERIVATIVES
BY THE METHOD OF CLICK CHEMISTRY
G. Samulionytė, J. Simokaitienė, J. V. Gražulevičius
Glass-forming carbazole-containing compounds are attractive for use in organic lightemitting diodes owing to their efficient blue electroluminescence. Organic molecules
containing in their structure such chromophores as carbazole have also been known as
good hole-transporting materials. Cu-catalyzed azide-alkyne cycloaddition ascribed to the
„click reactions“, is an attractive method for the synthesis of electroactive materials.
1,4-Disubstituted 1,2,3-triazoles formed in these reactions are highly stable under a wide
range of conditions [2].
In this work we report on the synthesis of electroactive compounds in which carbazole
moieties are held directly via the triazole rings. The structures of the new carbazole
derivatives having 1,2,3-triazole moieties are shown bellow.
N
N
N
N
N
N
N
N
N
N
N N
1
N
N N
N N
2
N
N
N N
N N
3
The structures of the synthesized compounds were confirmed by 1H and 13C NMR, IR
and mass spectrometries. The thermal, optical and photoelectrical properties of synthesized
compounds have been investigated. The optical band-gaps estimated from the absorbtion
edges of the dilute solutions are of values from 3.14 to 3.34 eV. The synthesysed
compouds form glasses witch the glass transition temperatures ranging from 105 to 173 oC.
Their thermal degradation stars above 333 oC. The ionization potencials of the synthesized
compounds estimated by cyclic voltammetry range from 5.39 to 5.50 eV.
References
1. Zhang, Q., Ning, Z., Tian, H. Dyes and Pigments, 81, 80–84 (2009).
102
MULTIARM STAR WITH POLY(ETHYLENEIMINE) CORE AND
POLY(ε-CAPROLACTONE) ARMS AS MODIFIERS OF
DIGLYCIDYLETHER OF BISPHENOL A THERMOSETS CURED
BY 1-METHYLIMIDAZOLE
C.Acebo1, X. Fernández-Francos1, F.Ferrando2, A. Serra1, J.M.Salla3, X.Ramis3
1
Department of Analytical and Organic Chemistry, Universitat Rovira i Virgili, Tarragona, Spain
Department of Mechanical Engineering, Universitat Rovira i Virgili, Tarragona, Spain
3
Thermodynamics Laboratory, ETSEIB Universitat Politècnica de Catalunya, Barcelona, Spain
2
Multiarm stars containing a hyperbranched poly(ethyleneimine) (PEI) core and poly(εcaprolactone) (PCL) arms of different length were synthesized by ring-opening
polymerization of ε-caprolactone from the PEI core and used to modify diglycidylether of
bisphenol A (DGEBA) formulations cured with 1-methylimidazole.1
Fig. 1. Synthetic route to the multiarm star copolymers PEI-PCLX
The curing process was studied by dynamic scanning calorimetry. It was not observed
much influence on the curing rate when the modifiers were added. In order to establish the
processability of the mixtures, the complex viscosity was determined by rheological
experiments. In all cases the viscosity values were relatively low and did not compromise
the processability of the mixtures.
By dynamomechanical properties of the thermosets were determined. The curves were
unimodal and as the proportion of modifier increased the maximum of tan δ was shifted
towards lower temperatures. The thermal stability, studied by thermogravimetric analysis,
was barely modified since the degradation onset temperature only slightly decreased.
Toughness behavior of neat DGEBA and DGEBA/PEI-PCLX modified thermosets
was investigated by impact test, and the morphology analyzed by electron microscopy on
the fracture surface of the samples. The formulation with 10% PEI-PCL30 had the highest
impact resistance, which was in agreement with the fracture surface of the material which
showed a more yielding fracture with thicker cracks.
Acknowledgements. The authors would like to thank MINECO (MAT2011-27039-C03-01, MAT201127039-C03-02) and Generalitat de Catalunya (2009-SGR-1512, FPI-2009). BASF and Huntsman for
providing Lupasol® and Araldite GY 240, respectively.
References
1. C. Acebo, X. Fernández-Francos, F. Ferrando, A. Serra, J.M. Salla, X. Ramis, React Funct Polym 73 431441 (2013)
103
CAlTIONIC POLYMERIZATION OF ISOBUTYLENE BY
AlCl3/ETHER COMPLEXES IN NON-POLAR SOLVENTS
D. I. Shiman, I. V. Vasilenko, A. N. Frolov, S. V. Kostjuk
Research Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya
St., 220030 Minsk, Belarus, [email protected]
Low molecular weight (Mn~ 500–5000 g/mol) polyisobutylene (PIB) with high exoolefin end groups content (highly reactive PIB (HR PIB)) is an important precursor to
motor oil and fuel additives. Today, HR PIB containing 75-85% of exo-olefin end groups
was obtained industrially using BF3-based initiating systems. We showed recently that
AlCl3•OBu2 initiated the polymerization of IB affording HR PIB (exo >90%) [1, 2].
In this work, the influence of ethers (linear: Et2O, Bu2O, Am2O, Hex2O, MeOPh;
branched: iPr2O, tBuOMe; and cyclic: THF) on the cationic polymerization of isobutylene
co-initiated by AlCl3 complexes with ethers in toluene or n-hexene at –20 C has been
investigated (see Table 1). We showed here that equimolar complexes of AlCl 3 with ethers
of moderate basicity (Bu2O; pKa= -5.4 and iPr2O pKa= -4.3) afforded PIB with the highest
exo-olefin terminal groups content (80–95%) and monomer conversion (80-90%). On the
contrary, the use such weak ether as anisole (pKa=-6.54) led to the “conventional”
polyisobutylenes containing mainly tri- and tetra-substituted olefinic end groups (> 95%).
The complexes of AlCl3 with tert-butyl methyl ether or tetrahydrofuran are characterized
by low stability at room temperature due to the ether cleavage by such strong Lewis acid as
AlCl3 and does not allow to obtain PIB with high exo-olefin end groups content [3].
Table 1. Polymerization of isobutylene co-initiated by AlCl3ether at –20 C
Ether
Et2O
Bu2O
Am2O
Hex2O
MeOPh
i
t
Pr2O
BuOMe
THF
–
Solvent
Conv
(%)
Mn
(g mol–1)
Mw/Mn
toluene
toluene
n-hexane
toluene
toluene
toluene
toluene
n-hexane
n-hexaneb
toluene
toluene
toluene
27
77
19
34
15
100
87
51
70b
100
33
100
3230
3785
7100
8340
4440
11200
2180
3810
5950b
4400
3680
6800
2.5
3.5
2.8
3.1
–
3.3
2.7
3.1
3.8b
1.7
3.4
5.5
Exo-olefin
end groups
(mol%)
80
93
78
83
56
5
95
86
71b
5
4
–
[AlCl3ether]=[AlCl3]=22 mM; [IB]=0.9 M; [H2O]1.7 mM (toluene)reaction time: 10 min, b[IB]=5.2 M
Acknowledgements. The authors thank BASF SE for the continuous financial support of this research.
References
1. I.V. Vasilenko, A.N. Frolov, S.V. Kostjuk. Macromolules, 43, 5503-5507 (2010),
2. I.V. Vasilenko, D.I. Shiman, S.V.Kostjuk. J. Polym. Sci. 50, 750-758 (2012)
3. D.I. Shiman, I.V. Vasilenko, S.V. Kostjuk, Polymer, 54, 235-2242 (3013).
104
SYNTHESIS OF CHARGE -TRANSPORTING MOLECULAR
GLASSES BY THE MOTHOD OF CLICK CHEMISTRY
G. Šimkus1, A. Tomkevičienė1, J. V. Gražulevičius1
1
Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50245,
Click chemistry represent relatively new, effective and very selective methods of
synthesis of organic compounds. High reaction rates at mild conditions and high yields of
the products are characteristic festures of click chemistry [1]. The methods of click
chemistry can be also used for the prepartion of organic glass-forming charge-tranporting
materials with high triplet energy. Such compounds are of special interest as potential hosts
of the emission layers of electrophosphorescent devices.
In this presentation we report on the synthesis and studies of several new carbazole and
triphenylamine derivatives that were synthesized by thiol-ene click reactions.
N
N
N
S
N
S
S
S
S
1
S
S
N
N N S
2
S
S
N
N
3
S
S
N N
N
4
The chemical structures of the synthesized compounds were confirmed by 1H and 13C
NMR, IR and mass spectroscopies. The thermal, optical, photophysical, electrochemical
and photoelectrical properties of the synthesized compounds have been studied.
References
1. C.E. Hoyle, C.N. Bowman. Angewandte Chemie, 49, 1541-1552 (2010).
105
SYNTHESIS OF COMPOSITIONALLY HOMOGENEOUS
GRADIENT COPOLYMERS VIA RAFT POLYMERIZATION
E. Sivtsov1, A. Gostev1,E. Chernikova2
1
2
A serious difficulty arises when it is necessary to synthesize a copolymer of
appropriate quality from monomers with a deep difference of their reactivity. If the radical
polymerization is considered as the most suitable method to obtain the copolymer a
successful solution of the trouble is possible only in the following cases: 1) when r1=r2=1
(azeotropic copolymerization); 2) when r1=r2=0 (alternating copolymerization). Otherwise
rather compositionally heterogeneous copolymers are obtained. If the difference in the
values of r1 and r2 is great a complex mixture of copolymers (including homopolymer of
the less active monomer obtained on high monomers conversions after complete
polymerization of the more active one).
The most promising way to solve this problem within the framework of radical
polymerization is using the RAFT polymerization. In this study compositionally
homogeneous copolymers of N-vinylsuccinimide (VSI) and n-butylacrylate (BA), 4vinylpiridine (4VP) and tret-butylacrylate (tBA), vinyl acetate (VA) and BA were
synthesized on high conversions using dibenzyltritiocarbonate (BTC) as a RAFT agent.
The monomers in each of the couples have very different reactivities (Table).
Table – The monomers reactivity ratios
M1
M2
VSI
4VP
VA
BA
tBA
BA
Calculation method
Ezrielev–Brokhina–Roskin
Kelen–Tudos
r1
r2
r1
r2
0.11
2.54
0.10
2.43
1.41
0.04
1.44
0.10
0
5.36
0.01
5.38
Using RAFT technique in copolymerization allows to obtain copolymers with high
composition homogeneity and narrow molecular-mass distribution from various vinyl
monomers. Thus, RAFT polymerization is practically a universal tool to avoid
compositional heterogeneity in radical copolymerization and simple in technological
realization as the conventional polymerization. It is important that the presence of RAFT
agent does not influence on the monomer reactivity but confines the composition
heterogeneity within a macromolecule.
It was found that effective control can be achieved if the only less active monomer in
monomers couple has chain transfer rate constant (Ct) to BTC high enough. For example,
the more active 4VP has Ct ~1 and the less active tBA Ct ~40; if the initial monomers
mixture contains an excess of tBA a linear correlation between molecular mass of
copolymer and conversion is observed. Even in the case of a little excess (58 mol.% in the
mixture) of the less effective in chain transfer 4VP polymerization has a pseudo-living
character.
The gradient microstructure of copolymers obtained was estimated on the base of
copolymers composition at the various degrees of monomers conversion, monomers
concentrations and molecular mass data. The whole reaction was divided into small
polymerization increments and for each one the probability of dyad (M1–M1, M1–M2 and
M2–M2) and triad formation as well as the average statistical length of the sequences of n
monomer units of M1 and M2 were calculated to describe the chain microstructure.
106
SYNTHESIS AND PROPERTIES OF SPIRO(FLUORENE-9,9'XANTHENE)-BASED MONOMERS
J. Songaila, J. Ostrauskaitė, J. Simokaitienė, J. V. Gražulevičius
Charge-transporting materials play a key role in organic light-emitting diodes, organic
thin film transistors as well as in other optoelectronic and electronic devices. Compounds
which can be used for in organic electronics must have a full set of properties. Such
materials must be extremely pure, must have high charge carrier mobility, suitable
ionization potencial, good film-forming properties, thermal and morphological stability.
-Conjugated materials based on spiro-annulated structures have attracted a great deal of
attention for blue-emission materials and charge-transporting hosts due to their spectral
stability and thermal and morphological stabilities [1].
In this presentation we report on the synthesis of new spiro(fluorene-9,9'-xanthene)
derivatives containing 3,6-di-tert-butylcarbazolyl groups at the C-2 and C-7 positions of
the core spiro-skeleton.
The spiro(fluorene-9,9'-xanthene)-based compounds 1-3 were preapred by multistep
synthetic route including condensation of 2,7-dibromofluorenone with resorcinol, the
reaction with epichlorohydrin or methyl bromide and Ullmann coupling reactions.
The structures of the synthesized compounds were confirmed by 1H and 13C NMR, IR
spectroscopies and mass spectrometry. Compounds 1 and 2 have reactive functional groups
and can be used in the synthesis of electroactive polymers. The thermal, optical and
photoelectrical properties of synthesized compounds have been investigated. All the
synthesysed compouds form glasses. Time-of-flight hole drift mobilities of the glassy
layers of the synthesized compounds exceed 10-3 cm2/Vs at high electric fields.
References
1. Z. Chu, D. Wang, Ch. Zhang, F. Wang, H. Wu, Z. Lv, Sh. Hou, X. Fan, D. Zou. Synthetic Metals, 162,
614– 620, (2012).
107
INVESTIGATION OF ELECTRO-ACOUSTIC EFFECTS IN
ORGANIC STRUCTURE
N. Kus1, P. Stakhira1, D. Volyniuk1,2, V. Cherpak1, J.V. Grazulevicius2, N.A. Kukhta2,
G. Barylo1, Z. Hotra1,3
1
Lviv Polytechnic National University, S. Bandera 12, 79013 Lviv, Ukraine, [email protected]
Lithuania
3
Rzeszów University of Technology, W.Pola 2, Rzeszów, 35-959, Poland
2
Progress of organic electronics is directly related to the search for new highly
functional organic materials and to the development of new generation devices based on
these new organic materials [1]. Along widely investigated devices such as organic
electroluminescent diodes [2], organic field effect transistors [3] and organic solar cells [4],
the research of electromechanical transducers, actuators based on organic materials [5] is
also carried out. It is shown that certain organic semiconductor materials can have different
functional applications. They can be used as light emitting active materials and nanoscale
electromechanical transducers [5]. An increase in the realization of such systems is due to
the growing interest in nanoactuators in electronics and biomedicine [6].
With an aim to study electroacoustic response of organic structures based on the
dendritic
derivatives
of
triazine
2,4,6-tris(4-((9,9-di(2-ethylhexyl)fluorene-2yl)ethenyl)phenyl)-1,3,5-triazine, 2,4,6-tris(4-(9,9-di(2-ethylhexyl)fluorene-2-yl)phenyl)1,3,5-triazine, and 2,4,6-tris(4-((9,9-di(2-ethylhexyl)fluorene-2-yl)ethynyl)phenyl)-1,3,5triazine we used U-shaped signals with different frequency range and pulse duration.
Registration of generated acoustic signals was performed using the developed high
sensitive electro-mechanical acoustic system. We have shown the way to use the electroacoustic effects in organic structures in the design of nanoactuators.
Ackowledgments. This research was supported by FP7 REGPOT-2012-2013-1 REGPOT-2012-2013-1 ICT
project CEOSeR (grant agreement No 316010). It was also supported by the Lithuanian–Ukrainian
Cooperation Programme in the Fields of Research and Technologies (project No TAP LU 01/2012)
References
1. Organic Electronics, Materials, Manufacturing and Applications, edited by H. Klauk, Wiley-VCH
Verlag, Weinheim (2006).
2. B. Wang, M. G. Helander, J. Qiu, D. P. Puzzo, M. T. Greiner, Z. M. Hudson, S. Wang, Z. W. Liu, Z. H.
Lu. Nat. Photonics 5, 753 (2011).
3. C. Melzer, H. von Seggern. Nat. Mater. 9, 470 (2010).
4. H. Hoppe, N. S. Sariciftci. J. Mater. Res. 19, 1924 (2004).
5. G. Dennler, N. S. Sariciftci, R. Schwödiauer, S. Bauer, H. Reiss. Appl. Phys. Lett. 86, 193507 (2005).
6. E. Smela. Adv. Mater. 15, 481 (2003).
108
SYNTHESIS AND PROPERTIES OF INDOLO[3,2-b]CARBAZOLE
MONOMERS AND CROSS-LINKED POLYMERS FOR
OPTOELECTRONIC DEVICES
E. Stanislovaitytė, J. Simokaitienė, J.V. Gražulevičius
Polymer light emitting device (PLED) fabrication technology is a leading nextgeneration technology in a series of high-efficiency flat-panel displays and lighting. Many
derivatives of a new structure have been investigated as charge transporting materials in
PLEDs trying to enhance their efficiency. Among the high-performance materials
indolo[3,2-b]carbazole derivatives are the most popular ones. These compounds comprise
the large planar and rigid conjugated structure allowing efficient charge-injection and
transfer [1, 2]. We synthesized indolo[3,2-b]carbazole derivatives containing reactive
oxiranyl, vinylbenzyl and vinyloxyethyl groups which can be used for the preparation of
cross-linked hole-transporting layers. The structures of monomers are shown in scheme.
R
R=
N
1: *
O
2: *
N
R
3: *
1, 2, 3
O
Scheme
Oxiranyl and vinyloxyethyl monomers were subjected to cationic photoinduced
polymerization. The conversions of monomers reached were around 60%. The monomer
containing vinylbenzyl groups was also polymerized thermally. The self polymerization of
monomer 3 starts at 230ºC. The molecular weights of the polymers were estimated by gel
permeation cromatography. Thermal, optical, photophysical and electrochemical properties
of the synthesized monomers and polymers were studied and will be presented.
References
1. S. Lengvinaite, J.V. Grazulevicius, S. Grigalevicius, R. Gu, W. Dehaen, V. Jankauskas, et al. Dyes
Pigments, 85, 183–188 (2010).
2. H. Shi, L. Shi, J. Dai, L. Xu, M. Wang, X. Wu, et al. Tetrahedron, 68, 9788–9794 (2012).
109
LOW-MOLAR-MASS AND POLYMERIC GLASS FORMING
CARBAZOLE DERIVATIVES CONTAINING TRI- AND
TETRAPHENYLETHYLENE GROUPS FOR OPTOELECTRONICS
J. Šutaitė, A. Tomkevičienė, J. V. Gražulevičius
Search for new materials with advanced properties is one of the major tasks of the
rapidly developing field of organic optoelectronics. Much attention is being focused on the
conjugated compounds. Such conjugated systems are featured with some interesting
optical and photophysical properties and have a high potential to be used as materials in
organic light-emitting diodes (OLEDs) [1], field effect transistors [2], and solar cells [3].
Due to efficient hole transport and excellent thermal stabilities, electron-rich carbazole
moiety is widely used in the design of hole-transporting and light-emitting materials [4].
Tri- and tetraphenylethylene moieties are chosen as the building blocks because of their
unique properties. They show a low photoluminescence quantum yield in solution but
bocome luminescent when aggregated, exhibiting aggregation-induced emission (AIE),
exactly the opposite behaviour to the aggregation-caused quenching (ACQ) effect [5]. Our
strategy for the synthesis of new series of carbazole derivatives containing tri- and
tetraphenylethylene groups is outlined in Scheme 1. The key step was Heck reactions of
bromide with vinylphenylcarbazole derivatives (1, 2, 3) in the presence of palladium(II)
acetate and tri-o-tolylphosphine to obtain compounds 4–6. Monomers 1, 2, 3 were also
used for the synthesis of polymers by chain growth polymerization.
Ar
I
*
HO
B
HO
N
N
1
Pd(PPh3)4, (t-Bu)3P,
2M K2CO3, toluene
Br
Br
N
N
N
2
4a,b
4a, 5a, 6a: Ar =
Ar
Pd(OAc)2, P(o-tolyl)3,
DMF, TEA
N
5a,b
Ar
*
Br
N
H
Pd(dba)3, t-BuONa
(t-Bu)3P, toluene
4b, 5b, 6b: Ar =
N
N
6a,b
3
Ar
Scheme1
Acknowledgements.This research was funded by the European Social Fund under the Global Grant measure.
References
1. M.T. Bernius, M. Inbasekaran, J. O′Brien, W. Wu. Adv. Mater., 12, 1737 (2000).
2. W. Wu, Y. Liu, D. Zhu. Chem. Soc. Rev., 39, 1489 (2010).
3. B.C. Thompson, Y.G. Kim, T.D. McCarley, J.R. Reynolds. J. Am. Chem. Soc., 128, 12714, (2006).
4. a) A. Tomkeviciene, J.V. Grazulevicius, K. Kazlauskas, A. Gruodis, S. Jursenas, T.H. Ke, and C.C. Wu.
J. Phys. Chem. C, 115, 4887 (2011); b) Y.M. Tao, H.Y. Li, Q.L. Xu, Y.C. Zhu, L.C. Kang, Y.X. Zheng,
J.L. Zuo, X.Z. You. Synth. Met., 161, 718 (2011).
5. a) W.Z. Yuan, P. Lu, S. Chen, J.W.Y. Lam, Z. Wang, Y. Liu, H.S. Kwok, Y. Ma, B.Z. Tang. Adv.
Mater., 22, 2159 (2010). b) Z. Yang, Z. Chi, T. Yu, X. Zhang, M. Chen, B. Xu, S. Liu, Y. Zhang, J. Xu.
J. Mater. Chem., 19, 5541 (2009).
110
SYNTHESIS OF CATECHOLIC GROUPS CONTAINING
COPOLYMERS OF DMAEMA
M. Kirsnytė, V. Pamedytytė, A. Vareikis
Department of Polymer Chemistry, VilniusUniversity, Vilnius, Lithuania, [email protected]
The aim of this work was synthesis and investigation of catecholic groups containing
copolymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA) that would mimic
unique adhesive proteins of mussels [1, 2]. During the work three possible pathways of
synthesis was explored: a) radical copolymerization of monomer already having catecholic
group; b) radical copolymerization of monomer having protected catecholic group, and c)
introduction of catecholic groups into already prepared copolymer.
For a) and b) pathways dopamine methacrylamide (DOPMA) [1] was chosen as
catecholic group containing monomer. Other monomers were DMAEMA and
methacryloyloxyethyl trimethyl ammonium chloride. Radical copolymerization of
unprotected DOPMA with these monomers resulted in low molecular weight copolymers,
as was determined by SEC, DLS and viscosimetry. From this is evident, that phenolic
hydroxyls from DOPMA inhibit radical chain growth [1]. Moreover, if environment is too
basic, these low molecular weight copolymers were unstable, tend to darken and crosslink
during isolation and purification steps. Crosslinking and darkening was successfully
prevented using acetate buffer of pH 4.
Silylation of DOPMA [3] with trimethylchlorosilane in DMF was successful, but due
to the difficulties of purification the yield of protected monomer was low (5-7%).
Nevertheless, copolymerization of protected DOPMA with DMAEMA was
straightforward and synthesized copolymers have not only high molecular weight, but they
are well-stable against oxidation and stable in a slightly-basic media. Deprotection of
copolymers was carried out with simultaneous stabilization by the use of acidic
environment.
We have found that rather simple and reliable way is c), when catecholic groups was
introduced into DMAEMA copolymer using 2-chloro-3’,4’-dihydroxyacetophenone as
DMAEMA unit quaternizing agent. Modification in such a way can be done already
having desired molecular weight, composition and purity of DMAEMA copolymer.
Additionally, quaternization enables easy regulation of ratio between tertiary and
quaternary amino groups, and by this, tailoring solubility of copolymer.
Random copolymer of DMAEMA with vinyl acetate (90 mol% units of DMAEMA)
successfully quaternized with 2-chloro-3’,4’-dihydroxyacetophenone. Target degree of
quaternization was set to 20 and 30 mol% respectively. Both synthesized copolymers are
well-soluble in water and, surprisingly, they are very stable against oxidation and
crosslinking in the air. At the same time, they can be easily oxidized and crosslinked with
strong oxidizers like sodium tetraoxoiodate(VII).
Acknowledgements.This work was supported by the European Social Fund Agency under project “High
Tech Materials Developing Research and Application” No. VP1-3.1-ŠMM-08-K-01-014.
References
1. E. Faure, C. Falentin-Daudré, Ch. Jérôme et all. Prog. Polym. Sci., 38, 236-270 (2013).
2. Q. Ye, F. Zhou, W. Liu. Chem. Soc. Rew., 40, 4244-4258 (2011).
3. J. Nishida, M. Kobayashi, A. Takahara. J. Polym. Sci. A: Polym. Chem., 51, 1058-1065 (2013).
111
RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE
INITIATED BY FUNCTIONALIZED ALUMINUM ALKOXIDES: A
SIMPLE ROUTE TO THE BIODEGRADABLE MACROMONOMERS
I.V. Vasilenko1, Yu.A. Piskun1, S.V. Kostjuk1, K.V. Zaitsev2
1
Research Institute for Physical Chemical Problems of the BelarusianStateUniversity, Minsk, Belarus,
[email protected]
2
Chemistry Department, Moscow State University, Moscow, Russia
In the last few decades, a great interest is revealed to the synthesis of amphiphilic
comb-like and graft copolymers. The ability of amphiphilic copolymers to form
thepolymer particles consisting of a hydrophobic core and hydrophilic polymer chains
covalently fixed on the particle surface in polar media are widely used for drugs
encapsulation. Well-known that amphiphilic copolymers of ethylene glycol, caprolactone (CL), D,L- and L-lactide etc. are widely used for biomedical applications.
Well-defined graft copolymers are most frequently prepared by either a) a "grafting
through" or b) a "grafting from" controlled polymerization process. The "grafting through"
method (or macromonomer method) is one of the simplest ways to synthesize graft
copolymers with well-defined side chains. By generally accepted coordination-insertion
mechanism of ring-opening polymerization (ROP) of cyclic esters in the presence of metal
alkoxides as initiators alkoxide group, which originally presents at the metal atom, is
transferred to the end of the polymer chain.1Proposed by us strategy for one-pot synthesis
of graft copolymers is based on 1) synthesis of functionalized aluminum alkoxides; 2) ROP
of -caprolactone; 3) radical copolymerization of macromonomer (poly(-caprolactone)
PCL) and maleic anhydride (MA) (see Scheme).
Scheme.Synthesis of macromonomers using functionalized aluminum alkoxides as initiators
Anionic ROP of -caprolactone in bulk initiated by a number of organoaluminum
compounds modified by unsaturated alcohol, Me3-nAl(O(CH2)4OCH=CH2)n (n = 1 (1), 2
(2), 3 (3)) has been investigated. Well-defined polymers of CL with Mn in the range from
5,000 to 30,000 g mol–1 and relatively narrow MWD (Mw/Mn1.6) were synthesized. All
synthesized polymers were characterized by near quantitative functionality (Fn(CH=CH2)=95 %). The obtained macromonomers were then copolymerized with MA to
give desired graft-copolymers (see Scheme).
Acknowledgements. The authors thank Belarusian Republican Foundation for Fundamental Research,
project number X12P-139.
References
1. O. Dechy-Cabaret, B. Martin-Vaca, D. Bourissou. Chem. Rev., 104, 6147-6176 (2004).
112
THE EFFECT OF ALKALI CATALYST CONTENT AND WATER
CONTENT IN ORGANOSOLVE WHEAT STRAW LIGNIN ON
PROCESS OF IT OXYPROPYLATION AND CRARACTERISTICS
OF LIGNOPOLYOLS OBTAINED
A. Arshanitsa, L. Vevere, G.Telysheva
Latvian State Institute of Wood Chemistry, Riga, Latvia.
Elaboration of sustainable processes with the most profitable utilization of all products
obtained in the technological cycle is the basic position of modern biorefinery concept.
Lignins separated as by-products in the result of lignocellulosics chemical processing can
be considered as a renewable aromatic polyols suitable for crosslinked polyurethane (PU)
production. Structural heterogeneity, the weak solubility of parent technical lignins in
organic solvents and low reactivity with isocyanates restricts its application as
macromonomer in PU systems. The process of lignins oxypropylation in alkali conditions
using anionic polymerization mechanism is one of the ways to decrease lignin molecular
and functional heterogeneity obtaining liquid products soluble in organic solvents.
The novel wheat straw organosolv lignin (BIOLIGNINTM) produced on CIMV pilot
plant (France) was oxypropylated at propylene oxide lignin ratio equal 7/3 in laboratory
scale high pressure Parr reactor using different KOH content and water content in lignin. It
was shown that in dependence of reaction condition the yield of solid non-liquified fraction
varied in the range 0.1-9.9%. The liquid lignopolyols obtained are a mixture of propylene
glycols and copolymers of lignin with propylene oxide. To separate homopolymer and
copolymer fractions the liquid products were treated by refusing hexane, the residue was
dissolved in acetone and lignin copolymer was precipitated in water. Whole lignopolyols,
homopolymer fractions and oxypropylated lignin fractions were characterized by methods
of wet chemistry, FTIR spectroscopy, 1H NMR spectroscopy and differential scanning
calorimetry. The reactivity of lignopolyols and constituent fractions with pure 4,4-diphenyl
diisocyanate was studied in dioxane solution at 25oC using dibytiltin dilaurate as a catalyst.
Reactivity of lignopolyols was tenfold higher than the reactivity of fractionated but non
modified lignin. The reactivity of oxypropylated lignin fraction was lower in comparison
with reactivity of whole lignopolyol and polypropylene glycol fractions, but was fourfold
higher than reactivity of fractionated non but modified lignin. The lignopolyols obtained
were tested in composition of crosslinked PU elastomers. The tensile and thermal
characteristics of lignopolyol based PU were studied.
Acknowledgment. The financial support from 7th Collaborative project BIOCORE contract 241566 is
gratefully acknowledged.
113
AMPHIPHILIC MULTIBLOCK-COPOLYMERS: SYNTHESIS
AND PROPERTIES
D. Vishnevetsky, E. Chernikova
Polymer Department, Faculty of Chemistry, Moscow State University, Moscow, Russia,
E-mail: [email protected]
At present, there is a considerable interest in polymeric materials with special
properties. A unique place among them is occupied by block-copolymers, including
amphiphilic ones, which depending on the chemical nature of constituent blocks have
found wide application in various fields on engineering and medicine. The literature data
related to the synthesis of block-copolymers and investigation of their properties mostly is
dealt with a few number of narrowly-dispersed di- and triblock-copolymers, which have
been synthesized mainly via the living anionic mechanism. The information about the
possibility of block-copolymers synthesis with more then three blocks by other living
techniques is rare.
The goal of the present work is to develop the approach to obtaining of narrowdispersed amphiphilic pentablock-copolymers with well-defined length of blocks, their
different chemical nature and various sequences in the chain and to investigate their
thermal and solution properties.
At first, the narrow-dispersed pentablock-copolymers based on polystyrene, poly(nbutyl acrylate) and poly(tert-butyl acrylate) were obtained by means of the reversible
addition-fragmentation chain transfer (RAFT) technique using a bifunctional RAFT-agent
dibenzyl tritiocarbonate.
The characteristics of synthesized products were examined by GPC, IR- and 1HMRspectroscopy. The mechanism of block-copolymerization was studied.
The obtained block-copolymers were subjected by acid hydrolysis and the blocks of
poly(tert-butylacrylate) were converted into polyacrylic acid blocks. The solubility of
obtained amphiphilic pentablock-copolymers in different solvents, thermal stability and
their behavior in organic media were studied. The results obtained demonstrated that the
properties of amphiphilic multiblock-copolymers are more strongly affected by the
composition of blocks (the molar ratio of components) than their sequence in a chain.
However, we showed the principal possibility of self-organization of amphiphilic blockcopolymers in the organic media.
Acknowledgement. This research was supported by the state contract from Russian Ministry of
Education and Science (16.512.11.2059 from 15.02.2011)
114
SUPPLEMENTAL REDOX INTERMEDIATES ENHANCING SARA
ATRP OF HYDROPHYLIC MONOMERS IN AQUEOUS SOLUTIONS
C. Visnevskij, R. Makuska
Atom transfer radical polymerization (ATRP) is one of the most popular methods of
controlled radical polymerization, which relies on reversible reaction of a low-oxidationstate metal complex with alkyl halide generating radicals and the corresponding highoxidation-state metal complex with a coordinated halide ligand. The reversible reaction
ensures that most of polymer chains grow at the same time and enables synthesis of a wide
spectrum of polymers with control over architecture, molecular weight and polydispersity.
The amount and stability of low-oxidation-state complex can be controlled by redox
reactions in AGET, ARGET, SARA and ISARA techniques; by radical reduction reactions
in Reverse, SR&NI and ICAR techniques, and electrochemically in eATRP [1, 2].
In the present work, we studied the effect of different supplemental redox
intermediates (SRI) and reducing metals on ISARA ATRP of hydrophilic monomers [2(methacryloyloxy)ethyl] trimethylammonium chloride (METAC), 2-hydroxyethyl
methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), methacrylic
acid (MAA), and poly(ethylene oxide) methyl ether methacrylate (PEOMEMA). ISARA
ATRP is developed in our laboratory for polymerization of hydrophilic monomers in
aqueous solutions and is based on simultaneous use of CuCl2, ligand Me6TREN, reducing
metals copper or iron and SRI [3]. Molecular weight, size and polydispersity of the
prepared polymers were determined by SEC with triple detection, and the structure was
approved by 1H NMR spectroscopy.
Cyclic voltammetry measurements of single polymerization components and various
complexes present in reaction mixtures revealed that only SRI with the oxidation potentials
higher and reduction potentials lower than the oxidation potential of the deactivator Cu II/L
were suitable. The most effective SRI were oxidized forms of ascorbic acid, hydroquinone
and iron (III) chloride when they were used in pair with reducing metals iron or copper. All
SRI systems were suitable for polymerization of METAC enabling to synthesize polyMETAC with molecular weight Mn up to 70 000 and Mw/Mn lower than 1.4. Livingness of
poly-METAC was demonstrated by chain extension with 4-vinylpyridine and 1-vinyl-2pyrrolidinone resulting in block copolymers with Mw/Mn lower than 1.2.
Control of HEMA polymerization was a little bit more complicated than that of
METAC and was realized using zerovalent iron as a reducing agent only. Contrarily, for
ISARA ATRP of DMAEMA and MAA, zerovalent copper was a better choice, because of
weaker complexation of the monomer with CuI/CuII compared to FeII/FeIII. Before
polymerization, MAA was neutralized with different amines to maintain good solubility of
the neutralized monomer and stability of the activator/deactivator system. Polymerization
of PEOMEMA by ISARA technique was less controllable giving brush polymers with Mn
up to 1 500 000 but rather high polydispersity (Mw/Mn> 1.6).
Acknowledgements.Financial support from the Research Council of Lithuania under the project MIP51/2012 is gratefully acknowledged.
References
1. K. Matyjaszewski. Macromolecules, 45, 4015-4039 (2012).
2. K. Matyjaszewski, J. Xia. Chem. Rev. 101, 2921-2990 (2001).
3. C. Visnevskij, R. Makuska, Macromolecules, Doi 10.1021/ma400536j (2013).
115
PREPARATION AND INVESTIGATION OF PLANE POLYMERIC
BRUSHES WITH BRUNCHES OF PBLG AND PLGA ON SI
SURFACE
E. Vlasova, B. Volchek, E. Pruchkina
Institute of Macromolecular Compounds, Russian Academy of Sciences, 199004, Saint-Petersburg, Bolshoi
Prospect 31, Russia, [email protected]
Polymeric brushes consisting of poly-(-L-benzyl glutamate) (PBLG) chains
connected by their carboxylic ends to silicon plates were prepared by Surface-Initiated
Vapor Deposition Polymerization (SIVDP) of N-carboxy anhydride of -benzylglutamate (NCA--BG) on the amino groups of aminoalkyl-silanes of the silicon
substrates (triethoxysilane, APES) or (-aminopropyl or trimethoxysilane, APMS)1.
PLGA silicon brushes were prepared by treatment of PBLG brushes with mixture of
trifluoroacetic acid and trifluorosulfonic acid.
FTIR spectroscopy was used for
determination of conformational and
orientational characteristics and also
molecular masses of polymer chains
grafted to the surface.
The influence of chemical structure of
modifying spacer groups and outer
conditions on the characteristics of plane
polypeptide brushes was established.
Real concentration of PBLG chains,
connected to the plates was determined
according to the fact that  - helix –
IR absorption spectra of PGBG brushes
prepared on APES spacer in gaseous phase: washed
random coil and random coil -  - helix
with chloroform (1), placed in chloroform (2)
transition in mixes of chloroform:
dichloracetic acid while heating or cooling
for PBLG polymeric molecules in solution
shows line character.
The peculiarities of α-helical structure (random coil transfer of polymer chains in
brushes under the action of denaturants) were investigated.
It was found that grafting of rigid macromolecules to surfaces results in diminishing
concentration border of LC formation as compared with the same parameter for polymer
solution.
Permeability of polymer brushes for organic substances (polystyrene, p--BLG,
polyethylene glycol, dodecanol, tridecanoic acid) was investigated with the aim to use of
such polymer systems as models for studying of properties of membranes.
References
1. Y. Wang,Y-C Chang. Langmur, 18, 9859 (2002).
116
ELECTRO-ACTIVE POLYMERS CONTAINING
FRAGMENTS
E. Zaleckas1, R. Zostautiene1, L. Liu2, B. Zhang2, Z. Xie2, S. Grigalevicius1
1
Department of Organic Technology, Kaunas University of Technology, Radvilenu plentas 19, LT50254,
2
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun 130022, China
Aromatic amine-containing polymers and low molecular weight derivatives are among
the most studied materials for optoelectronic and electronic applications due to their high
hole mobility and photoconductive properties. Some of the materials have been
commercialized in a number of devices and processes (photocopying machines, laser
printers, etc.) [1]. N-Phenyl-N-naphtylamine moiety is also interesting for the design and
synthesis of organic semiconductors. It is aromatic unit providing a high thermal,
morphological, chemical and environmental stability. A wide variety of functional groups
can be attached to its nitrogen atom [2]. Usually N-phenyl-N-naphtylamine -based
materials exhibit lower ionization potentials and demonstrate better hole injection and
transport properties as compared to other aromatic amines [3].
We will report the synthesis and properties of new polymers (1 and 2) containing
pendent and electronically isolated N-phenyl-N-naphtylamine fragments. The application
of the materials for hole transporting layers in OLEDs was demonstrated.
1
2
The polymers represent amorphous materials with glass transition temperatures of 71–78
°C and thermal decomposition starting at temperatures > 320 °C. The synthesized materials
have been tested as hole transporting layers in simple OLED devices with Alq3 as the
emitter/electron transporting layer. The green devices containing hole transporting film of
polymer 1 exhibited the best overall performance with a driving voltage of 4.5 V,
maximum photometric efficiency of 3.6 cd/A and maximum brightness of 2850 cd/m2.
Acknowledgements. Postdoctoral fellowship (Ernestas Zaleckas) is being funded by European Union
Structural Funds project ”Postdoctoral Fellowship Implementation in Lithuania“.
References
1. P. Strohriegl, J. V. Grazulevicius, J. Pielichowski, K. Pielichowski, Prog. Polym. Sci. 28, 1297 (2003).
2. A Balionyte, E. Lideikis, S. Grigalevicius, J. Ostrauskaite, E. Burbulis, V. Jankauskas, E. Montrimas,
J.V. Grazulevicius, J. Photochem. Photobiol. A: Chem. 162, 187 (2004).
3. V. Vaitkeviciene, S. Grigalevicius, J.V. Grazulevicius, V. Jankauskas, V.G. Syromyatnikov, European
Polymer Journal, 42, 2254 (2006).
117
XRD STUDY OF CdSe-CdS FILMS ON POLYAMIDE CONVERSION
INTO Ag2Se-Ag2S FILMS
S. Žalenkienė, V. Krylova
Department of Inorganic Chemistry, KaunasUniversity of Technology, Kaunas, Lithuania,[email protected]
A composite material consisting of polymers modified by thin films of desirable
semiconductors has attracted an increasing interest because of characteristic physical and
chemical properties. These properties determine the potential application.
Cadmium selenide (CdSe) and cadmium sulfide (CdS) belong to the II–VI compound
semiconductor materials with n-type electrical conductivity and are often used in
optoelectronic device and for thin films fabrication. These films have applications in
manufacturing of electronic devices: thin film transistors and γ-ray detectors [1]. Silver
selenide (Ag2Se) and silver sulfide (Ag2S) belong to the I–VI compound semiconductor
materials. Ag2Se is a well-known super-ionic conductor. It has been used as
thermochromic material for non-linear optical devices, photo-chargeable secondary
batteries. Ag2S shows n-type electrical conductivity. Thin films of Ag2S have applications
in photoconducting cells, IR detectors, solar selective coating, photovoltaic cell and
photochemical cells [1].
Ion-exchange reactions have been extensively studied in the general areas of catalysis
and thin film technology [2]. A number of cations such as Ag+, Sb3+, and Cu+ have been
used to replace Cd2+ in thin films made of CdSe and CdS [3].
In this study, thin CdSe-CdS films were deposited on polyamide 6 (PA) surface by
successfully using a cation-exchange reaction between Cd2+ and Ag+ to convert CdSe-CdS
into Ag2Se-Ag2S.
For the conversion of CdSe-CdS to Ag2Se-Ag2S, CdSe-CdS/PA films were introduced
into the AgNO3 solution with pH 56 at room temperature in the presence of excess of
Ag+. The replacement of Cd2+ by Ag+ is spontaneous because of the high mobility of Ag+
and their large solubility product differences.
The films were investigated by XRD. Structural studies of the deposits on polyamide
are limited by the crystallinity of the PA film itself. The intensity of its peaks in
2θ≤23°exceeds the intensity of cadmium and silver chalkogenides peaks several times.
Therefore, the area of 2θ≥23° was investigated in more detail. The XRD patterns of the
samples showed the peaks at 2θ = 23.5, 28.43, 48.55, 53.21 and 55.77°. The peaks at 2θ =
23.53 and 48.55° correspond to orthorhombic naumannite – Ag2Se (71-2410) [4], at 2θ =
28.43° to hexagonal wurtzite-type CdS (41-1049) [5], at 2θ = 55.77° to wurtzite CdSe (2330) [6], and at 2θ = 53.21° due to the monoclinic silver sulfide acanthite Ag2S (14-72)
[4]. The replacement of Cd2+ by Ag+ restored the CdSe and CdS structure. After ion
exchange Ag2Se and Ag2S peaks grew continuously as Cd2+ was replaced by Ag+.
As seen from the XRD results, the partial conversion of CdSe-CdS/PA to Ag2SeAg2S/PA led to the coexistence of CdSe, Ag2Se, CdS and Ag2S structures.
References
1. H. M. Pathan, C. D. Lokhande,Bull. Mater. Sci. 27, 85-111 (2004).
2. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry; CambridgeUniversity Press:
Cambridge, U.K., 1997.
3. M. Ristova, M. Ristov, Appl. Surf. Sci. 181, 68-77 (2001).
4. D. Kelly,A. Singh, Ch. A. Barrett, C. O’Sullivan, C. Coughlan, F. R. Laffir, C. O’Dwyer, K. M. Ryan,
Nanoscale, 3, 4580-4583 (2011).
5. A. Phuruangrat, N. Ekthammathat, T. Thongtem, S. Thongtem, J. Alloy. Compd., 509, 10150-10154
(2010).
6. B. Li, M. Jing, G. Rong, Y. Xu, Y. Xie, Eur. J. Inorg. Chem., 2006, 4349-4354 (2006).
118
SYNTHESIS AND PROPERTIES OF ARYLMETHYLENE-1,3INDANDIONE BASED MONOMERS
V. Zilinskaite, A. Tomkeviciene,D. Gudeika, J.V. Grazulevicius
Organic molecules containing acceptor and donor molecular moieties belong to a
relatively new class of materials Among such materials, arylmethylene-1,3-indandiones
constitute an interesting class of compounds exhibiting high hyperpolarizability,
intramolecular charge transfer ability, and interesting photoconducting properties, which
are important for the possible applications in such fields as nonlinear optics an
optoelectronics [1-3].
The aim of our work was the synthesis of arylmethylene-1,3-indandione monomers
with different reactive functional groups. The key step was Knoevenagel condensation of
1,3-indandione with formyl derivatives (a–c) in ethanol to obtain compounds 1 and 2
(Scheme 1). Monomers 1 and 2 were also used for the synthesis of polymers by cationic
polymerization.
O
O
O
O
O
O
O
Cl
BTEAC, 1200C, 1 h.
O
N
O
a
O
Br
O
O
Ethanol,
40OC, 12 h.
N
1
O
OH
O
O
O
O
NaH, 600C, 20 h.
O
O
N
N
Cl
b
O
N
NaOH, Na2SO4
TBAHS,600C, 6 h.
2
O
O
O
N
c
Scheme 1
Acknowledgements.V. Žilinskaitė thanks Research Council of Lithuania for Student Research Fellowship.
References
1. L. Valkunas, D. Juodzbalis, A. Urbas, A. Gruodis, A.D. Durandin, E.A. Silinsh, A. Klimkans, S.
Larsson. Adv. Mater. Opt. Electron, 3, 221 (1993).
2. S. Jursenas, A. Gruodis, G. Kodis, V. Gulbinas, E.A. Silinsh, L. Valkunas. J. Phys. Chem. B, 102, 1086
(1998).
3. G. Meshulam, G. Berkovic, Z. Kotler, A. Ben-Asuly, R. Mazor, L. Spapiro, V. Khodorkovsky. Synt.
Met., 115, 219 (2000).
119
MOISTURE INFLUENCE ON MECHANICAL PROPERTIES OF THE
CNT/EPOXY RESIN NANOCOMPOSITE WITH DIFFERENT
NANOFILLER CONTENT
A. Borisova, T. Glaskova, A. Aniskevich
Institute of Polymer Mechanics, University of Latvia, LV-1006, Riga, Latvia
Different types of epoxy resins are quite durable materials with highly competitive
physical properties, but having relatively low elasticity and high fragility. Such drawbacks
of epoxy resin might be partially neutralized by using different nanofillers. Because of
carbon nanotubes (CNT) exceptional characteristics they are considered as effective
nanofiller which would be capable to improve stiffness, conductivity, resistance to
environmental conditions, etc. Important influence on epoxy resin long-term applicability
what depends on such characteristics as durability, stiffness and others also environment
conditions causes, especially moisture.
Therefore, the objective of the current study is to establish the moisture effect on
mechanical properties of CNT/epoxy nanocomposite (NC) with different carbon nanofiller
content.
Epoxy resin Araldite LY564 and curing agent Aradur XB 3486, as well as masterbatch
Epocyl 1040 with 3% wt. of multiwall CNT were used in different proportions for sample
preparation. NC specimens with different CNT contents (0, 0.01, 0.11, 0.27, 1.09, 1.63,
and 2.17% wt.) were conditioned for 610 days in desiccators with atmosphere relative
humidity (RH) 8, 73 and 93%. When weight of specimens were stabilized the NC were
tested with different physical methods in order to determine the dependence on physical
properties versus moisture level and filler content. Experimental methods as quasistatic
tensile tests (elastic properties) and hydrostatic weighting (density) have been applied.
Based on experimental research of the NC specimens the effect of moisture and filler
content was determined. Research showed influence of CNT content on the dried NC
mechanical properties, where elastic modulus maximally increasesfor 7%, tensile strength
for 6%, and deformation at break for 23%. Because of high CNT density, the density of the
material linearly increases (maximally for 1%) with increasing the nanofiller content.
During moisture absorption NC specimens absorbed 1.4% and 2.5% of humidity at RH
73 and 93%, consequently. Significant changes in mechanical properties was observed on
the moist NC (93% RH), where elastic modulus of neat resin decreased by 39%, and the
tensile strength by 8%. Comparing diffusion coefficient D of NC at moisture level 73 and
93% RH (where it has value 2.2·10-6cm2/h and 1.9·10-6cm2/h, respectively), it was
observed that D has smaller values for higher moisture level (93% RH). The filler effect on
the coefficient D is small, but it can be seen that D decreases with increasing the CNT
content in the NC.
During research it was established that absorbed moisture affects the NC mechanical
properties considerably. However, NC improvement because of CNT is minimal, and
nanofiller content in our case doesn’t show significant effect.
120
MICROSTRUCTURE AND PROPERTIES OF BACTERIAL
CELLULOSE
L. Belkova1, R. Treimane2, P. Semjonovs2, I. Denina2, A. Treimanis1, U. Grinfelds1
1 - Latvian State Institute of Wood Chemistry, Riga, Latvia, [email protected]
2 -Latvia University Institute of Microbiology and Biotechnology, Riga, Latvia
Bacterial cellulose (BC) is often called a masterpiece of nature’s art. Since its
remarkable properties were found fifteen years ago, the interest has steadily increased. BC,
an exopolysaccharide produced by bacteria of genera Komagataeibacter (previously
known as Gluconacetobacter), Aerobacter et al., possess excellent mechanical properties,
water holding properties and good biological affinity. It can be obtained in higher purity
and exhibits a higher degree of polymerisation and crystallinity index as compared to plant
cellulose.
In this study BC was produced by a Komagataeibacter hansenii strain isolated from
Kombucha black tea. The basic growth medium used for the strain was Hestrin and
Schramm (HS) medium which consisted of 20 g/L glucose, 5 g/L peptone, 5 g/L yeast
extract, 2.7 g/L Na2HPO4 and 1.15 g/L citric acid. Inoculum was prepared by transferring a
single colony from the HS working culture plates into 100 ml of HS medium in 500-mL
bottles and incubating the culture at 30 oC for 7 days. Then the cellulose was purified by
treatment with 0.5 M NaOH at 90 oC for 1 h, followed by washing with deionised water to
remove medium components.
In the study, SEM microscope “Vega TS 5136M” with Au sputtering was used.
The samples of BC were prepared in the form of thin 40-400 µm films. The films
consisted of lamellar structures, formed by long cellulose fibrils. The quantity of lamellas
throughout the film thickness was 2-5 units. Width of cellulose fibrils was100-150 nm, and
length could reach 50 µm. Fibrils were strictly oriented in lamella, while in the film,
different lamellas can differ among themselves in terms of fibrils’ orientation. However, on
the whole, the films may be considered to be mainly oriented. In some regions of the film,
partially globular structures were observed (obviously, due to the effect of the mechanical
mixing of suspensions).
The BC films exhibited high water retention values and tensile strength.
Fig. 1. Bacterial cellulose film.
Fig. 2. Fibrillar structure of the bacterial cellulose.
Acknowledgements. The microstructure study was performed in the framework of the State Research
Programme “NatRes”, and the microbiology part – ERAF Project No.108 “Application of Natural
associations of Microorganisms for the Acquisition of Polyfunctional Synbiotic Drinks of Mass Consumption
and Their Concentrates”.
121
ELECTRODEPOSITION OF CdSe NANOFIBERS AS PHOTOACTIVE MATRIX FOR POLYMER SOLAR CELLS
J. Kois, S. Bereznev, J. Gurevits, E. Mellikov, A. Öpik
Department of Materials Science, Tallinn University of Technology, Tallinn, Estonia,
[email protected]
Bulk heterojunction solar cells based on composites of inorganic photoabsorber
nanoparticles (A2B6, etc.) and conjugated polymers are attractive due to their solution
processability as well as the ability to tune each component in order to achieve composite
films optimized for solar energy conversion.Using semiconductor nanoparticles or
nanomatrix as electron acceptor combined with the polymer as the electron donor gives
these devices the additional advantage that light is absorbed by both components [1].
CdSe is an important A2B6 semiconductor with high absorption coefficient and nearly
optimum band-gap energy (1.7 eV), and is a prospective material for fabrication of
photovoltaic devices based on stable CdSe nanodots and nanofibers [1-2].
Self-assembled arrays of CdSe nanofibers with diameter of 40 nm and length around
2 μm were electrodeposited onto glass/ITO substrates in aqueous media. Thermal
treatments of CdSe nanofibers were applied and the influence of treatment on morphology,
optical and electrical parameters were investigated. Scanning electron microscopy (SEM)
study of CdSe structures revealed the change in the morphology of CdSe structures from
nanofibers to pearl chain-like nanostructures after thermal treatment at 350 °C in air. Also
CdSe nanostructures were characterized by UV–VIS absorption spectroscopy and X-ray
diffraction spectroscopy (XRD). The poly(3-octylthiophene) (P3OT) functional layers
were deposited on CdSe nanowires by spin-casting technique to prepare hybrid
photovoltaic (PV) structures. Obtained CdSe nanowires/P3OT PV structures were
characterized and partially optimized by additional post-deposition thermal treatment.
Fig. 1. SEM images of CdSe nanofiber films: (a) electrodeposited and annealed (b) at 250 °C, (c) 350 °C and
(d) 410 °C.
Acknowledgements.We are grateful to the financial support from the Estonian Science Foundation (G8655
and G8714).
References
1. S. Dayal, N. Kopidakis, D.C. Olson, D.S. Ginley, G. Rumbles. Nano Lett., 10, 239-242 (2010).
2. S.K. Min, S. Joo, R.S. Mane, K.D. Jung, C.D. Lokhande, S.H. Han. J. Photochem. Photobiol. A, 187,
133-137 (2007).
122
FORMATION AND CHARACTERIZATION OF PECTIN-ZEIN
MICROSPHERES
J.T. Bobokalonov1, J. Liesiene1, Z.K. Mukhidinov2, G.F. Kasimova2,
A.S. Nasriddinov2
1
[email protected]
2
Institute of Chemistry named after V.I. Nikitin, Academy of Sciences, Dushanbe, Republic of Tajikistan
Improving delivery techniques that minimize toxicity of a drug has a significant effect
on its efficacy [1]. The application of natural polymers as materials with low toxicity,
biocompatibility and biodegradability for tailoring a drug carriers are one of priorties of
parmacetical industries. Several our works have been published relating to the application
of natural polymers, such as proteins and polysaccharides, for drug carrier development
[2,3].
In this work high methoxyl apple pectin and corn zein were used for the preparation of
microspheres. Pectin-zein (P/Z) microspheres were formed using two methods: a) by
mixing of pectin solution to an ethanolic solution of zein containing CaCl2 (30 mg Ca2+ per
g of pectin) at room temperature, and b) by dropwise adding an aqueous pectin solution to
an ethanolic solution of zein containing bivalent metal ions (CaCl2, ZnSO4). The resulting
microspheres were washed with water and EtOH (50 vol %) in order to remove non-bound
components and dried at 25–30°C [2].
The microspheres formation was characterized by means of FTIR spectroscopic,
microscopic and turbidimetric methods. From the data obtained it could be suggested that
the microspheres are of the core-shell structure. The pectin is in the core of a microsphere
and the shell is formed by zein.
The model drug piroxicam (PX) was encapsulated within core-shell microspheres by
adding PX to zein etanolic solution during the preparation of the microspheres. Drug
release study shows that the release rate of PX in vitro does not depend on the ratio of the
biopolymers in the range of P/Z 1:2 to 6:1. This is probably because of a hydrophobic
interaction between methyl groups of methoxyl pectin and hydrophobic parts of zein.
Moreover, hydrophilic groups of zein are able to interact with that of pectin by hydrogen
bonding, which contribute to retard the release of the drug at the low pH. Both swelling
behaviors and drug loading efficiency were found dependent on P/Z ratio: the more zein in
complex, the less swell the beads. The presence of zein suppressed beads swelling.
Whereas, drug loading efficiency increased as zein fraction increased in the complex. From
overall results of kinetics and physical characterization, it can be concluded that the P/Z
microspheres developed can be used as a drug carrier. A further study on morphology,
temperature stability and drug targeting is under progress.
Acknowledgements.The authors J.T. Bobokalonov and J. Liesiene are thankful to Research Council of
Lithuania for funding support in the frame of the project “Postdoctoral Fellowship Implementation in
Lithuania”.
References
1. C. Kaparissides et al. Journal of Nanotechnology online. 2, 1-11 (2006).
2. Z.K. Mukhidinov et al. Pharmaceutical Chemistry Journal, 44, 564-567 (2011).
3. Z.K. Muhidinov et.al. In: Gum and Stabilisers for the Food Industry, 16, RSC Publishing, Cambridge
UK. ed. P.A. Williams and G.O. Fillips, 401-406 (2012).
123
COLOUR PROPERTIES OF DYED RAW LINEN FABRIC
PRETREATED WITHENZYMES
A.Bernava1, S. Reihmane2
1
2
Institute of Polymer Materials,Riga Technical University, Riga, Latvia, [email protected]
Institute of Polymer Materials,Riga Technical University, Riga, Latvia, [email protected]
Linen textiles appear to be some of the oldest in the world: their history goes back
many thousands of years and dyed flax fibers founded in a prehistoric cave in Georgia
suggest the use of woven linen fabrics earlier to 36,000 BC. Nowadays flax fibers return in
the fashion industry thanks to freshness, comfort and elegance of linen clothing. Flax
industry is very important for the development of Latvian economy, due to broad range of
application of flax fibres and seeds.
Textile processing industry is one of the major environmental polluters.There are
several new technologies using enzymes, able to modify fiber parameters, achieve desired
properties and improve processing results and ecology in the area of bast fibre processing
and fabric finishing [1]. Only few researches are devoted to the influence of enzymes treatment
on dyeing processes. Direct dyes are popular for cellulosic fibers dyeing due to easy use.
Lack of these dyes is only moderate colour fastness characteristics [2].
The aim of our investigation is assessment of enzymes treatment influence on raw
linen fabricdyed with thetriad ofdirectSolphenyl dyes (Yellow GLE, Blue FGLE and
Scarlet BNLE 200 %) colour and colour fastness properties.
For experimentsraw linen fabric in plain woven technique with fabric surface density
of 162.8 g/m2 modifiedwith cellulose and pectinase (1% and 2%) solutions in waterwas
used. The dyeing of pre-treated samples was performed by exhaustion procedure according
to the recommendation of dye producer (bath ratio 50).
The enzymes pre-treated and supplementary dyed samples before and after washing (5
and 10 times in standard solution of olein soap and sodium carbonate) were tested with
Easy Colour QA device, to determine L*, a* and b* values in CIELab - 76 colour
space.Calculated lightness difference (L*), common colour differences (E), colour
saturation (C) and hue (H) show the influence of pectinase and cellulase enzymes
treatment on effectiveness of colour.
The influence of enzymes is different and depends on used dye. For example, lightness
of red fabric modified with 1% pectinase enzyme after 5 washing cycles is invariable in
comparison with untreated sample when reduce is 26%. After 10 washing cycles major
decrease of lightness (36-40%) is observed for yellow fabric modified with both enzymes
(2% solution).
The colour fastness to rubbing of dyed samples was tested under wet and dry
conditions with testing device AATCC Crocmeter M238AA. The dry colour fastness to
rubbing is higher than wet. It varies from excellent 5/5 for fabric dyed with Blue FGLE,
modified with 1% cellulase enzyme to 3/4 for fabric dyed with Scarlet BNLE 200 % and
Yellow GLE dye modified with both enzymes.
References
1. J. Marek, V.Antonov, M.Bjelkova, P.Smirous., H.Fischer, S.Janosik, Abstr .of Int.Conf. on Flax and
Other Bast Plants, 159-169 (2008).
2. D. Fakin, A. Ojstršek Color.Techn. 124, 216-222 (2008).
124
THE EFFECT OF NANOSTRUCTURED OXIDE BASED MODIFIER
ON THE STRUCTURE AND PROPERTIES OF THERMOPLASTIC
POLYMERS
I. Bockovs1, R. Merijs Meri1, J. Zicans1, R. Berzina1, J. Krastins2, I. Zalite2
1
2
In recent years there is an increasing interest in polymer nanocomposite research.
Much effort has been devoted to the investigation of structure and exploitation properties
of polymer nanocomposites. This has been resulted in increased use of polymer
nanocomposites for various commercial applications. At present moment polymer
nanocomposites have penetrated almost in every field of life – medicine, sport and leisure
industry, electronics and electrotechnics, construction and building industry, packaging,
automotive industry etc. Consequently one should consider that polymer nanocomposites
once will find themselves in the waste stream. Besides it should be taken into the account
that, due to decreasing natural resources, in future the development of industry demanded
materials should be based on the use of secondary materials. On this score, in spite of the
fact that broad spectrums of various thermosetting and thermoplastic polymers are
presently used as matrices of polymer nanocomposites, undisputable advantage should be
given to thermoplastics, considering that they can be recycled.
The current research addresses some of the above mentioned issues. Post-consumer
beverage bottles originated recycled polyethylene terephthalate (RPET) is used as matrix
for the development of polymer nanocomposites. Metallurical wastes are used for
manufacturing of various functional magnetic nanofillers by plasma synthesis (MWNF).
RPET/MWNF nanocomposites have been obtained by melt compounding using twin screw
extruder. MWNF content in the RPET matrix has been changed from 0 to 5 wt. %.
Calorimetric, mechanical, dielectric and magnetic properties of RPET/MWNF
nanocomposites have been investigated.
Results of the investigation show that at the presence of MWNF composites possess
certain paramagnetic behaviour. Besides it, by addition of MWNF, Young’s modulus and
strength of the composites are increased. Ultimate deformation of the investigated
nanocomposites remains practically intact unless the content of MWNF is below 5 wt. %.
Acknowledgements.The research is carried out within the framework of the ERDF project Nr.
2010/0209/2DP/2.1.1.1.0/10APIA/VIAA/028
125
DEVELOPMENT OF A SURFACE IMPRINTING STRATEGY BASED
ON A COVALENTLY IMMOBILIZED PROTEIN
R. Boroznjak, A. Tretjakov, V. Syritski, J. Reut and A. Öpik
Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia
Preparation of surface imprinted polymers (SIPs) has been shown to be the most
promising way for protein-recognition material synthesis[1-3]. Use of an
electropolymerisation technique for preparation of SIPs allows to easily integrate their with
different sensor transducer surfaces providing possibility for real-time label-free
monitoring of the binding events. In order to create IgG-SIP thin films we proposed a
surface-imprinting strategy based on covalent immobilization of IgG on a gold surface via
a cleavable linker followed by electrochemical formation of a nanometer thin polymer
film. The removal of IgG was then carried out by destruction of the linker cleavable bond
so that complementary binding sites were created on the surface of the film. It was
reasonably supposed that the linker cleavage procedure might be a critical step affecting
dramatically polymer matrix and consequently IgG-SIP recognition properties. Therefore
the stability of the polymer film under the conditions of the linker cleavage treatment
should be carefully investigated in order to avoid polymer degradation during the IgG-SIP
preparation.
In this study different cleavable linkers such as disuccinimidyl tartrate (DST), 3,3´dithiobis[sulfosuccinimidylpropionate]
(DTSSP)
and
ethylene
glycolbis(sulfosuccinimidylsuccinate) (Sulfo-EGS) were used to covalently immobilize
IgG on a gold surface and two electrosynthesized polymers PEDOT/PSS and polypyrrole
(PPy) were used as a matrix for imprinting. The influence of linker cleavage conditions
such as treatment in mercaptoethanol for DTSSP, sodium metaperiodate for DST,
hydroxylamine for Sulfo-EGS on the stability of PEDOT and PPy thin films was
investigated using electrochemical techniques: cyclic voltammetry and impedance
spectroscopy. It was found that PEDOT/PSS films were stable under hydroxylamine
treatment cleavage but they could not withstand the sodium periodate treatment.
Acknowledgements. The financial support of the Estonian Ministry of Education and Research (grant
PUT150) is gratefully acknowledged.
References
1. R. Schirhagl, P.A. Lieberzeit, D. Blaas, F.L. Dickert, Adv Mater, 22, 2078-2081 (2010).
2. A. Nematollahzadeh, W. Sun, A. Aureliano, et al. Angew. Chem. Int. Ed. 50 (2), 495-498 (2011).
3. G. Ertürk, L. Uzun, M.A. Tümer, R. Say, A. Denizli, Biosensors & Bioelectronics, 28, 97-104 (2011).
126
THE INVESTIGATION OF KNITTED MATERIALS BONDED
SEAMS STRENGTH UNDER BIAXIAL TENSION
G. Busilienė, E. Strazdienė, V. Urbelis
Department of Clothing and Polymer Products Technology, Kaunas University of Technology, Kaunas,
Due to new and innovative technological achievements in clothing and textile
industries stitched seams are successfully replace by seamless adhesive joints. Currently
the most widely used Bemis thermoplastic adhesive films are made from polyurethane,
polyester, polyamide, polyolefin and vinyl. Such bonded seams are lighter in weight, are
washable, resistant to dry cleaning, retain soft hand and offer high rigidity and strength in
different knitted fabrics, as well as in coated and laminated materials. Bonding conditions:
temperature, duration, pressure and seam type are specified taking into account the
composition of the film and materials to be joint [1 – 3].
In order to simulate the deformation behavior of knitted materials during product
exploitation biaxial deformation method performed by punching is oftenly applied [4 – 5].
Bonded seams maintained stretching impact on both transverse and longitudinal directions,
the strength of bonded seam was characterized by the first breaking point. The paper
presents the investigations of knitted materials bonded seams mechanical behavior under
multicycle biaxial tension by changing the directions of seam components what effects
materials strength, deformation-relaxation behaviour and residual deformation
characteristics. Thus, the goal of this investigation was to determine strength
characteristics of polyester/elastane knitted fabrics systems and their bonded seams under
biaxial tension. The objects of the investigation were two flexible polymer materials of the
same in fiber composition (93 % PES, 7 % EL), but different in knitting patterns (plain
jersey and rib 1×1). Bonded overlap seams were performed with parallely and differently
oriented knitted material strips, joined by polyurethane thermoplastic film. Multicycle
punching tests were performed with special device, attached to standard tension machine.
Testing conditions: Pc = 50 N; number of punching cycles – 50.
The results of multicycle punching tests show that cyclic punching characteristics were
mostly influenced by thermoplastic polyurethane film, rather than flexible polymer
material directions in bonded seams.
References
1. R. Korycki. FIbres & Textiles in Eastern Europe, 5 (88), 112-116 (2011).
2. Ž. Jakubčionienė, V. Masteikaitė. Materials Science, 1, 76-79 (2010).
3. Ž. Jakubčionienė, V. Masteikaitė, T. Kleveckas, M. Jakubčionis, U. Kelesova. Materials Science, 2, 7679 (2012).
4. E. Strazdienė, M. Gutauskas. Textile Research Journal, 73 (6), 530-534 (2003).
5. E. Strazdienė, M. Gutauskas. International Journal of Clothing Science and Technology, 3/4 (13), 176185 (2001)
127
MULTIFUNCTIONAL BLENDS FOR COMPACT WET FINISHING
OF LEATHERS
M.Crudu1, C.Gaidau1, A. Crudu1, M. Popescu2, M. Ionescu3
1
INCDTP-Leather and Footwear Research Institute (ICPI), Ion Minulescu St. 93, 031215, Bucharest,
Romania, [email protected]
2
S.C. PIELOREX SA Jilava, Romania
3
SC EUROPLASTIC LTD, Bucharest, Romania
This paper presents experiments of using new blends for wet finishing of bovine
leathers in compact system. The blends were obtained by means of original technologies
using low-cost raw materials (even wastes from the leather industry, as well as other
industries). Using these materials in leather processing leads to many economic (low cost),
environmental (reduction or elimination of potentially toxic substances), technical and
social (with implications starting from tannery workers who will no longer handle toxic
substances to end-users of leather items) advantages.
- Wet multifunctional materials were obtained and tested for wet finishing of hides
with retanning, fatliquoring and dyeing properties;
- Reduction of sulphates in the effluents from compact retanning was 45%-75% and
reduction of chloride 55%-60%;
- Chromium salts from effluents are completely reduced in the case of compact FOC
(free of chrome) leather;
- Reduction of ash content in the effluents from compact retanning was 47%-60%;
- The leather wet finishing with newly multifunctional materials gave comparable
physical properties to classical retanning.
- The economic effects to applying compact materials and technologies of bovine
leather wet finishing are significant and refer to reducing processing time by 45%, water
consumption by 30%, labour by 40%, auxiliary materials by 30%.
Acknowledgement. This work was supported by a grant of the Romanian National Authority for Scientific
Research, CNDI–UEFISCDI, EUREKA project number 307/2011
References
1. K.H. Munz. XXII IULTCS Congress, Brasil, 363 (1993).
2. H. Csnaka. UNIDO, Ljubljana (1995).
3. D. Papa Konstantinou, D. Tecnologie Conciane, March-April, 83-85 (2001),
4. S. Rajamani and T. Ramasami. World Leather, May, 37-39 (2007).
5. TFL Eco Guidelines (2011), Salt & Nitrogen Reduction in the Leather Making Process,
[email protected].
6. M. Crudu, C. Gaidau, A. Crudu, M. Popescu, M. Ionescu, V. Valeika, V. Plavan. Conference Chemistry
and Chemical Technology, Kaunas, Lithuania (2012).
128
LEATHER FINISHING WITH FIlLM FORMING POLYMERS
DOPED WITH NANO PHOTOCATALYSTS
C. Gaidau, A. Petica, M. Fleancu, C.Sendrea, A.M.Mocioiu*, M.Ionescu**
Department of Leather Research, *INCDTP-ICPI Division, Bucharest, Romania, [email protected]
**S.C. EUROPLASTIC L.T.D., Bucharest, Romania
Over the last few years the use of photocatalytic coatings based on nano TiO2 has
gained great attention due to the possibility of photo decomposition of organic soils as
ecological alternative to solvent use [1,2].Leather industryrepresents a new area of
application of nano materials doped film forming polymers with photocatalytic properties
for consumer goods.
The paper presents the method of synthesis and main characteristics of nano TiO2 with
enlarged photocatalytic activity in UV domain shifted to Vis wavelength, by doping it with
different N generators. In order to acquire more information about the reactions of the
photocatalyst materials with photon energies, UV-Vis diffuse reflectance spectra were
recorded.
The photocatalytic degradation under UV irradiation (λ=365 nm) for a 20 ppm Orange
II dye solution, in the presence of 0.1 g/L TiO2 and doped-TiO2 was measured in time by
UV-Vis absorbance spectra and allowed to select the nano doped-TiO2 as the best variant.
The optimization of film forming acrylic polymers doped with nano TiO2 by different
leather surface finishing methods is presented in connection to the photocatalytic activity.
The photocatalytic decomposition of Orange II dye and pen ink as organic soil models
under UV-Vis irradiation for 167 hours allowed to select the nano TiO2 concentration and
finishing technology. The SEM (Fig.1), EDAX, contact angle analyses of leather surface
finished with doped polymers showed the film characteristics and composition.
Fig. 1. The SEM images of leathers finished with film forming polymers control (left) and sample (right).
The color analyses of irradiated leather surfaces were measured by Datacolor Check II
Instrument with color management software interface (Datacolor) and showed a decrease
from 23.3 to 13.6 of yellowness indicator as effect of photocatalytic activity.
Contact angle measurement results proved that the hydrophobic leather surface
properties increase with positive effect on soil repellency behaviour.
These results proved the soil repellency property of leather surface finished with
nanoparticles doped polymers.
Acknowledgements. This work was supported by a grant of CNDI– UEFISCDI, project number PN167.
References
1. Y. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C: Photochem. Rev., 1, 9-17 (2000).
2. B.O.Bitlisi, A.Yumurtas, J. Soc. Leather Technol. Chem, 92, 183-186 (2008).
129
NEW GUANIDINE-CONTAINING POLYMER SORBENTS
M.Gorbunova, T. Batueva
Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia,
[email protected]
Compounds containing quanidine groups show a broad spectrum of bactericide effects,
and they are used as medicines and fungicides [1–3].Theguanidine-containing compounds
are stable to heat, which are the good additives for polymer materials. Moreover such
alkylguanidines attract the attention of researchers as extraction agents and sorbents of
dicyanoaurate ions from aqueous and alkaline solutions [4, 5]. That is why quanidine
group introduction into high molecular-weight compounds is undoubtedly of interest. New
allyl monomer, 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride (AGC), shows promise
for this purpose.
2,2-Diallyl-1,1,3,3-tetraethylguanidiniumchloride was found to be copolymerized with
N-p-carboxyphenylmaleimide and N-phenylmaleimide in the conditions of free-radical
initiation, the copolymers being characterized by statistical distribution of monomer units
with high tendency of the comonomer units toward alternation in the polymer chain.
The structure of the polymers obtained was identified by NMR 13C. Analysis of the
values of chemical shifts of the signals and their multiplets shows AGC to copolymerize
with N-p-carboxyphenylmaleimide and N-phenylmaleimide both double bonds
participating. Cyclolinear copolymers obtained are soluble owing to intramolecular
cyclization when formation of the polymer chain and to the absence of intermolecular
crosslinks.
Physicochemical and functional properties of 2,2-diallyl-1,1,3,3-tetraethylguanidinium
chloride copolymers have been investigated. Specific surface area and porosity of the
copolymers under investigation have been determined by using the low temperature
adsorption method. Electron microscope investigations in surfaces of the polymers have
evinced that they have a spongy microstructure.
Sorption capacity of the copolymers toward Re(VII) ions has been investigated. The
process is described by the Langmuir isotherm. The pH is the most important parameter for
sorption process of Re(VII). In the conjoint presence of Re(VII) and Mo(VI) in a solution
of acid and ammoniac mediums, rhenium can be separated from molybdenum by using the
sorbents under investigation at pH > 4.5 or at hydrochloric acid concentrations 0.1 mol L-1
and more.
Acknowledgements. Financial support by the Russian Foundation for Basic Reseach (grants № 11-0396001-r_ural, 11-03-96003-r_ural) is gratefully acknowledged.
References
1. Chemical Encyclopedia. Ed. by I. L. Knunyants, Sovetskaya Entsiklopediya, Moscow (1988).
2. T. Ikeda, S. Tazuke. Polym Prepr., 26, 226-227 (1985).
3. P. Gilbert, L.E. Moore. J Appl Microbiol., 99, 703-715 (2005).
4. Patent USA № 5198021 (1993).
5. A.V. Golounin, I.A. Larionova. International Symposium on Sorption and Extraction, Vladivostok, 28-30
(2008).
130
NEW LUPANE-CONTAINING POLYMERS FOR MEDICAL
APPLICATION
M. Gorbunova, G. Krainova, I. Tolmacheva, V. Grishko
Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia,
[email protected]
Triterpene derivatives of lupane type are of significant interest due to the broad
spectrum of their biological properties and availability of nature compound – betulin.
Betulin and its derivatives can be used as medical drugs. Betulinic and betulonic acids
have proved to possess antitumoral and antiviral activities[1-3]. That is why triterpene
introduction into soluble polymer matrix is undoubtedly of present interest.
It was found that betulonic and 2-hydroximinobetulonic acids react with allylamine
with formation of allylamides of corresponding acids. Allylamides of betulonic (AAB)
and 2-hydroximinobetulonic acids (AAHB) were found to be not homopolymerized but
copolymerized at low rates with N-vinylpyrrolidone (VP), vinylacetate (VA), acrylonitrile
(AN) in the presence of free-radical initiators.
It was determined that at AAB and AAHB copolymerization with VP and AN in the
conditions of free-radical initiation the copolymers are characterized by statistical
distribution of monomer units.The rate of copolymerization of AAB and AAHB with VP
and AN significantly reduces with increase in the molar fraction of allylamides in an initial
monomer mixture.The rate of copolymerization of allylamides with AN is higher than that
of allylamides with VP.Investigation carried out showed that low rates of AAB and AAHB
with VA copolymerization are observed. In this case, particularly at copolymerization
during 10 hours, the polymer yield does not exceed 5 %.
Investigation of biological properties of copolymers shows that AAB with VP
copolymer has a 4-fold higher cytotoxic activity with respect to melanoma MS compared
with initial AAB and can be used in medicine and biotechnology.
Acknowledgements. Financial support by the Russian Foundation for Basic Reseach (grant № 11-03-96003r_ural_а) and youth project of Ural Division of RAS (№ 13-3-NP-59) is gratefully acknowleaged.
References
1. Т.G.Тolstikova, I.V. Sorokina, G.А. Tolstikov, А.G. Tolstikov, О.B. Flekhter. Rus. J. Bioorg. Chem.,
32(3), 261-276 (2006).
2. P.A. Krasutsky. Natural Product Reports, 23(6), 919-942 (2006).
3. S. Alakurtti, T. Mäkelä, S. Koskimies, J. Yli-Kauhaluoma. Europ. J. Pharm. Sciences, 29(1), 1-13 (2006).
131
NANOSTRUCTURED ZnO CONTAINING ELASTOMERE
MODIFIED POLYOXYMETHYLENE COMPOSITES
A.Grigalovica1, R.Merijs Meri1, J.Zicans1, J.Grabis2
1
2
In different industries there is a demand for new functional materials with advanced
properties. Properties of materials can be significantly improved by introduction of
nanostructured additives in the matrices of common polymers.
Polyoxymethylene (POM) is an excellent engineering thermoplastic, which is
considered as an alternative for metals in many applications due to its good mechanical
characteristics, chemical resistance, low wear and self-lubricating properties. Modification
of POM with ZnO can further improve tribological, elastic, thermal and weathering
properties of the material. At the same time POM and its nanocomposites could be
insufficiently ductile at low temperature range. Therefore it is often necessary to modifiy
POM with elastomers.
In our work we used ethylene octene copolymer (EOC) to modify POM. Elastomer
content in this blend was changed in the interval from 10 to 50 wt.%. Various POM/EOC
blends were modified with ZnO nanofiller to improve mechanical and thermal properties
of the composite. The content of ZnO in the composite was changed from 0 to 5 wt.%.
Results of the investigation show that certain amount of elastomer additive (up to 30
wt. %) allows improving impact toughness of the composites.Addition of ZnO nanofiller in
the amount of 2-5 wt. % allows improve stiffness, strength and thermal resistanceof the
investigated nanocomposites.Properties of ZnO modified composites unfortunately are
strongly affected by incompatibility of it ingredients, especially at higher EOC content.
Acknowledgements.This work has been supported by the European Social Fund within the project «Support
for the implementation of doctoral studies at Riga Technical University».
132
CELLULOSE-BASED HYDROGELS FOR WOUND DRESSING
S. Gustaite1, J. Kazlauske1, J. Liesiene1, M. Nasiri Boroumand2, V. Dutschk2
1
Kaunas University of Technology, Radvilenu pl. 19, LT-50254
[email protected]
2
Twente University, Drienerlolaan 5, 7522 NB Enschede, Netherlands
Kaunas,
Lithuania,
e-mail:
Wound healing is a complicated process of cells degradation and regeneration. Wound
dressings are usually used to promote re-assembly of the connective tissue and epidermal
layer and create favorable conditions for healing. Numerous materials and biomaterials
have been developed for use as a wound dressing. Special attention has been paid to
hydrogels. Hydrogels currently used for wound healing are believed to possess most of the
properties of an ideal wound dressing: an immediate pain control, a control of drug dosage,
transparency toallow healing follow up, absorb and prevent the loss of body fluids, a
barrier against bacteria, oxygen permeability, easy removal from the wound bed, because
the moist interface between the dressing and the wound prevents dressing adherence [1].
The aim of this work was to evaluate the applicability of cellulose-based hydrogel sponges
with immobilized special additives as a wound dressing material.
In this work, a cellulose hydrogel was prepared by the regeneration of cellulose from
cellulose diacetate according to [2]. The cellulose-based sponges further were prepared by
lyophilization of the macroporous gel of regenerated cellulose. It was found out that the
morphology of the sponges depended on the conditions of their drying before and after
immobilization of active compounds. The pores of the samples dried at different conditions
varied from 20 μm to 2000 μm.Various active compounds, such as antibiotic neomycin,
tea tree essential oil, phenolic compounds from pot-marigold or chamomile, were
immobilized in the cellulosic matrix to promote wound healing processes and provide
strong antibacterial properties. Active compounds immobilized together with water-soluble
hydroxyethylcellulose or carboxymethylcelluloses were slowly released from the sponges.
In the case of the tea tree essential oil with hydroxyethylcellulose the release rate of
phenolic compounds was the slowest. This kind of the sponges can be used for wound
healing with prolonged drug release. All matrices with immobilized active ingredients
showed the antibacterial activity to Gram- (Pseudomonasaeruginosa, Escherichia coli) and
Gram+ (Staphylococcus aureus, Bacyllus cerius) bacteria.
Water contact angles and the total absorption time of a water droplet into the substrate
were measured. Samples modified with carboxymethylcellulosewere more hydrophilic and
revealed shorter absorption times compared to those modified with hydroxyethylcellulose.
The sponges fabricated were able to absorb up to 80 % of moisture.
Mechanical properties of cellulose-based sponges were studied. The tensile strength of
the samples was approx. 140 kPa and Young's modulus approx. 2.7 N/mm2.
Acknowledgment. This study is related to the activity of the European network action COST CP1101
“Colloidal Aspects of Nanoscience for Innovative Processes and Materials”.
References
1. T.D. Turner. In: Chronic Wound Care: A Clinical Source Book for Healthcare Professionals (D.L.
Krasner, G.T. Rodeheaver, R.G. Sibbald, eds): Wayne, PA, HMP Communications, 293-310 (2001).
2. Lithuanian Patent 2299 (1993).
133
CHARACTERIZATION OF STYRENE COPOLYMER BASED
NANOCOMPOSITES WITH NANOSTRUCTURED CLAY
J. Bitenieks1, R. Berzina1, T. Ivanova1, R. Merijs Meri1, J. Zicans1, V. Kalkis2
1
2
Research field on polymer nanocomposites is continuously expanding. Increasing
amount of polymer-nanofiller combinations are investigated. In recent years an interest is
devoted to polymer blends as possible matrices of polymer nanocomposites. Research on
such systems is important also from environmental viewpoint, while post-consumer
polymer waste streams usually consists from the mixture of various polymers. For an
example polymeric part from the electronic waste stream generally consists from
acrylonitrile-butadiene-styrene copolymer and its blends, polystyrene and its blends,
polycarbonate and its blends, styrene-acrylo-nitrile copolymer, polypropylene and other
engineering polymers.
This research is devoted to evaluation of the effects of layered silicate modifier,
commonly known inorganic nanofiller, on the structural and mechanical characteristics of
acrylonitrile-butadiene-styrene copolymer (ABS) blends with polycarbonate (PC).
Primary polymers have been used for manufacturing of different compositions of the
aforementioned blend. PC/ABS blend compositions, either unmodified or reinforced with
commercially available silicate nanofiller, have been manufactured by melt compounding
using twin screw extruder. The amount of ABS in the composites has been varied from 0
to 40 wt. %. The amount of commercial layered silicate nanofiller in the composite has
been changed in the range from 0 to 2 wt. %. The effects of ABS as well as nanostructured
silicate modifier on the structural and tensile stress-strain characteristics are analyzed in the
research. The effects of various technological conditions on the structure and properties of
PC based nanocomposites are also considered.
Results of the investigation show that by rising ABS content in the blend modulus of
elasticity and strength are increased, while ultimate deformation is decreased. Besides it
has been determined that optimal nanofiller content in the PC/ABS compositions is below
1,5 wt.%. Certain correlations between the indicators of the above mentioned mechanical
properties and certain structural characteristics (glass transition temperatures of the
polymeric components) of the investigated composites, explaining possible mechanisms of
the reinforcement, have been also analyzed.
134
PROPERTIES OF POLYURETHANES BASED ON TALL OIL
ESTERS WITH INTUMESCENT FLAME RETARDANTS
V. Yakushin, I. Sevastyanova, D. Vilsone, M. Kirpluks
Latvian State Institute of Wood Chemistry, Riga, Latvia, [email protected]
At present,intumescent flame retardants, instead of halogen-containing ones, tend to be
used increasingly wider in polymers [1-3]. As a rule, the choice of the most efficient flame
retardants for each type of polymers is an individual issue. This study investigates the
effect of the concentration of 3 main intumescent flame retardants and their ratio in
different combinations on the properties of polyurethanes based on tall oil esters.
Tall oil fatty acids and triethanolamine ester (OH number 349 mg KOH/g) and
polyisocyanate Voratec SD 100 (Dow Chemical) (NCO 31.5%, functionality 2.7) in the
molar NCO/OH ratio = 1.1 were used for polyurethane preparation. Ammonium
polyphosphate Exolit® AP 422 (Clariant International Ltd, BU Additives), Pentaerythritol
98% ALDRICH (Sigma-Aldrich Co. LLC.), and Melamin 99% ALDRICH, (SigmaAldrich Co. LLC.) were used as intumescent flame retardants. All flame retardants were
preliminary mixed with the polyol.
For the mechanical and thermal test, polyurethanes were prepared in the form of free
films (ASTM D 4708-99) from toluene solutions. For the flammability test, polyurethane
coatings 150-200 m in thickness were applied on 100×100×16 mm standard wood
samples.
Tensile tests of polyurethane films were performed on a universal testing machine
Zwick/Roell (500 N) according to the requirements of the standard ASTM D 882-10.
Thermal stability and glass transition temperature of polyurethanes were determined using
TGA/SDTA 851e and DSC 851e METTLER TOLEDO, respectively. Combustion
performance of the polyurethanes was studied using a FTT Cone Calorimeter (Fire Testing
Technology Ltd.). Testing was performed according to ISO 5660 at a heat flux of 35
kW/m2.
The change of tensile properties, glass transition temperature, thermal stability as well
as flammability parameters in the cone calorimeter test (MAHRE, total heat release, total
smoke release, etc.) of polyurethanes, with increasing the content of each of the 3 flame
retardants separately up to 30%, was investigated. It has been found that, at the content of
some flame retardants equal to 25%, it is possible to achieve a substantial effect of
decreasing flammability and enhancing the thermal stability of the polyurethane at not so
essential decline of its mechanical properties.
The effect of the ratios of double and triple combinations of the mentioned flame
retardants on the thermal stability and flammability of polyurethanes with a 25% additive
of flame retardants was investigated. The ratios in those combinations are established for
the flame retardants, at which the temperatures of the maximum rate of weight loss for the
final steps of decomposition and the value of the char yield at 600 °С increase to a greater
extent, but, on the contrary, flammability indexes in the cone calorimeter test (MAHRE,
total heat release, total smoke release) decline to a greater extent.
Acknowledgements.The present study was financially supported in the framework of the State Research
Program 5 “Sustainable Use of Local Resources (Mineral Deposits, Forest, Food and Transport) – New
Products and Technologies (NatRes)”.
References
1. S. V. Levchik, E. D. Weil. Polym. Int. 53, 1585-1610 (2004).
2. S. Bourbigot, M. Le Bras, S. Duquesne, M. Rochery. Mater. Eng. 289, 499-511 (2004).
3. Q. Zhang, Y. Chen. J. Polym. Res. 18, 293-303 (2011).
135
STRUCTURE AND PROPERTIES OF SILICONE ELASTOMERS
AND SILVER NANOPARTICLES COMPOSITES
V. Jankauskaitė, A. Lisauskaitė
Faculty of Design and Technologies Kaunas University of Technology, Studentu st., 56, LT-51424 Kaunas,
Lithuania
Silicones due to their biocompatibility and biodurability have found widespread
application in orthopaedic and medicine fields. Silicones are synthetic polymers whose
skeletal backbone is made up of silicon–oxygen bonds [1]. The basic repeating unit of a
linear polysiloxane molecule has the structure –(RR‘SiO)n–. The most common member of
the siloxane family is polydimethylsiloxane (PDMS), when both R and R’ are methyl
groups.PDMS has found many applications due to their unique properties, which arise
mainly from the nature of the siloxane bond (Si-O).
However, PDMS is characterized by poor mechanical properties. The reinforcing
fillers are added to overcome this problem. Most studies have been focused on the use of
synthetic and inorganic fillers such as fumed or precipitated silica, carbon black, boron
nitride, to improve silicones mechanical behaviour [2]. Much less researchers have been
turn on bio-based materials.
Interest in cellulose-reinforced nanocomposites has increased in recent years. Cellulose
is a linear-chain carbohydrate polymer characterized by a high molecular weight
homopolymer of -1,4-linked anhydro-D-glucose units. Cellulose characteristics and
chemical properties are closely associated with its molecular structure. Amorphous and
crystalline regions are present within solid-state cellulose. Amorphous regions can be
easily hydrolyzed by acid, while crystalline regions have a higher acid resistance. Using
acid treatment of cellular cellulose microcrystalline cellulose and cellulose nanocrystals
(NCC) can be produced. This material is a very promising reinforcement for polymers [3].
In this study the influence of NCC nanoparticles size and concentration on the PDMS
morphology and mechanical properties have been investigated. Nanocomposites
morphology was characterized by various methods (AFM, SEM, optical microscopy, etc.).
Nanocomposite mechanical behaviour was evaluated by tensile and compression set
testing.
It was obtained that a fairly rough surface is characteristic for NCC particles.
Overview of composite surface shows a uniform dispersion of NCC particles in PDMS
matrix. At higher filler loading MCC particles form aggregates, but in some cases
separation take place during mixing.
NCC increase PDMS tensile strength, elongation at break and compression resistance.
Degree of properties changes depend on the nanoparticles content.
References
1. Q. Chen, Sh. Liang, G.A. Thouas. Progr. Polym. Sci., 38 (3-4), 584–671 (2013)
2. D.R. Paul, J.E. Mark Progr. Polym. Sci., 35 (7), 893-901 (2010).
3. I. Siro, D. Placket. Cellulose, 17 (3), 459-494 (2010).
136
STUDIES OF BLENDS OF POLY (VINYL ALCOHOL) AND POLY
(VINYL ACETATE)
N. Jelinska1, M.Kalnins1, E.Auzins1, A. Kovalovs2
1
2
Poly (vinylalcohol)(PVA) is a hydrophilic semi-crystalline polymer produced by
polymerization of vinyl acetate monomer to form poly (vinyl acetate) (PVAc), and
subsequent hydrolysis of PVAc to PVA. PVA is a non-toxic water soluble synthetic
polymer with excellent film forming properties. PVA is a polymer for great interest
because of its many desirable characteristics specifically for various biomedical and
packaging applications [1].
PVA and PVAc composite films were prepared by casting two-componentwaterbasedsystemblends: a solutionofthe rigidPVAand emulsionofcompliant plasticized PVAc[2,
3]. Natural fillers - monmorillonite clay (MMT) and microcrystalline cellulose (MCC)
were added to PVA/PVAc blends. Diethylene glycol (DEG) is chosen as a plasticizer of
films.
Effect of adsorbed water vapor amount on elastic properties of films was evaluated in
this work. Films were stored in desiccators with following relative humidity: 60%, 75%
and 90%. Storage time in each case was determined by achieving constant moisture
content. Elastic properties of films were identified by using thin-walled cylindrical
specimens (TWCS Method).
The experiments were carried out in 96 hours. It is considered that with water content
increasing modulus of elasticity decreased for all composites films. Depending on the
nature of filler, the tendency of water vapour adsorption and changing of modulus of
elasticity is different.
For example, for PVA films filled with MMT after constant water amount adsorption
modulus of elasticity is increased with increase of MMT content. In case of PVA films
filled with MCC – modulus of elasticity has similar values.
The modulus of elasticity of clean PVA/PVAc films does not change significantly with
increase of water content.
Acknowledgements.This study was financially supported by the Latvian Ministry of Education and Science
according to Contract No. V7632.1.
References
1. M. Mohsin, A. Hossin, Y. Haik. Materials Science and Engineering A, 528, 55-61 (2010).
2. N. Jelinska, M. Kalnins, V. Tupureina, A. Dzene. Scientific Journal of Riga Technical University,
Material Science and Applied Chemistry, 1 (21), 925-930 (2011).
3. N. Jelinska, M. Kalnins. Mechanics of Composite Materials, 47, 236-250 (2004).
137
POLYOLEFIN/NANOCLAY NANOCOMPOSITE FILMS FOR
PACKAGING EXPLOITATION PROPERTIES
J. Kajaks, K. Kalniņš, E.Sidorovs
Institute of Polymer Materials, RigaTechnicalUniversity, Azenes str. 14/24, Riga, LV-1048, Latvia
About 50 % of produced polyolefins are utilized in packaging industry. Packing
materials of food products. have specific demands. These packing have to be not only high
mechanical properties but also very low gas, air and different liquids permeability: barrier
properties. Last years for packaging food stuffs are used multilayer films which do not
satisfy all requests for food products. Therefore necessary to look for new materials. One
of the way is to utilize nanocomposite materials which have excellent barrier properties,
for example polyolefines containing nanoclay particles. The aim of this work was to
investigate nanonoclay additives influence on linear low density polyethylene (LLDPE)
and low density polyethylene (LDPE) composites mechanical and barrier properties. As
polymer matrixes were used LDPE LD 171BA and LLDPE 1018 CA. As the filler was
used modified montmorillnonite (MMT) nanoclay grade DELLITE CW 9 (1, 3, 5 wt.%).
As interfacial modifier was used MAPE grade LICOCENE 4351 (Tm =1180C) with acid
group content 43 mg KOH/g. Composites were prepared by mixing of components on two
rolls mill, then cooled, granulated and pressed in 0,8-1 mm thick sheets from which were
cut off specimens for tensile tests. Fluidity was estimated by melt flow index method MFI
(T=190oC, P=2.16 kg). Water sorption experiments were done at room temperature
(+230C). For gas (N2) permeability tests were prepared films with thickness 0.1-0.25 mm
and total square of films more than 15 cm2.
Tensile test results showed that additions (1-5 wt.%) of nanoclay improve only LDPE
tensile properties (optimal concentration 2-3 wt.%), but in the case of LLDPE influence of
nanoclay on mechanical properties is negligible. To improve of the spread of clay particles
in polyolefine matrix interfacial compatibilizer MAPE (5, 10, 15 wt. %) was used which
promote of improvement of tensile properties up to 40-100 % (optimal content of MAPE
10 wt.%). Presence of nanoclay in LLDPE and LDPE decrease of composite melt fluidity
about 50-100%, but addition of MAPE increase of MFI numerical values till 1.5 times.
For optimal composition of composites LDPE+2wt.% nanoclay, LDPE+2wt.%
nanoclay+10wt.% MAPE and pure LDPE and pure LLDPE and LLDPE+3wt.% nanoclay
films were examined N2 gas permeability. Amount of gas (V) what diffuse trough films in
time of unit increase for all films, but the speed of diffusion the smallest is for composite
containing only nanoclay particles. Small increase of gas (N2) permeability to compare
with nanoclay containing system is observed for nanoclay+MAPE containing composite.
The greatest gas diffusion show pure LDPE film (difference from modified systems is
about 2 times). The greatest calculated coefficient of gas permeability (P) have LDPE, but
for two another systems P difference is very small. The smallest calculated numerical value
of diffusitivity coefficient (D) is observed for composite LDPE+2wt.% nanoclay+10wt.%
MAPE, moreover the difference from another investigated systems is nearly 5 times. In the
contrary gas solubility coefficient (S) of composite LDPE+2wt% nanoclay+10wt.% MAPE
is the highest, but the smallest S is for material containing only 2 wt.% nanoclay particles+
LLDPE film. The gas permeability this material is two times lower than LDPE. Leading
nanoclay in LLDPE matrix unchange barrier properties so strong as in the case of LDPE
matrix. As it was able to wait water uptake at room temperature during 7 days of pure
LLDPE and LDPE is low (0.02-0.07%) and for composites with nanoclay 2wt.% and
nanoclay 2 wt.%+10wt.%MAPE the increase of absorpted amount of water is negligible. It
means, that investigated nanoclay particles containing systems is not only good mechanical
properties, but also excellent barrier properties.
138
NATURAL OIL BASED POLYMERS WITH PHOSPHOESTER
CROSS-LINKS
S. Kašėtaitė, J. Ostrauskaitė, J.V. Gražulevičius
[email protected]
Among all renewable resources, natural vegetable oils are considered to be one of the
most important classes of renewable sources because of the wide variety of possibilities for
chemical transformation, universal availability, and low price and they are preferred by the
chemical industry as alternative [1].
The linseed oil and camelina oil polymers with phosphoester cross-links have been
synthesized by the reactions of the epoxydized linseed oil or epoxydized camelina oil and
1-hydroxyethane-1,1-diphosphonic acid using different molar ratios of the starting
materials. The chemical structure of the cross-linked polymers was confirmed by IR
spectroscopy. The yield of the insoluble fraction of the cross-linked polymers obtained
after Soxhlet extraction in chloroform for 72 h was ca. 80 %. The mechanical and thermal
properties of the cross-linked polymer films, and the swelling in the different solvents were
studied.
It was established that the linseed oil and camelina oil based polymers with
phosphoester cross-links are the amorphous materials with the glass transition temperatures
in the range from -5 ºC to 7 ºC. Their thermal degradation temperatures at the weight loss
of 10 % are in the range of (265-313) ºC.
The degree of swelling of the cross-linked polymers in toluene and chloroform reached
48% after 3.5 h at 18 ºC. The degree of swelling in distilled water reached only 6.5% after
3.5 h at 18 ºC.
The hardness of the polymer films measured with a Hepler consistometerranged from
40 N/mm2 to 64 N/mm2. The tensile strength of the cross-linked polymer films ranged from
4.66 MPa to 18.42 MPa. The elongation at break of the films was found to be in the range
of (20.36-49.56) %.The Young modulus ranged from 6.37 N/mm2 to 13.51 N/mm2.
The investigation of the hydrolysis and biodegradation in soil confirmed that the
linseed oil and camelina oil polymers with phosphoester cross-links are biodegradable.
Acknowledgements.This research was funded bya grant No. MIP-057/2012 from the Research Council of
Lithuania.
References
1. U. Biermann, W. Friedt, S. Lang, W. Luhs, G. Machmuller, J.O. Metzger, M.R. Klaas, H.J. Schafer,
M.P. Schneiderusch. Angew. Chem. Int. Ed., 39, 2206–2224 (2000).
139
OPTIMAL DESIGN OF POLY (VINYL ALCOHOL)/POLY (VINYL
ACETATE) BLENDS FILMS BASED ON THE PLANNING OF
EXPERIMENTS
A. Kovalovs1, A. Chate1, N. Jelinska2
1
2
Institute of Materials and Structures, Riga Technical University, Riga, Latvia, [email protected]
The aim of this work is the development of a method to design PVA/PVAc (Poly
(vinyl alcohol)/Poly (vinyl acetate)) blends containing nanofillers with predicted
properties: elastic properties and strength-deformation characteristics of a composite film.
PVA is extensively used in paper coating, textile sizing, and fabrication of flexible
water soluble packaging films. PVA has found application also in pharmaceutical,
biomedical and biochemical fields, due to its attractive characteristics, such as
biocompatibility, biodegradability and good water-solubility [1].
PVA and PVAc composite films prepared by mixing of water systems: PVA solution
and PVAc emulsion with subsequent drying at room temperature. They show wide range
of strength-deformation characteristic, which can be controlled by component ratio. Effect
of small amounts (1 - 10 wt %) of nanoparticles: monmorillonite clay (MMT) and
microcrystalline cellulose (MCC) has also had an influence on structural and strength
deformation characteristics of PVA, PVAc and PVA/PVAc blends.
The solution of the predicted properties is divided into the following stages: choice of
control parameters and establishment of the domain of search, elaboration of plans of
experiment for the chosen number of reference points, execution of the experiments
(physical experiment or computer simulation), determination of simple mathematical
models from the experimental data, design of composite on the basis of the discovered
mathematical models and at the end verification experiments at the point of optimal
solution.
In each of these stages it is possible to solve a problem by various methods. So, there
are many ways to obtain the plans of experiment. In the present investigation an
experimental approach for planning of experiments is used. The tensile tests were carried
out by a Zwick/Roell universal testing, according to EN ISO 527.
Mathematical models using data of experiments can also be obtained by various
methods. The method of polynomial approximation of the table data has been at the basis
of creating RESINT program, which was used in this research. This method is based on
selection of simple functions using least squares. [2].
Simple mathematical models obtained from data of experiments are used as objective
functions and constraints in the optimal design problem [3]. In the present investigation
penalty function method with random search is used [4].
The last stage is verification experiments in the point of optimal solution. As objective
of design also other properties of material may be used.
Acknowledgements.This study was financially supported by the Latvian Ministry of Education and Science
according to Contract No. V7909.1.
References
1. J. Cuppoletti. Nanocomposites and Polymers with Analytical Methods, In Tech, London (2011).
2. V. Eglais. Problems of Dynamics and Strength, 39, 120-125 (1981).
3. M.S. Bazarra, C.M. Shetty. Nonlinear Programming, Theory and Algorithms. Wiley, New York (1979).
4. Janusevskis, T. Akinfiev, J. Auzins and A. Boyko. Proceedings of the Estonian Academy of Science, 10
(4), 236-250 (2004).
140
DEFORMATION CHARACTERISTICS OF GENUINE LEATHER,
MANUFACTURED USING NATURAL MINERALS
O.P. Kozar 1, O.R. Mokrousova 2, V.P. Konoval 3
1
Mukachevo State University, Mukachevo, Ukraine, [email protected]
Kyiv National University of Trade and Economics , Kyiv, Ukraine
3
Kyiv National University of Technologies and Design, Kyiv, Ukraine
2
Expansion of natural leather production manufactured with the help of new
technologies creates some opportunities for production shoes with improved hygienic and
operational properties. However, properties of these skins should be studied according to
peculiarities of cutting operations, forming and fixing shoe uppers.
Deformation properties are the most important properties of leather materials, because
they largely determine the quality of basic technological operations of shoe production and
the convenience of the product and the ability to retain the form during operation. It is not
possible to optimize processes and formation of cutting because of lack of information
about the physical and mechanical properties of the skins, what indicates the urgency of
this study.
The main purpose of this work is to study the deformation properties and physical and
mechanical properties of new materials for leather uppers made using natural minerals.
Genuine leather for shoe uppers after modification with organic-mineral compositions
at the stage of filling-tanning was used. Modified dispersion of natural minerals montmorillonite and zeolite in amounts of 3 and 4% by weight of sliced semifinished rawstaff respectively was used as a filler. As a control sample natural leather for shoe uppers,
obtained by the existing technology of leather factory JSC "Chinbar" (Kyiv) was used.
Tanikor FTG was applied for processing of control skins.
The results of the established physical and mechanical properties when tested in
uniaxial tention of the skins and ball burst attachment [2,3] indicate that the breaking load
and tensile strength at break of skin with mineral filling are slightly higher than control
skin, there is a tendency to a slight decrease in absolute and relative elongation at 10MPa
and disrupture. Increase of the load and elongation at ball burst compared to the control
sample is observed. Thus, modification of semi-finished leather with montmorillonite
dispersion increases resistance by 62.2% and the dispersion of zeolite - by 36.7%.
A characteristic feature of the application of modified zeolite dispersions for filling
semi-finished leather is compression of macroporous structure. Mineral particles fill the
gaps between the structural elements of the dermis. It fills the peripheral areas effectively,
increases the thickness of finished leather, but slightly reduces the outcome of the area,
provides high rigidity, tensile strength and reduced elongation. These effects of the
introduction to the structure of the dermis can be positively used in the manufacture of
high-strength leather, density, such as the manufacture of plantar skins and leather uppers
for a special purpose.
References
1. V.V. Shcherbakov, G.K. Rukhadze, A.N. Kalita, V.A. Polischuk. Leather and Footwear Industries, 12,
19 (1989).
2. Standard 938. 11. "Leather. Tensile Test Method "
3. GOST 938.16 "Method of leather and facial layer determining with ball burst attachment".
141
EXTRACTION METHODS OF FRUCTO-OLIGOSACCHARIDES
FROM JERUSALEM ARTICHOKE TUBERS
T. Krivorotova1, J. Sereikaite1, P. Glibowski2
1
Department of Chemistry and Bioengineering, Vilnius Gediminas Technical University, Vilnius, Lithuania,
[email protected]
2
Department of Milk Technology and Hydrocolloids, University of Life Science, Lublin, Poland
The Jerusalem artichoke (Helianthus tuberosus L.) (JA) is a member of the same
Compositae family as the sunflower (H. annuus L.). The plant grows under different
pedoclimatic conditions and shows a good frost and drought tolerance as well as a
resistance to pests and diseases. The JA is a high biomass yielding plant. Moreover, JA
tubers do not contain starch and accumulate carbohydrates as inulin that has a positive
physiological effect in humans. Thus, JA tubers can be used for food or animal feed, as a
raw material for the industrial production of fructose and fructans [1] or as a source of
bifidogenic factors in human nutrition [2].
The purpose of the study was to investigate the composition and purity of FOS
extracted from Jerusalem artichoke (JA) flour using HPLC and NMR spectroscopy.Two
genetic variants of JA, i.e. Albik and Rubik, which were cultivated in Lithuania, were used
for investigation.
Four methods were used for the extraction of free sugars and FOS from JA flour. The
first extraction method of FOS was carried out in distilled water at 86ºC for 30 min, and
the extracts after separation from plant pulp were dried. In the next methods extracts
separated from plant pulp were additionally blenched with activated carbon or acidificated
to pH~4 to decrease the Maillard reactions and then activated carbon was added [3]. In the
last method FOS (without free sugars) were precipitated from extracts using ethanol or
acetonitrile.
The 1H NMR analysis suggests that more pure FOS was obtained by precipitation
method. In the case of first three methods some organic and amino acids such as
glutamine, arginine, valine, citric acid and fructose were found. The overlapping of protons
signals of free Fru and FOS makes difficulties to determine the average degree of FOS
polymerization (DP). However, in the case of precipitation method FOS did not contain
free fructose. Therefore, FOS protons signals were obtained without overlapping. Proton
integration of the H-1 signals of terminated Glu at 5.44 ppm and the H-3 (or H-4) signals
of fructosyl residue at 4.27 (or 4.11) ppm suggested the following means of DP: 15 (Albik,
precipitant ethanol), 23 (Albik, precipitant acetonitrile). The average degree of FOS
polymerization determined by HPLC was as follows: 10.2 (Albik), 8.0 (Rubik), dried
extracts; 10.5 (Albik), 8.0 (Rubik), second extraction method; 10.2 (Albik) 10.8 (Rubik),
third extraction method; 9.7 (Albik), 13.4 (Rubik), fourth precipitation method.
Acknowledgement. Postdoctoral fellowship is being funded by European Union Structural Funds project
”Postdoctoral Fellowship Implementation in Lithuania”.
References
1. Z.-M. Chi, T. Zhang, T.-S. Cao et Al. Bioresource Technology, 201, 4295–4303 (2011).
2. Z. Zalan,J. Hudacek, J. Sci. Food Agric., 91, 672–679 (2011).
3. M. Tchone, G. Barwald, C. Meier, British Food J., 693, 701 (2005).
142
SELF-ASSEMBLING DIBLOCK COPOLYMERS AS VEHICLES FOR
POORLY SOLUBLE DRUGS
L. Kunitskaya, T. Zheltonozhskaya
Department of Chemistry, TarasShevchenkoNationalUniversity of Kyiv, Kyiv,Ukraine,
[email protected]
Amphiphilic block copolymers consisting of hydrophilic and hydrophobic components
are well established for the preparation of micellar drug carriers. The application of
micelle-type polymeric nanocontainers is considered as one of the most perspective ways
to realize the targeted delivery of toxic water-insoluble drugs into certain cells of living
organisms.
It was shown earlier that asymmetric triblock (TBC) copolymers contain
biocompatible chemically complementary polyacrylamide and poly(ethylene oxide)
(PAAm-b-PEO-b-PAAm) formed special micellar structures in aqueous solutions [1].
The present work focuses on the study of bulk structure and self-assembly symmetrical
diblock copolymers MOPEO-b-PAAm enclosed polyacrylamide (PAAm) and
monomethoxy-poly(ethelene)oxide (MOPEO). Block copolymers of such type belong to
the intramolecular polycomplexes which have hydrophobic areas of binding between
PAAm and PEO blocks and hydrophilic units of PAAm chains. Their self-assembly in
solutions form the spherical micelles capable of binding most of organic molecules and
inorganic ions.
Structural investigations have been carried out by the differential scanning calorimetry
(DSC). Four samples of PAAm-b-MOPEO with different length of MOPEO blocks
(MvMOPEO=7,5102÷5,0103) have been investigated. The therminal transitions observed
in copolymers before the beginning of thermal-oxidative degradation were studied. The
lack of crystalline phase on the DSC thermogramms and comparative analysis of glass
transition parameters in copolymers and individual PАА shows the total compatibility of
the polymer components in the samples i.е. the homogeneous structure of diblock
copolymers. The destruction of crystalline ranges of MOPEO in structure of diblock
copolymers proves the interaction between MOPEO and PAAm blocks.
By the viscometry it has been established that adding of dimethyl formamide to the
water solutions of MOPEO-b-PAAm leads to decrease of viscosity for all samples because
of H-bonds destruction between PAAm and MOPEO blocks. Investigation of
water/alcohol solutions of MOPEO-b-PAAm shows that tendency to micelle formation
depends on the length of MOPEO block and increases with increasing molecular weight of
MOPEO. It was determined that NaCl solution simplifies the association of MOPEO-bPAAm macromolecules as compared to water.
In order to estimate the binding ability of MOPEO-b-PAAm micelles with respect to
toxic hydrophobic drugs their action with one of the most effective anticancer agent
doxorubicin (DOX) has been examined. The essential influence of doxorubicin on DBC
micelle formation due to interaction between DOX and DBC was established. It offers new
prospects for the using such diblock copolymers as vehicles for delivery of poorly soluble
toxic drugs.
References
1. T.B. Zheltonozhskaya at al. Mol. Cryst. Liq. Cryst. 536, 390 (2011)
143
SURFACE ROUGHNESS AND WETTABILITY OF WOOD SAMPLES
DEPENDING OF THE COATING
L. Laiveniece1, A. Morozovs2
1
2
Forest Faculty, Latvia University of Agriculture, Jelgava, Latvia, [email protected]
Faculty of Food Technology, Latvia University of Agriculture, Jelgava, Latvia
The wettability of the surface depends on many factors, both physical and chemical.
Surface roughness has a significant influence on the wettability even for seemingly smooth
surfaces and is important for many practical wetting and spreading processes [1]. Wood is
a complex material, and its surface roughness depends on many factors, for example, wood
species, type of wood, machining properties and grain orientation [2, 3]. The aim of this
study was to assess wood heterogeneity on polyurethane (PU) adhesive wettability.
Surface roughness of wood samples was examined with AFM in the laboratory of Riga
Technical University in 2013. Wood samples of non-dried Scots pine (Pinus sylvestris L.)
(MC = 15%) were cut from rectangular timber so that the wood tracheids are open and the
grain orientation to the surface was 45 ° to avoid predominance of the wood radial and
tangential heterogeneity. Afterwards wood samples were coated with PU glues. The coated
wood samples were sawn in smaller ones with thickness less than 2 mm with circular
saw.The smoothness behaviour of the wood surface was determined with AFM in 1020
µm large areas. The wetting behavior of the wood samples was characterized by the
contact angle method (goniometer technique). The surface free energy components of a
wood were calculated from measured values of contact angles of three test liquids.
Obtained average surface roughness of Scots pine samples with coating of glue I was
283.01 nm, 332.44 nm (on late wood), 234.01 nm (on early wood); with coating of glue II
was 249.32 nm. The surface roughness of wood depends on processing technique of
surface, machining properties, grain orientation, and type of wood and may vary from 4033000 nm [4, 5]. In table summarized results of contact angle and surface energy values of
glues, wood and coated wood samples.
Surface
Glue I (on glass)
Glue II (on glass)
Wood
Wood with glue I
Wood with glue II
Results of contact angle and surface energy values
Contact angle (± SD), °
Surface energy, mN m-1
Water
Diiodomethane
Ethylene glycol
Total
Base component
80.12 ± 0.64
47.20 ± 1.03
60.63 ± 1.35
36.38 ± 2.80
9.91
73.04 ± 0.99
42.00 ± 0.78
57.53 ± 0.55
34.16 ± 1.66
14.45
63.97 ± 6.12
26.75 ± 2.15
43.60 ± 4.45
44.45 ± 0.06
17.31
82.80 ± 0.28
31.03 ± 3.21
61.25 ± 2.48
42.88 ± 0.98
8.99
74.23 ± 1.76
35.90 ± 4.95
62.97 ± 4.31
38.82 ± 3.06
12.81
The wood surface values increase values of contact angle with polar liquids (water and
ethylene glycol) due to roughness of cross-cut surface of wood and open wood cell
cavities. The increase of the glue surface energy above the wood surface could be caused
by changes of the glue chemical composition by wood extractives and artefact of surface
roughness that will be proved experimentally.
References
1. T.T. Chau, W.J. Bruckard, P.T.L. Koh, A.V. NguyenInt. J. Adhes. Adhes., 31, 127-134 (2009).
2. M. Gindl, G. Sinn, W. Gindl, A. Reitener, S. Tschegg. Colloid Surface A., 181, 279-287 (2001).
3. A. Malkoçoğlu Build. Environ., 42, 2562-2567 (2007).
4. S. Wang, R. Mahlberg, S. Jämsä, J. Nikkola, J. Mannila, A.C. Ritschkoff, J. Peltonen. Prog. Org. Coat.,
71, 274-282 (2011).
144
POLY(URETHANE-UREA) MICROCAPSULES FOR
IMMOBILIZATION OF MALTOGENASE
S. Maciulyte, G. Valungeviciute, J. Razumiene, I. Sakinyte, T. Kochane,
I. Gerasimcik, S. Budriene
Department of Polymer Chemistry, Vilnius University, Naugarduko str. 24, Vilnius LT-03225, Lithuania,
[email protected]
Microencapsulation is defined as a process in which tiny particles or droplets are
surrounded by a coating wall or embedded in a homogeneous or heterogeneous matrix, to
give small capsules and therefore building a barrier between the component in the capsule
and the environment [1]. The most available technologies for microencapsulation use a
liquidas a suspending medium (complex coacervation, interfacial and in situ
polymerization or solvent evaporation from emulsions) or a gas as suspending medium
(spray-drying or spray cooling, fluidized-bed coating or co-extrusion) [2]. The present
work focuses on the synthesis and properties of poly(urethane-urea) (PUU) capsules
encapsulated with enzyme maltogenase (MG) from Bacillus Stearothermophilus intended
for application in sustained release enzyme formulations. MG is used for saccharification
of starch in production of high maltose syrups. PUU capsules were synthesized from
poly(vinyl alcohol) and 1,6-hexamethylene diisocyanate (HMDI) by inverse emulsion
method. The emulsion water-in-oil was formed, where the dispersed phase was PVA
solution in water or in 0.1 M citrate buffer and the external phase was toluene or butyl
acetate. Surfactants Span 60, 80 and 85 were used as emulsifiers. After emulsification,
HMDI was added to reaction mixture. PUU capsules shells were formed by polyaddition
reaction using catalyst dibutyltin dilaurate (DBTDL). The encapsulation of MG was
carried out during or after formation of capsules. The structure of shell of capsules has
been proven by chemical analytical methods and by FT-IR spectra. Thermal stability of
dried capsules was studied by simultaneous thermal analysis. The surface area and the pore
size of shell of microcapsules were determined by using BET and BJH methods,
respectively. The influence of initial reaction conditions, such as concentration of used
surfactant, PVA and DBTDL, molar ratio of PVA and HMDI, phase-volume ratio of
emulsion, agitation rate, reaction temperature and time on yield and structure of shell of
capsules and quantity of encapsulated hydrophilic material were investigated. Depending
on reaction conditions, the range of PUU capsules size distribution was 25-700
µm.Capsules encapsulated with MG were studied as enzyme delivery systems. The highest
efficiency of immobilization of MG in capsules was obtained when PVA was dissolved in
citrate buffer and the external phase was butyl acetate. MG release from capsules
depended on the shell structure.
Acknowledgements. This work was funded by the European Social Fund under National Integrated
Programme Biotechnology & Biopharmacy, grant VP1-3.1-SMM-08-K01-005.
References:
1. P. Calvo, A.L. Castaño, M. Lozano, D. González-Gómez. Food Res. Int. 45, 256-261 (2012).
2. F. Nazzaro, P. Orlando, R. Coppola. Curr. Opin. Biotechnol. 23, 182-186 (2012).
145
EFFECT OF POLYMERIC COMPOUNDS ON ISOELECTRIC POINT
OF COLLAGEN
L. Maistrenko, O. Andreyeva
Department of Leather and FurTechnology, Kyiv National University of Technologies and Design, Kyiv,
Ukraine; [email protected]
To determine the technological properties of new polymeric compounds − derivatives
of unsaturated maleic (product Кro) and acrylic (products TP, CP) acids the effect of
treatment of fibrous collagen − the main protein substance of the animal skin, leather and
fur skin tissue, by these compounds was investigated.
As it is known, one of the characteristic parameters of collagen is its isoelectric point −
the pH at which the number of ionized acidic and basic groups is the same. For direct
determination of isoelectric point potentiometric method is frequently used, for indirect
determination − a method of measuring the degree of swelling, fixation of acid and basic
dyes and ions from solutions of mineral salts. In the isoelectric point value of all these
parameters is minimal.
Isoelectric point of 1.0 % gelatin solution, as collagen derivative, was determined by
combining potentiometric and photocolorimetric methods, that allowed to consider
maximum protein deposition in this state. To fix the pH of the solutions a modern pH
gauge − unit PH-013M (measurement error ±0.01 pH) has been used.
It has been determined by experiment, that as a result of treatment by polymer, a shift
of the isoelectric point of gelatin took place from 4.89 towards lower pH values at 0,160,53 units: for product Kro − to 4.73, product TP − to 4.55, product CP − to 4.36, that
indicates the chemical nature of the interaction in the system «gelatin-polymer».
To determine the isoelectric point of fibrous collagen of derma of leather semi-finished
item, produced of goat raw stock, colorimetric method developed in France has been used.
The method is based on searching the pH at which the derma has zero reactivity, and helps
determine the isoelectric point of semi-finished item before dyeing by acidic and basic
dyes, such as acid fuchsine and methylene blue. Isoelectric point corresponds to the pH, at
which the greatest absorption (i.e. smallest fixation) of both dyes is observed. In this case
the color of semi-finished item’s front face is the most dim.
On the basis of mentioned above, goat semi-finished item was treated by polymeric
compounds in the amount of 2.0 % of the shaved weight (in terms of dry residue) during 1.0
h at 30 °C, consumption of water is 200 %. As in the previous experiment (gelatin treatment
by polymer), the shift of the protein isoelectric point toward lower pH values has been
detected: for product Kro − from 5.50 to 5.30, product TP − to 4.95, product CP − to 4.20.
The position of isoelectric point of collagen in the acidic pH area Professor Mikhailov
A.N. explains by certain excess of amino acids with acidic side chains over amino acids
with side chains of the basic character. Presence in the collagen structure of peptide bonds
(increase of its number decreases the pH value) is also important. Thus, in our case the
shift of isoelectric point of derma collagen to more acidic area indicates the interaction of
polymers with basic nitrogen-containing groups of the protein.
The data obtained are confirmed by the results of IR spectroscopic studies and explain
the changes in the structure of collagen and properties of derma in the case of using the
polymeric compounds for the manufacture of natural leather.
146
ESTIMATION OF ELECTROSPUN WEB FROM PA6.6
NANOFIBRES
J. Malašauskienė, R. Milašius
Department of Textile Technology, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
Electrospinning is a prevalent method to produce nanofibres from polymer solution or
melt. The structure of web from electrospun nanofibres depends on the solution properties,
technological and ambient parameters. The influence of these parameters sometimes is
evident, but not always. It is possible that sometimes researchers achieve controversial
results because there is no common methodology for the structure of nanofibres
characterization.
Fiber diameter is one of the most important structural characteristics in electrospun
webs. The analysis of various works showed that distributions of nanofibres diameter
always are different. To compare parameters with different kinds of distribution is not
correct from mathematical point. Only the average value of nanofibres diameter can not
characterize the structure of nanofibres precisely, because changes in average value do not
mean the same changes in modal value and other characteristics. In order to compare the
diameter of nanofibres with an average value it is necessary to use other characteristics.
The goal of this paper is to analyze the dispersion of nanofibres diameter and to
propose new criterions for the quality of nonwoven structure estimation.
The substratum material was covered by a layer of PA6.6 fibres using “Nanospider TM”
equipment (ElmarcoCheczRepublic). The distance between electrodes was 13 cm; the
applied voltage was 70 kV. The structure of electrospun web was determined using a
scanning electron microscope (SEM) Quanta 2000 (FEI). The diameter of fibres was
measured using an image analysis system LUCIA 5.0.
The analysis of mathematical distribution of nanofibres diameter showed that the
shape of distribution usually is not normal but is actually compound from several normal
distributions. In this paper the percentage quantity and the modal value of the first
distribution, also the average diameter of two modal values are proposed for estimation of
web structure. These parameters, with the average value of nanofibres diameter more
precisely allow to estimate the influence of main parameters on the structure of electrospun
web.
References
1. W. Sambaer, M. Zatloukal, D. Kimmer, Polymer Testing, 29, 82–94, (2010).
2. G.A.V. Leaf.: Practical Statistics for the Textile Industry: Part I, The Textile Institute, Manchester, 1984.
3. J. Malašauskienė, R. Milašius. Journal of Nanomaterials, Article ID 416961, doi: 10.1155/2013/416961
(2013).
147
SOME FUNCTIONAL PROPERTIES OF COMPOSITE MATERIAL
FROM RECYCLED TIRES IN WATER MEDIUM
R. Plesuma1, L. Malers2
1
2
Department of Polymer Material Technology, Riga Technical University, Riga, Latvia.
Department of Polymer Material Technology, Riga Technical University, Riga, Latvia,[email protected] .
Production of composite material must be considered as one of the most perspective
directions of scrap tires reuse in the combination with polymer binder [1].
In our previous investigations optimization of composition and technology of
composite material’s production from mechanically grinded scrap tires and polyurethane
type binder were realized [2]. It was also cleared up ,that mechanical properties of the
composite material are strongly dependent not only from the composition of material and
activity of polymer binder , but also from technological parameters (molding pressure,
temperature) and environmental conditions (relative air humidity) [3-5].
Present research must be considered as a continuation of our previous investigations
of composite material and the goal of this work was to study some functional properties
of composite material considered to be potentially important from the aspect of the
utilization of material - water permeability (introduced method), absorption and swelling
(LVS EN 12087) after definite exposition time in water ,as well as frostresistance of
composite material according to modified LVS EN 12091:2002, examined through
changes of strength-deformation properties of composite material before and after frostresistance test.
Mentioned above properties of the composite material were examined in correlation
with composition of material, activity of the polymer binder, particle size distribution of
rubber crumb , molding pressure and temperature as material production technological
parameters.
The dependence of all the tested properties from the composition of material was
cleared up. Water absorbtion and swelling of the composite material showed close
correlation with activity of polymer and thus underline importance of crosslinking degree
of polymer binder. Molding pressure and rubber particle size distribution demonstrate
direct influence on the water absorption and permeability of the composite material, but
temperature as technological factor has significant impression on swelling of the material.
It was estimated also, that composite material must be considered as frost- resistant
because of obtained results after realized frost – defrost tests with simultaneously influence
of water.
Obtained results are useful for practical application of selected composite material
with desirable and predictable functional properties.
References
1. J.E. Mark, B. Erman, R. Erich. The Science and Technology of Rubber, 3rd ed., Elsevier Inc., USA,
(2006).
2. L. Malers , R. Plesuma, L. Locmele. Mechanics of Composite Materials, T45 (1), 1-6 (2009).
3. L. Malers, R. Plesuma, L. Locmele, A. Megne, I. Mateusa-Krukle, M. Kalnins. Abstracts of Baltic
Polymer Simposium 2010, Kaunas University of Technology, 55 (2010).
4. L. Malers, R. Plesuma, L. Locmele. Scientific Journal of Riga Technical University, Material Science
and Applied Chemistry, 23, 103-106 (2011).
5. R. Plesuma, A. Megne, I. Mateusa-Krukle, L. Malers. Progress in Rubber, Plastics and Recycling
Technology, 3 (2013) (in press).
148
STRUCTURE AND PROPERTIES OF LIQUID CRYSTAL MODIFIER
AND LAYERED SILICATE CONTAINING POLYMER HYBRID
COMPOSITES
R. Merijs Meri1, J. Zicans1, T. Ivanova1, I. Elksnite1, M. Kalnins1, V. Kalkis2
1
2
In recent years increasing attention is devoted to improving modification effectiveness
of polymer nanocomposites. On this score it is important to tailor interfacial interaction
between polymer matrix and nanostructured filler. Interfacial interaction between matrix
and filler can be regulated by means of organomodification of nanofiller, which is
especially important in the case non-polar polymers, such as polyolefines, styrene
polymers and others. Besides interfacial issues, another method, leading to improved
modification effectiveness of composite materials, is hybridization. It should however be
mentioned, that research on hybrid polymer nanocomposites is in its infancy.
The current research addresses some of the previously mentioned modification
efficiency issues. Consequently the effect of either aliphatically of aromatically modified
clay on the structural, mechanical and thermal characteristics of polyethylene based
nanocomposites is evaluated. Besides it the effects of simultaneous addition of organoclay
and high-molecular rigid rod liquid crystalline modifier on the structural, mechanical and
thermal characteristics of polyethylene are investigated.
It has been shown that in the presence liquid crystalline modifier some elastic
properties of polyethylene-organoclay nanocomposites can be considerably increased.
Besides it should be mentioned that in the presence of liquid crystalline modifier rheology
of polyethylene-organoclay nanocomposites can be successfully modified.
149
THE INVESTIGATION OF WATER SORPTION ON THE
ANTIMICROBIAL TREATED PLAIN AND PLATED KNITS
A. Mickevičienė, R. Treigienė
Department of Textile Technology, KaunasUniversity of Technology, Kaunas, Lithuania
The clothing for sport and leisure has to ensure a good human being and be harmless.
Sweat is secreted intensively while moving actively. It is a good medium for growth of
microorganisms. The growth of microorganisms on textiles causes an unpleasant odour,
results many skin troubles (allergic sensitisation, itching, acne, rashes) and a loss of textile
properties including fabric rotting, staining, discolouration and quality deterioration [1 –
3]. In order to avoid the above mentioned it is important that clothes would absorb and
evaporate sweat quickly enough.
The aim of this work was to investigate water sorption on the antimicrobial treated
plain and plated knits.
There were used two groups of plain plated knits. The knits of I group were knitted of
the same base and face yarns which were cotton, bamboo-viscose and polyester. The knits
of II group were formed of base yarn which was the textured polyester (PES) thread of 20
tex and the face yarns were the same as in the I group. The knits were treated in an
antimicrobial solution of iSys AG and organic-inorganic binder iSys MTX (CHT,
Germany) as well as the knits treated in the same conditions as treated in antimicrobial
solution, however, an antimicrobial material and binder weren’t used. The last mentioned
samples were named as blank treated.
It was established that the usage of antimicrobial materials in the finishing process
changed sorption characteristics of investigated knitted fabrics. The water sorption of all
knits due to antimicrobial treatment significantly decreased comparing with blank treated
knits (Fig.1). It was noticed that water sorption values after antimicrobial treatment for all
II group knits were similar from 47 % (C1PES) till 66 % (P3PES). Meanwhile water
sorption values after antimicrobial treatment for pure cotton, bamboo-viscose and polyester
knits (I group) were different. The samples C2 and B1 sorbed the most water in I group,
respectively 147 % and 267 %. Sample C1 sorbed at least 52 %. Such water sorption
results were influenced by using organic-inorganic binder during antimicrobial finishing,
which formed the sol-gel layer on the fiber.
Fig. 1. The water absorption of blank and antimicrobial treated knits
References
1. B. Filipowska, E. Rybicki, A. Walawska, E. Matyjas-Zgondek. Fibres & Textiles in Eastern Europe, 19
(4), 124-128 (2011).
2. Y. Gao, R. Cranston. Textile Research Journal, 78 (1), 60-72 (2008).
3. L. Teufel, B. Redl. Lenzinger Berichte, 85, 54–60 (2006).
150
TRANSFORMATION OF COLLAGEN HIERARCHICAL
STRUCTURE AT NANO- AND MICROLEVELS INFLUENCED BY
MODIFIED MONTMORILLONITE
O. Mokrousova1, Y. Dzyazko2
1
2
Kiev National Trade and Economics University
V.I. Vernadskii Institute of General & Inorganic Chemistry of the NAS of Ukraine
Collagen is the main protein of the derma of animals has a multilevel structure, which
defies a porous structure finished leather and provides it with necessary operating and
hygienic properties. High-quality leather is obtained in the result of technological
treatments with physical and chemical transformation of collagen of derma. This is shown
in significant changes in porous structure and specific surface area of collagen of derma.
The derma, as a porous material has pores of various sizes, which vary from 0.001 to
200 microns and form micro-(r ≤ 1 nm), meso-(1 nm ≤ r ≤ 200 nm) and macro porous (r ≥
200 nm) structure. The molecular level of derma structure is organized with
macromolecules with a thickness of ~1.5 nm from the triplet polypeptide chains. This
allows to purposefully influence the nature of porosity in the process of leather production
and to handle performance characteristics of a wide range of leathers. Supramolecular level
formed from microfibrils ~3-5 nm, and nadfibrillyarny - includes fibrils ~50-200 nm. Then
fibrils form primary fibers with the size ~5 microns and diameter more than 200 microns.
Hence derma has a hierarchical structure with the dimensions of structural elements, which
differ by approximately 5 orders of magnitude [1].
The technology of the leather production involves preparation, tanning and
aftertanning processes. Preparation processes are aimed at the separation of collagen
structure and the removal of non-collagenous proteins. In tanning processes occurs the
fixation and stabilization of the resulting structure of derma. The final formation of
porosity is achieved in aftertanning processes: retanning, filling, fattening, etc. A positive
role is played by the mineral filling of leather with the use of dispersions of modified
montmorillonite, which promotes quality formation of the derma. This is achieved by
sealing, screening of the structural elements of derma, obstacle their bonding during
process of drying of leather.
The investigation is devoted to study of transformation of collagen hierarchical structure.
For studies samples of the skin after preparatory processes, tanning and aftertanning processes
were used. Porometric measurements were performed at 0.1 MPa using octane or water as
working liquids. The samples were previously vacuumized at 353 K [2].
The results of investigation showed that a natural leather has a very wide range of pore
sizes. As well, pores of different radii have a particular function, which was shown by the
high volume porosity and specific surface area of skin. A large proportion of nano-and
micro pores has a regular structure and forms a total surface of the pores. Macro pores
determine the porosity of derma. It is proved that the processes have different effects on
the transformation of the collagen structure. Mineral filling contributes to ordering of the
porous structure at fibrils, intensifies transportation of moisture in respective pores, which
improves elasticity and operational properties of leather.
Reference
1. E. Heidermann, Ubeerlegungen. Das Leder, 6, 149–154 (1995).
2. O.R. Mokrousova, Y.M. Volfkovich, N.F. Nikolskaya. Leather and Shoes Manufacturing, 6, 19-24
(2010).
151
RIGID POLYURETHANE FOAMS FROM OXYPROPYLATED
WHEAT STRAW LIGNIN
A. Paberza, A. Arshanitsa, U. Cabulis
Rigid polyurethane (PU) foams are used as thermal insulation, for example in
refrigerators and construction materials. Polyols for rigid PU foams production are derived
mostly from petrochemical products but it can be replaced by polyols obtained from
natural raw materials (vegetable oils, tall oil, lignin etc.). Lignin is the most abundant
aromatic polymer in the nature and it is isolated from chemical pulping or biorefining as
byproduct. The most common lignin utilization is steam and power production through
combustion but research in value added products is continuing [1].
Organosolve lignin from CIMV biorefinery (France) was used in our work. Different
lignin and propylene oxide (PO) ratio (0.15-0.40) was used to get lignopolyols. Obtained
lignopolyols were brown, long-term stable liquid with viscosity higher than 1720 Pa·s.
Commercial polyol Lupranol 3300 was substituted by each lignopolyol in the compositions
of rigid PU foams to investigate lignopolyol effect to density, closed cell content, physicalmechanical properties and water absorption.
Lignopolyol did not affect the closed cell content of samples – it is more than 90% for
all foams. Water absorption is better for samples obtained from lignopolyols than neat
foams. Compressive strength increases for foams where lignin and PO ratio is from 0.2 to
0.4 (Fig.1). For materials with ratio up to 0.15 compression strength is decreased because
lignopolyol hydroxyl value is lower (OH=280 mg KOH/g) than Lupranol 3300
(OH=400 mg KOH/g) used for neat foams. For lignopolyols with lignin and PO ratio
>0.20 hydroxyl value is approximately the same or higher (OH=400-470 mg KOH/g).
Compressive strength, Mpa
0,35
0,30
Parallel to foaming direction
Perpendicular to foaming direction
0,25
0,20
0,15
0,10
0,05
0,00
Neat 0.15 0.20 0.25 0.30 0.35 0.40
foams
Lignin and PO ratio for synthesized lignopolyols
Fig. 1. Compressive strength of rigid PU foams obtained from Lupranol 3300 (reference sample L3300) and
from lignopolyols with different lignin and propylene oxide ratio.
Lignopolyols synthesized from CIMV lignin by oxypropylation reaction is prospective
material to obtain rigid PU foam with improved characteristics such as water absorption
and compression strength.
Acknowledgements.The financial support of BIOCORE project (FP-241566) by the EC through the FP7 is
greatfully acknowledged.
References
1. X. Pan, J.N. Saddler. Biotechnology for Biofuels, 6, 12 (2013).
152
CELLULOSE/HYDROXYAPATITE FRAMEWORKS FOR BONE
TISSUE REGENERATION
O. Petrauskaite1, J. Liesiene1, I. Jaruseviciute1, G. Juodzbalys2, J. Maminskas2,
A. Stumbras2, P. Daugela2
1
[email protected]
2
Lithuanian University of Health, Department of Maxillofacial Surgery, Lithuania
Polysaccharides have found increased interest for the preparation of highly porous
three-dimensional scaffolds for bone tissue in-growth. Significant attention is focused on
cellulose due to its surface chemistry, biocompatibility and non-toxicity. However,
disadvantage of natural cellulose is its morphology which does not corresponds to
requirements for bone scaffolds as it has to be highly porous with interconnected pores
similar to natural spongy tissue. The structure of scaffold should be accessible for cell
adhesion, proliferation, differentiation and vascularisation [1].
The present work explores cellulose/hydroxyapatite frameworks for bone tissue
regeneration. Composites were prepared by regeneration of cellulose from its acetylated
derivative and adding hydroxyapatite. A highly porous structure of the scaffolds was
obtained by freeze-drying method. The biological characterization of the scaffolds was
conducted with MG63 human osteoblastic cells, for a period of 7 days. The matrix seeded
with the cells was evaluated by the scanning electron microscopy (SEM). SEM imaging
revealed that cells adhered well to the matrix and proliferated actively throughout the
culture period.
Fig. 1. 3D and 2D micro-computed tomography images of cellulose/hydroxyapatite scaffold.
Micro-computed tomography analysis was performed for the morphological
characterisation of the scaffolds (Fig. 1). The porosity of constructs was of 72% with mean
pore diameter of 490 µm.
References
1. G. Chen, T. Ushida, T. Tateishi. J. Macromol. Biosci., 2, 67-77 (2002).
153
APPLICATION OF COLLAGEN-CONTAINING WASTE TO
PRODUCE OF BIOPOLYMERS AND COMPOSITES WITH
PREDICTABLE PROPERTIES
V. Plavan
Department of Leather & Fur Technologies and Department of Technological Safety, Kiev National
University of Technologies & Design, Kiev, Ukraine, [email protected]
In practice there are no effective processing technologies of the collagen-containing
waste from leather industry. Some technologies are very time- and energy consuming,
others - inefficient, resulting in the tens of thousands of tons of waste from leather industry
disposed of in landfillsand quarries, than does more environmental damage.
Protein hydrolysates are products of partial hydrolysis of proteins which containing the
essential amino acids, trace elements and so on. There are two main ways of obtaining
protein hydrolysates: chemical - under the influence of acids and alkalis and biological under the enzymes action. Enzymatic method is the most suitable because implement in
softer conditions and prevents destruction of amino acids, carbohydrates and other
substances contained in waste.Collagen-containing tanned wastes were received from the
tannery "Chinbar" (Kiev) during production trials of non-chromium tanning technology. In
the research work alkaline-enzymatic methods have been used for obtaining the
hydrolysates. The degree of hydrolysis was determined by total nitrogen content in the
final product.
Alkaline-enzymatic method of hydrolysis at the consumption of protosubtilin of 1.25%
provides total nitrogen content in the final product of 12-14 g/l. The content of total
nitrogen is 19-20 g/l at the consumption of 3% protosubtilin. The content of total nitrogen
increased to 20-22 g/l using the enzyme alkaline protease in the same amount. To intensify
the process of hydrolysis the temperature of hydrogen peroxide treatment was increased to
70 oC. It is possible to short the duration of this treatment for 3-4 hours and contribute to a
higher degree of hydrolysis, as evidenced by increasing the total nitrogen content in a final
product to 23-24 g/l.
As a result of ion-exchange liquid column chromatography, the number of basic amino
acids increased due to hydrolytic decomposition of collagen as a result of breaking the
peptide bonds. Arginine content increased to 7.11 %, lysine – up to 5.94 %. In collagen
hydrolyzate (except lysine and arginine) essential amino acids are remained as valine
(4.05%), histidine (1.02%), which is a very important amino acid in the feeding of young
animals, also isoleucine and leucine (1.55 and 1.77%), methionine, threonine and
phenylalanine (0.68, 3.74 and 2.19 % respectively). The presence of amino acids with
reactive groups makes it possible to adjust the properties of hydrolysates [1].
Obtained hydrolyzate is balanced by theaminoacid composition and taking into
account the presence of nitrogen and phosphorus can be used for organic fertilizers and
growth promoters as feed additive in growing animals, and after further modification as a
component of composite materials and biopolymers.
Acknowledgements.Author is very grateful to the State Agency for Science, Innovation and Informatization
of Ukraine for the financial support.
References
1. Zhongkai Zhang, Guoying Li, Bi Shi. J. of the Society of Leather Techn. and Chem., 90, 23-27 (2006).
154
CATALYTIC CURING OF EPOXY RESIN APPLICABLE FOR THE
RESTORATION OF GLASS ARTEFACTS
D. Ragauskienė, J. Laurinavičiūtė
Department of Polymer Chemistry, Vilnius University, Naugarduko 24, Vilnius, Lithuania,
[email protected]
At the present time epoxy resins are the most appropriate materials for restoring
archaeological glass finds, as well as historical or modern glass artefacts. Unfortunately,
when epoxy resins naturally ageing in light they become yellow. Ceramic and glass
conservators in Lithuania have experience of using the epoxy resin Araldite 2020 based on
bisphenol A and they are going to introduce in the practice the epoxy resin Hxtal Nyl-1
consisting of the hydrogenated bisphenol A. Ageing under UVA irradiation corresponding
indoorconditions revealed that epoxy resin Hxtal Nyl-1 was more age-resistant than
Araldite 2020. Bisphenol A caused irreversible ageing of the cured Araldite 2020 resin
samples. Hydrogenated bisphenol A retarded ageing of Hxtal Nyl-1 resin samples, though
imidazole as a catalytic agent caused its insignificant yellowing.
Obviously, photochemical ageing of the cured epoxy resins depends on the resin itself
and hardener formulation. The main goal of this study was to find the best composition of
epoxy resin and hardener for the restoration of glass items. The samples were prepared
from commercial epoxy resin Eponex 1510 (Momentive (Hexion)) based on hydrogenated
bisphenol A, with five different aliphatic amines: diethylentriamine (DETA), isophorone
amine (IPDA), amine ethylpiperazine (AEP), and two different molecular weight
polyetheramines (D-320 and T-403). The applicablehardeners for hydrogenated bisphenol
A resin, e.g. Eponex 1510, were polyetheramines, e.g. Jeffamine T-403 (Huntsman), but
resin with these hardeners cures very long.
Catalytic curing agents are a type of Lewis bases based on tertiary amines, that
contribute to crosslinking of epoxy resin in conjunction with another curing agent such as
polyetheramine. The time of curing was shorten when mixture of hardeners
polyetheramine T-403 and isophorone amine (IPDA) was used together with catalytic
agent triethanolamine (TEOA) as well as commercially available Accelerator 399
(Huntsman), consisted from 65-79,9 %triethanolamine(TEOA), 4-10,9 % amine
ethylpiperazine (AEP) and20-34,9 %piperazine.
The best epoxy composition were reached when 100 grams of resin Eponex 1510 were
cured with the mixture of polyetheramine T-403 and isophorone amine hardeners (T403:IPDA = 18,1:13,2 g) and by adding 10 % of Accelerator 399 or modified composition
Accelerator 399a. Hardening time decreases to 3 days, and the samples remained ageresistant for two months exposed them under UVA irradiation. The ageing properties were
evaluated measuring colour changes and mechanical properties (hardness and elasticity) of
the samples. The chemical changes were assessed by FTIR spectroscopy and defined by
the number of epoxy groups.
References
2. Guo Yang, Shao-Yun Fu, Jiao-Ping Yang. Polymer, 48, 302-310 (2007).
3. Xa. Fernandez-Francos, W. D. Cook, A. Serra, et al. Polymer, 51, 26-34 (2010).
4. F. G. Garcia, M. E. Leyva, et al. Int. J. Adhesion 31, 177-181 (2011).
5. F. Delor-Jestin, D. Drouin, P.-J. Cheval, J. Lacoste. Polym. Degrad. Stab., 91, 1247-1255 (2006).
155
SILICON COLLOIDS LIGHT/UV STABILISERS OF POLYSTYRENE
AND POLYPROPYLENE
M. Bermejo1, M. Schmitt1, S. Sánchez-Ballester1 O. Gil-Castell1, R.Teruel-Juanes1,
M. Rosado-Gil1, L. Santonja-Blasco1, A. Martínez-Felipe1, I. Rodrigez2, F.
2
1
Meseguer A. Ribes-Greus
1
Camino de Vera S/N, 46022 Valencia, (Spain), [email protected]
2
Unidad Asociada CSIC-UPV Universitat Politècnica de València, Avda Tarongers s/n, 46022, Valencia
(Spain)
Oxidation of plastics by ultraviolet (UV) radiation exposure is an important limitation
for their use in packaging and other applications where there is direct contact with food or
drink. Severe polymer decomposition can occur when free-radical sites are generated along
the polymer backbone and react with the rest of the polymer or with oxygen molecules. A
strategy to guarantee a successful use of plastic materials is to incorporate additives which
can improve the resistance to light and weathering, enhance their physical properties and
ultimately respond to environmental health demands of new products. In this framework,
novel silicon-based materials have been recently developed, namely silicon colloids,
capable to trap/absorb light very efficiently in a large-span frequency range, covering the
visible and far infrared regions. These materials consist of almost perfectly spherical
silicon micro- and nano-particles with a very smooth surface. Experimental evidence and
theoretical insights show that silicon-colloid-based liquid suspensions and photonic
crystals made of two-dimensional arrays of particles have strong magnetic response in the
near-infrared region with small optical losses, making them suitable for several
technological applications [1, 2].
In this work, we present the preparation and characterisation of dispersions of silicon
colloids in polystyrene and polypropylene. The materials were prepared by mixing the
polymeric matrixes with the silicon colloids, added from 0.1 to 5% by weight percentage,
using a Banbury mixer. The probes, with thicknesses around 200 μm, were obtained by die
cutting the films previously prepared in a hot plate press. The degradation of the samples
was carried out in a Suntest XLS+ equipment at different irradiation times, by applying
600 W/m2 with a Xenon lamp, and using filters to simulate the solar radiation. The
degradation of the samples was evident by visual observation, and was further monitored
as a function of the irradiation time by means of DSC, TGA and DETA. The different
parameters calculated, such as the glass transition (Tg), the cristallization tempetarature
(Tcris), the melting temperature (Tmelt), the melting enthalpy (ΔHmelt) from the DSC; the
thermal stability, the peak temperature (Tpeak) and the onset temperature (Tonset) from TGA;
and the dielectric relaxation times. All these parameters indicate that the silicon colloids
inhibite degradation respect to the pristine polymers and showing their potential as
additives for light/UV stabilisation.
Acknowledgements. The authors would like to acknowledge the Spanish Ministry of Economy and Competitiveness, through the
Research Projects, UPOVCE-3E-013, ENE2011-28735-C02-01, FIS2009-07812, Consolider 2007-0046 Nanolight and the FPI-BES
2012-055316 pre-doctoral grants. Generalitat Valenciana is thanked for the PROMETEO/2010/043GRISOLIA/2012/003,
GRISOLIA/2013/036, APOSTD/2013/054, APOSTD/2013/036 and ACOMP/2013/143 programs. The Vicerectorate for Research of
Universitat Politècnica de València is also thanked for additional support through the PAID 05-09-4331, PAID-05-11/2806, PAID 0611-2037 and PAID-06-SP20120581 projects.
References
1. Lei Shi, Justin T. Harris, Roberto Fenollosa, Isabelle Rodriguez, Xiaotang Lu, Brian A Korgel, Francisco
Meseguer. Nature Comm. DOI 10.1038/ncomms 2934 (2013).
2. R. Rodriguez, R. Fenollosa, F. Meseguer and A. Perez-Roldan. Patent (2011).
156
BLENDS OF PAA AND IONOMERS LC COPOLYMERS FOR
ELECTROLYTES IN DMFC AND DEFC
P. Fernandez1, T.Lamberty1, S. Sánchez-Ballester1 O. Gil-Castell1, R.Teruel-Juanes1,
M. Rosado-Gil1, A. Martínez-Felipe1, V. Soria2, A. Ribes-Greus1
1
Camino de Vera S/N, 46022 Valencia, Spain , , [email protected]
2
Institut de Ciència dels Materials (ICMUV), Universitat de València (UVEG)
Direct Methanol and Ethanol Fuel Cells technology is an interesting alternative to
fossil fuels for energy conversion. Despite their multiple advantages, crossover of alcohol
from the anode to the cathode still limits the performance of DMFC and DEFC at large
scale. During recent years, most of the effort in this field has been focussed on designing
new polymeric electrolytes with an optimum combination of barrier properties and high
proton conductivities [1]. Thermotropic liquid crystal polymers (LCP) containing ionogens
(sulfonic acid groups), combine the formation of anisotropic liquid crystal (LC) structures
with the functionality of ionogens. Due to this duality, these polymers have potential
interest as electrolytes where the supramolecular structure of the polymer plays an
important role in the selective transport of charges.
In this work, we present the preparation and characterisation of new potential
electrolytes for low temperature fuel cells consisting of blends of commercial poly(acrylic
acid), PAA, with a liquid crystal copolymer, the so-called 6-MeOAzB/AMPS 05/05
polymer. The blends were obtained by solvent evaporation at 70ºC of mixtures of PAA
with 6-MeOAzB/AMPS 05/05, the latter being previously synthesised by radical
copolymerisation, and using dimethylformamide as solvent [2].
The proportion of 6-MeOAzB/AMPS 05/05 was varied in the mixtures to obtain
materials with different compositions (0, 25, 50, 75 and 100%, by weight percentage of
copolymer). The structure and stability were determined by means of NMR, FTIR, DSC,
TGA. The relaxation spectra of the polymers was studied in the frequency range of f = 10 2
/107 Hz and the temperature interval of T = -10ºC/120ºC. All the dielectric spectra were
modelled using Havriliak-Negami equations and the relationship between relaxation times
and temperature were determined.
The results show that the blends maintain the liquid crystal properties of the
corresponding homopolymer (6-MeOAzB) [3]. Moreover, the introduction of PAA
considerably increases the conductivity of the blends, respect to the copolymer 6MeOAzB/AMPS 05/05, and enhances the film forming properties of the resulting
materials.
Acknowledgements. The authors would like to acknowledge the Spanish Ministry of Economy and Competitiveness,
through the Research Projects, UPOVCE-3E-013, ENE2011-28735-C02-01, and the FPI-BES 2012-055316 pre-doctoral
grants. Generalitat Valenciana is thanked for the GRISOLIA/2012/003, GRISOLIA/2013/036, APOSTD/2013/054,
APOSTD/2013/036 and ACOMP/2013/143 programs. The Vice-rectorate for Research of Universitat Politècnica de
València is also thanked for additional support through the PAID 05-09-4331, PAID-05-11/2806, PAID 06-11-2037 and
PAID-06-SP20120581 projects.
References
1. Fuel Cell Systems Explained, 2nd Ed., Wiley: New York (2003)
2. Polymer 53, 2604-2612 (2012)
3. Ind. Eng. Chem. Res. (http://dx.doi.org/10.1021/ie3031339) (2013).
157
INFLUENCE OF MALEIC ANHYDRIDE AS COUPLING AGENT IN
PLA/SISAL BIOCOMPOSITES UNDER HYDROTHERMAL
DEGRADING CONDITIONS
J. Alonso, C. Moran1, O. Gil-Castell1, S. Sánchez-Ballester1, R.Teruel-Juanes1,
M. Rosado-Gil1, J.D. Badia1, A. Martínez-Felipe1, A. Ribes-Greus1
1
Camino de Vera S/N, 46022 Valencia, Spain,[email protected]
Natural fibers, due to their hygroscopic chemical constituents, usually attract water and
humidity. It has been studied that the moisture absorption by composites containing natural
fibers has numerous adverse effects on their structure and properties [1]. Numerous efforts
have been made to address this issue. Coupling agents are usually used to improve the
moisture resistance of composites with natural fibers [2].
In this study, PLA/sisal biocomposites were prepared by compression moulding for
30% of fiber. An accelerated hydrothermal degrading test was designed for temperatures
above the PLA matrix glass transition (65 and 85 ºC). Percentage of water at saturation for
different hydrothermal conditions was characterized. Changes occurred after the water
absorption processes were evaluated by thermal analysis and electron microscopy. Nonsignificant chemical changes were found in terms of back-bone chain scission. Surface
analysis showed an important physical degradation promoted by the formation of
microcracks around swollen fibers.
65 ºC
85 ºC
PLA30C
PLA30
Non degraded
Fig. 1. SEM micrographs for PLA30/30C at different
Fig 2. DSC thermograms for PLA/30C
hydrothermal condition.
at different hydrothermal condition.
Maleic anhydride used as a coupling agent slightly promoted smaller cracks on the
PLA/sisal biocomposites. Technologically speaking, the use of maleic anhydride did not
improve the biocomposite performance.
Acknowledgements. The authors would like to acknowledge the Spanish Ministry of Economy and Competitiveness,
through the Research Projects, UPOVCE-3E-013, ENE2011-28735-C02-01, and the FPI-BES 2012-055316 pre-doctoral
grants. Generalitat Valenciana is thanked for the GRISOLIA/2012/003, GRISOLIA/2013/036, APOSTD/2013/054,
APOSTD/2013/036 and ACOMP/2013/143 programs. The Vice-rectorate for Research of Universitat Politècnica de
València is also thanked for additional support through the PAID 05-09-4331, PAID-05-11/2806, PAID 06-11-2037 and
PAID-06-SP20120581 projects.
References
1. N. Stark J Thermoplast Compos Mater, 14, 421–32 (2001).
2. J.Z. Lu, Q. Wu, H.S. McNann. Wood Fiber Sci, 32 (1), 88–104 (2000).
158
INFLUENCE OF SISAL FIBERS ON THERMAL DECOMPOSITION
OF POLI(HYDROXIBUTYRATE-CO-VALERATE)
BIOCOMPOSITES
O. Gil-Castell1, M. Rosado-Gil1, S. Sánchez-Ballester1, R.Teruel-Juanes1, C. MolinerEstopiñán1, A. Martínez-Felipe1, J.D. Badia1, A. Ribes-Greusa
1
Camino de Vera S/N, 46022 Valencia, Spain, [email protected])
Poly(hydroxyl-butyrate-co-hydroxyvalerate) (PHBV) are the best known polymers of
polyhydroxyalkanoates family (PHA). However, one of their main drawbacks concerning
technical applications is their low impact strength. Natural fibres such as sisal [4] are used
as reinforcing agents in order to improve the mechanical properties of the initial
biopolymer making these materials suitable for a wide range of technical applications.
Thus these materials are an important source of polymeric waste that should be dealt with.
Thermal recovery technologies such as pyrolysis or controlled combustion would be a
solution to manage these plastic wastes.
The main aim of the present work is the energetical valorisation of PHBV/sisal
composites at different percetages (10%, 20%, 30 %). by means of pyrolisis or controlled
combustion. Maleic acid was added to the mixture as coupling agent. An accurate
methodology [1] to evaluate these processes in terms of thermal stability, decomposition
kinetics and emitted gases has been developed. All the samples were submitted to nonisothermal thermogravimetric experiments with the aim to simulate its thermal behaviour.
Moreover, a kinetic analysis (combination of Flynn-Wall-Ozawa, Kissinger-AkahiraSunose, Vyazovkin, Master-Curves and Perez-Maqueda Criado methods) was performed
to obtain the characteristic parameters in the decomposition profiles. Statistical Design of
Experiments (DOE) was applied to study the influence of the characteristic factors on the
main response values for the observed decomposition processes.
Every sample presented two main steps during the decomposition process. The major
loss mass was obtained during the first thermo-degradation stage. The second
decomposition increased its presence with the increasing percentage of sisal. The trigger of
decomposition happened for PHBV at temperatures above 275ºC. An improvement of the
thermal stability of PHBV with the addition of sisal was observed in all cases. A nucleation
and growth type, which gives importance to the formation of gas bubbles in the melt, was
the kinetic model valid. All these results will be of great interest to identify the process and
to obtain the optimum conditions to design the reactors.
Acknowledgements. The authors would like to acknowledge the Spanish Ministry of Economy and
Competitiveness, through the Research Projects, UPOVCE-3E-013, ENE2011-28735-C02-01, and the FPIBES 2012-055316 pre-doctoral grants. Generalitat Valenciana is thanked for the GRISOLIA/2012/003,
GRISOLIA/2013/036, APOSTD/2013/054, APOSTD/2013/036 and ACOMP/2013/143 programs. The Vicerectorate for Research of Universitat Politècnica de València is also thanked for additional support through
the PAID 05-09-4331, PAID-05-11/2806, PAID 06-11-2037 and PAID-06-SP20120581 projects.
References
1. J.D. Badia, L. Santonja-Blasco, A. Martinez-Felipe, A. Ribes-Greus. Bioresource Technology, 111, 468–
475 (2012).
159
THE EFFECT OF COUPLING AGENTS ON THE PHYSICAL AND
MECHANICAL PROPERTIES OF WOOD-PLASTIC COMPOSITES
K. Saar, I. Repeshova, K. Liimand, T. Poltimäe, J. Kers
Department of Polymer Materials, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia.
E-mail: [email protected]
Wood-plastic composite is an excellent example of a constantly evolving and
developing way of thought. The material is environmentally friendly, sustainable and
efficient and by its definiton it increases the demand for green products. The most current
issue is to extend the life cycle of the products by enabling recycling. A large portion of
litter and trash is composed of plastic materials, which have a long decomposition cycle.
The use of wood in the composition of mixed compounds allows the material to absorbe
water and thus enable and encourage rapid decomposition. Wood is also a widely available
resource, which can reduce the cost of materials in the production process.
Purpose of this work is to investigate the effect of coupling agents on the physical and
mechanical properties of wood-plastic composites. For that purpose seven composites were
developed which had different composition and three different binding agents were used:
triethoxyvinylsilane, polyvinyl alchohol and maleic anhydride.
Under microscope it was visible that the materials were coherent and only a few
microscopic airbubbles were present. The impact of binding agents becomes visible in
mechanical testing. The wooden filler decreased the elasticity of the polymer by making
the material more brittle and at the same time improving flexural strength. The mechanical
properties of the material are influenced by the size of wood dust particles – if the particle
size is over 1.25 mm then the orientation of particles impacts the mechanical properties of
the specimen.
160
INVESTIGATION OF APPLICATION OF PEDOT-PSS ON
ANTISTATIC TEXTILES
A. Sankauskaitė1, P. Bekampienė1, S. Varnaitė-Žuravliova1, I. Prosyčevas2,
M. D. Tumėnienė1, A. Abraitienė1
1
Textile institute of Center for Physical Sciences and Technology, Demokratų g.53.LT-48485,Kaunas,
2
Institute of Materials Science Kaunas University of Technology, Savanorių 271, LT-50131, Kaunas,
Lithuania
New functionalized textiles with shielding properties based on nanotechnologies are
used for improving safety of consumers in industrial and health care sectors. This paper
presents investigation of application of some conductive polymers on polyester textiles.
The commercially available conductive polymer poly(3,4-ethylenedioxythiophene)-poly(4styrenesulfonate) (PEDOT-PSS) under the trade name CleviosTM was applied with the low
pressure nitrogen (N2) plasma pre-activated and non-plasma treated polyester textiles
surface by different finishing methods: directly printing, padding and coating. The surface
and vertical resistances, shielding factor and half decay time of polyester woven and nonwoven samples with different concentration of PEDOT-PSS applied with various finishing
methods were determined. Woven and non-woven textiles pre-activated with N2 plasma
and printed with conductive paste CleviosTM SV3 have showed excellent electrostatic
shielding results. Sufficient shielding properties of textile samples were achieved in case of
immersing of samples in to the 10% wt. of PEDOT-PSS CleviosTM PH 1000 aqueous
dispersion. The embedding of higher concentration of Clevios PHTM 1000 (100 g/l) in to
the micro-porous PU coating also significantly improves the electrostatic performance of
investigated woven and non-woven fabrics.
Acknowledgments. The work was carried out in the frame of the Eureka project E! 5799 BATAN Barrier
Textiles and Nanomaterials.
161
INFLUENCE OF CHITOSAN CONTENT ON SURFACE ACTIVITY
OF LIGNIN-BASED POLYELECTROLYTE COMPLEX
V. Shakels1, G. Shulga1, S. Livcha1, M. Dzenis2
1
2
Latvian State Institute of Wood Chemistry, Riga, LV 1006, Latvia, [email protected]
Riga Technical University, Riga, LV 1048, Latvia
The polyanionic nature allows soluble lignin to form interpolyelectrolyte complexes
(LPCs) with polycations in aqueous media. The soluble lignins are active, but chitosan
(Ch) is inactive at the air-water interface. However, these polyelectrolytes may be used as a
stabiliser of the oil-in-water (O/W) emulsion. In the present work, the behaviour of LPC
consisting of kraft lignin (KL) and Ch at the air-water interface depending on the chitosan
content and the environment was studied. Softwood KL with Mw = 4160 (by SEC) and
chitosan (Ch) (DD = 78 %) with Mw = 4x105 (by viscometry) were used. LPC was obtained
in the reaction mixtures by mixing the aqueous solutions of both polyelectrolytes within
the pH interval of 4.4-8.2 at 293K.The surface tension (σ) and surface pressure at the airwater interface were measured by the Wilhelmy plate, using tensiometer Kruss K100 and
KSV NIMA Langmuir trough, respectively. The stabilizing effect of LPC in terms of the
volume and time of water separation was studied in the rapeseed oil-in-water emulsion
emulated with a Disperser T10 (IKA).
The possibility to form both non-stoichiometric (soluble) and stoichiometric
(insoluble) LPC particles depended on the chitosan content in the reaction mixtures. All the
reaction mixtures were characterized by remarkably lower values of σ at the air-water
interface in comparison with the initial KL and Ch solutions. The greatest decrease in σ
took place in the reaction mixtures, in which the soluble LPC particles were characterized
by the optimum hydrophilic/hydrophobic balance values. With decreasing pH, increasing
the concentration and the ionic strength, adsorption ability of the soluble LPC particles at
the air-water interfaces grown that was testified by decreasing the surface tension and
increasing the surface pressure at the air-water interface. It was found that the formed
soluble LPC particles had a more pronounced stabilising action on the O/W emulsions than
the initial KL and Ch. The sizes of the stabilised emulsion drops were varied from 1.6 mk
to 3.0 mk, but their zeta potential was changed from -28 mv to -46 mv at pH 6.0,
depending on the chitosan content in the reaction mixtures. The emulsion drops stabilised
with KL and Ch were characterised by higher sizes and a lower aggregative stability.
Fig. 1. Drop images (x200) of the O/W emulsion stabilised with initial KL (on the left) and soluble
KL/Ch polyelectrolyte complex (on the right)
162
EFFECT OF STORAGE TIME ON THE AQUEOUS SOLUTION
PROPERTIES OF POLYELECTROLYTE COMPLEX BASED ON
SODA LIGNIN
G. Shulga, S. Vitolina, B. Neiberte, A. Verovkins, J. Brovkina, S. Livcha, V. Shakels
Latvian State Institute of Wood Chemistry, 27 Dzerbenes Str., LV 1006, Riga, Latvia, [email protected]
Aspen wood is one of the major wood species in Latvia. The sawdust formed during its
processing is used mainly for energy needs. At thesame time, it can serve as a feedstock for
obtaining soda lignin, which is used for production of environmentally friendly and
inexpensive surface active agents. The soda delignification for obtaining lignin has some
essential advantages in comparison with the sulphate process due to a lower pollution of
waste water and the absence of unpleasant sulphur odorants. To improve the surface
activity of soda lignin, it was subjected to chemical modification. One of the promising
modes to obtain macrosurfactants is the formation of polyelectrolyte complexes (PEC).
The target of this study was to investigate the effect of the storage time of the watersoluble PEC formed as a result of the interaction of aspen soda lignin (ASL) with branched
polyethyleneimine (PEI) in alkaline solutions on their surface activity at the air-water
interface and viscosity. The composition of the formed reaction mixtures was expressed by
the mass ratio of the polyelectrolytes (PEI/ASL). The surface tension of the reaction
mixtures at the air-water interface and the surface pressure of the interface layers were
measured using a tensiometer “Kruss K100” and a KSV NIMA Langmuir Trough,
respectively. The sizes and zeta potential of the obtained PEC particles were measured by
dynamic light scattering using Malvern Nanosizer NZ.
It was shown that, after 2 h, the surface activity of the formed water-soluble PEC at the
air-water interface considerably exceeded the activity of ASL and PEI, irrespective of the
PEC composition and environments, indicating a synergetic effect, governed by the
structural peculiarities of the formed complex particles, namely, by their hydrophilichydrophobic balance. This was testified by a decrease in the surface tension and an
increase in the surface pressure at the water-air interface of the PEC water solution due to
the formation of the interface ASL/PEI films. The surface pressure-area isotherms of the
PEC films demonstrated regions of reduced compressibility in intermediate film areas
(plateau). The further compression impact led to an increased compressibility, which
testified the formation of multilayers at the air-water interface. With increasing PEC
composition, the final pressure of the PEC-based films grew. Under the same conditions,
the LS adsorption at the interface was low, which reflected by its low surface pressure (πA) values. The sizes of the water-soluble PEC particles non-linearly depended on the
reaction mixture composition and varied within a range of 190-330 nm. With increasing
PEC composition, the Z potential of the obtained soluble PEC particles tended to decrease.
After 24 h of the reaction mixture preparation, for the whole composition of the PEC, the
surface tension at the air-water interface remarkably decreased, but the surface pressure
was enhanced, indicating the manifested re-organisation of the polymeric films due to their
structurisation, which can be associated with changing the structure of the adsorbed PEC
particles in time, leading to their hydrophobisation and strengthening of
intermacromolecular interactions in the polymeric films. With increasing storage time, the
reduced viscosity of the PEC solutions in alkaline medium increased.
163
THE EFFECT OF RECYCLING DURATION AND FILLING ON THE
PROPERTIES OF POLYCAPROLACTONE-BASED
THERMOPLASTIC POLYURETHANE
V. Skrockienė, K. Žukienė, A. Lisauskaitė
Department of Clothing and Polymer Products Technology, Kaunas University of Technology, Kaunas,
Lithuania,[email protected]
Thermoplastics are quite easy to material recycle. A problem is that the material
properties deteriorate for every time the plastic are recycled. There are two solutions to this
problem; recycle the material in products that requires lower material properties, or mix the
recycled material with fillers, e.g. improve the materials properties [1]. Low temperature
biodegradable polycaprolactone-based thermoplastic polyurethane (TPU) is used for short
life orthopedic devices. However, the biomedical application of TPU creates large amount
of production waste. The possibility of recycling and secondary use of TPU was
investigated in [1, 2]. It has been found that recycled TPU blends have worse mechanical
and shape memory properties compared with the pristine materials.
Therefore, in this work the effect of the recycling duration and the organically
modified (Cloisite 30B) and non-modified (Nanofil 116) montmorillonite fillers content on
the morphology, melt flow, mechanical properties, and hydrolytic degradation of TPU
waste (rTPU) were investigated. rTPU and rTPU/fillers composites were obtained by
mastication on the open mill up to 1700 s. The structure of the composites was
characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD).
XRD analysis shows the interlayer spacing of Cloisite 30B in rTPU increases with the
increase in mastication time. Exfoliated composite of rTPU and Cloisite 30B clay was
obtained at a mastication time of 1700 s. In the other hand rTPU was not intercalated
within Nanofil 116 clay layers and "phase separated" structure was formed.
Results show that recycling decrease rTPU crystallinity in 50 %. However, the
increase in crystallinity of rTPU was found, when fillers were incorporated. The
rheological properties of rTPU were improved after recycling processes. Nanofil 116 clay
slightly increases melt flow index of rTPU with increasing the filler mixing time.
Meanwhile, the exfoliation of modified Cloisite 30B particles deteriorates rheological
properties of rTPU.
The mechanical properties of rTPU were deteriorated with the increasing of recycling
time and the incorporating of montmorillonite does not change this trend. SEM showed a
poor dispersion and the adhesion between Nanofil 116 fillers and matrix.
During hydrolytic degradation, weight loss of rTPU increases by both the increasing of
recycling time and incorporating of the fillers. The degradation of rTPU composites with
Cloisite 30B fillers proceed faster than that with Nanofil 116 ones, due to the higher
interaction with rTPU matrix.
References
1. S. M. Al-Salem, Lettieri, J. Baeyens. Waste Management, 29, 2625-2643 (2009).
2. V. Jankauskaitė, A. Laukaitienė, V. K. Mickus. Mater. Sci. Medz., 15, 142-147 (2009).
3. K. Žukienė, V. Jankauskaitė, V. Betingytė, A. Baltušnikas. J. Appl. Polym. Sci., 128, 2186 - 2196 (2013).
164
HIGH DENSITY RIGID POLYURETHANE FOAMS OBTAINED
FROM RESIDUES OF PET INDUSTRY AND MODIFIED WITH
CLOISITE TYPE NANOPARTICLES
L. Stiebra, U. Cabulis, M. Kirpluks
Polyurethane (PU) foam commercial applications are increasing, especially in
construction and transportation systems. The main raw materials of PU foams are polyol
and isocyanate, both derived from petroleum. As demands for environmentally friendly
products are rising petrochemical polyols are replaced with renewable polyols [1].
Production of Neopolyol® based on transesterification of PET by diethylene glycol in the
presence of functional additives is used. This process allows to obtain stabile low cost
polyols with excellent quality. Hydroxyl number of different Neopolyols® varies from 240
to 380 mgKOH/g; viscosity from 3000 to 6000 mPa·s; acid number <1 mg KOH/g, water
content <0.1 % [2].
In order to achieve better physical and chemical properties PU matrix was reinforced
with montmorillonite (MMT) type nanoparticles. Since MMT is not compatible with
hydrophobic polymers they are modified with a dimethyl dehydrogenated tallow
quaternary ammonium and methyl tallow bis-2-hydroxyethyl quaternary ammonium.
Commercially these organoclays are known as Cloisite®15A and Cloisite®30B (produced
by Southern Clay Products, Inc.). Before PU systems were foamed, nanoparticles were
dispersed in polyols using Ultrasonic Cell Crusher, Model Sonic 650W (ultrasonic
frequency 20-25 kHz, and maximum power of 650 W) at 30 oC. The process time and
nanoclay concentration was varied.
The results showed that compression strength of nano-reinforced PU foams increased
by 10% (from 4.0 to 4.4 MPa). Nanoclay-polyol mixture viscosity increases as nanoclay
content increases (10000 - 70000 mPa·s)
a
b
Fig. 1. Scanning electron micrographs of PU foams a) without fillers, b) modified with nanoclays
For samples scanning electron micrographs (SEM) were taken. Figure 1 shows the
image of PU foams without fillers (a) and modified with nanoclays (Cloisite15A) (b). It is
seen that foam cell number increased and foam cell size with introduction of nanofillers
decreased. The smaller cell size of foams filled with nanoclays can be explained by nano
particle surface that works as a nucleation site.
References
1. H. Fan, A. Tekeei, G.J. Suppes, F.H. Hsieh. Int. J. Polym. Sci., 8 (2012)
2. I. Vitkauskiene, U. Cabulis. SusPolyUrethane, Mövenpick, Amsterdam, 2013.
165
IMMOBILIZATION AND CATALYTIC PROPERTIES OF
MALTOGENIC α-AMYLASE ON PUU MICROPARTICLES
A. Strakšys1,A. Dulko1, J. Razumiene2, I. Sakinyte2, T. Kochane1, S. Budriene1
1
Department of Polymer Chemistry, Vilnius University, Naugarduko 24, LT-0322, Vilnius, Lithuania,
[email protected]
2
Institute of Biochemistry, Vilnius University, Mokslininku 12, LT-08662, Vilnius, Lithuania
Poly(urethane-urea) (PUU) as a functional materials have a wide application in many
areas. PUU particles are used for coatings, adhesives, paints, powder moulding, biomedical
and biotechnological purposes.Native enzymes are expensive and sensitive for
environment. Immobilization of enzymes is a very effective alternative in overcoming
problems of instability and repetitive use of enzymes. The use of an immobilized enzyme
permits to the control of the reaction: the simple filtering of the enzyme to stop the
reaction. Immobilized enzymes could be used several times or reused for long times in
reactors and, in addition to that, some critical enzyme properties have to be improved like
stability, activity, inhibition by reactions products [1].
The aim of the present study is synthesis of PUU microparticles from poly(vinyl
alcohol) (PVA) and 4,4’-methylenebis(cyclohexyl isocyanate) (DCHMDI) and to apply
PUU microparticles for immobilization of maltogenic α-amylase (MG). PUU was
synthesized by one-step method according to our previous works [2, 3]. Initial conditions
of synthesis of PUU were influenced the structure of obtained PUU and properties of
immobilized MG. Changing the initial molar ratio of PVA and DCHMDI from 1:2 to 1:3
during synthesis of PUU, microparticles resulted in increasing efficiency of immobilization
(EI) of MG from 60.4 % to 87.6 %. When initial molar ratio of PVA and DCHMDI was
changed from 1:3 to 1:6, EI of MG onto PUU decreased from 87.6 % to 49.33 %.
Immobilization of MG onto PUU microparticles depends on reaction time and temperature
of synthesis of PUU, too. Prolongation of reaction time from 60 to 150 min, when PUU
microparticles were synthesized using initial molar ratio of PVA and DCHMDI 1:3,
resulted in decreasing EI of MG from 91.2 % to 59.0 %. Meanwhile, increasing reaction
temperature from 70 to 110 oC resulted in increasing EI of MG from 76.2 % to 97.3 %.
Immobilization of MG onto PUU microparticles, obtained at 130 oC, was unsuccessful. No
enzymatic activity was achieved in this case. Storage stability of immobilized MG on PUU
microparticles was investigated after 14 and 28 days storage in citrate buffer, pH 5.0, at
4 oC. Immobilized MG was stable in time when PUU microparticles were synthesized at
various reaction temperatures and time and after 28 days storage from 95 % to 41 % of
residual activity was remained. The residual activity of native enzyme was determined,
too. After 14 and 28 days storage, residual activity of native MG decreased to 70.1 % and
56.8 %, respectively. Immobilization of MG onto PUU microparticles could pass by
covalent attachment and by physical adsorption, caused by hydrogen bonds and Van der
Waal’s forces.
Acknowledgements. This work was funded by the European Social Fund under National Integrated
Programme Biotechnology & Biopharmacy, grant VP1-3.1-SMM-08-K01-005.
References
1. B. Krajewska. Microb. Technol., 35, 126-139 (2004).
2. T. Romaskevic, E. Viskantiene, S. Budriene, et.al. J. Mol. Catal. B: Enzym., 64, 172-176 (2010).
3. S. Budriene, E. Udrenaite, E. Viskantiene, T. Romaskevic, A. Zubriene, G. Dienys. Baltic Polymer
Symposium, Lithuania, Programme and Proceedings, Kaunas, 41-42 (2004).
166
THE EFFECT OF PLASMA TREATMENT ON THE TENSILE
PROPERTIES OF NATURAL FIBER REINFORCED PLA
COMPOSITES
A. Širvaitienė1, V. Jankauskaitė1, P. Bekampienė2
1
Faculty of Design and Technologies, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
2
SRI Center for Physical Science and Technology Textile Institute, Kaunas, Lithuania
After the extensive use of synthetic materials due to ecological concern the natural and
biodegradable polymer composites has been attracted great interest. Natural fibers, such as
flax, hemp, sisal and jute, are environmentally friendly reinforcement alternative to high
performance fibers. To improve the strength of natural fiber reinforced composites the
water based chemical treatments of fiber are commonly used. In comparison with these
treatments the non-thermal plasma technology is environmentally friendly and energyefficient [1, 2].
The aim of this study was to determine the effect of plasma treatment conditions on the
tensile properties of natural fiber reinforced poly(lactic acid) (PLA) composites. As
reinforcement fiber flax and cotton yarns were used.
It was received that the most effective plasma treatment is at 100 W discharge power
and 60 s treatment time. Due to fiber treatment the tensile strength of cotton yarn
reinforced composites increased up on 96% and that of flax yarn – 61%, respectively.
References
1. T. Desmet, R. Morent, N. De Geyter, Ch. Leys, E. Schacht. Biomacromolecules, 10 (9), 2351-2378
(2009).
2. S. Sever, S. Erden, H.A. Gülec, Y. Seki, M. Sarikanat. Mater Chem Phys., 129, 275-280 (2011).
167
MICROBIOLOGICAL INVESTIGATION OF SHORT TIME
PRESERVED SKIN
J. Širvaitytė1, K. Beleška1, V. Valeikienė1, V. Valeika2, R. Alaburdaitė2
1
Department of Organic Technology, Kaunas University of Technology, Kaunas Lithuania,
[email protected]
2
Many and various microorganisms live in hair of animals hide/skin. After flaying the
microorganisms taint flesh side of hide/skin and through this side pass into derma. High
content of moisture (62-65%), soluble in water proteins and fats stimulate the fast
reproduction of microorganisms, especially which cause putrefaction. A preservation of
hide/skin stops the growing of microorganisms.
The aim of research was the investigation of short term preservation of skin using
various preserving materials.
Seven methods of preservation were tested for rabbit skin preservation (see Table).
The preserved skin samples were stored at 28oC. The quality of the preserved skin was
estimated according to total amount of bacteria in skin tissue, which was determined after
2, 7, 14, 21 and 28 days of storage (see Table). The total amount of microorganisms was
determined using „dilution and pouring“ method. Testing specimens were inoculated on
plates with agar (Liofilchelm, Italija). The inoculated Petri plates were incubated at 35–
37oC temperature, for 48 h. After the incubation was determined concentration of CFU ml1
(colony forming units).
Table. Dependence of total amount of microorganisms in skin samples on storage duration
Storage duration, days
Preservation method number, used materials
(% on fresh skin mass) and way of them carry
2
7
14
21
28
up on skin
Total amount of microorganisms, CFU ml-1
1st, NaCl – 15, top dressing
1.4x104
2.3x107
2.3x107
2.3x107
2.1x106
nd
4
7
9
9
2 , NaCl – 15 + Na2SiF6 – 1, top dressing
1.1x10
2.8x10
3.5x10
5.5x10
1.8x106
rd
3
5
9
8
3 , NaCl – 15 + Na2B4O7 – 1, top dressing
9.2x10
1.1x10
1.8x10
8.0x10
1.5x104
th
3
6
7
7
4 , NaCl – 15 + Al2(SO4)3 – 1, top dressing
1.3x10
3.8x10
2.3x10
8.0x10
2.5x105
th
5 , NaCl – 15 + thyme essential oil – 5, top
0
2.6x103
2.6x103
2.6x103
0.01x106
dressing
6th, C2H5OH – 100, spraying
1.6x10-5 3.2x103
3.2x103
3.2x103
0.03x106
th
7 , C2H5OH (96 %) 99.4 + thymol – 0.06 % ,
0
0
0
0
0.02x106
spraying
Note. Total amount of microorganisms in skin before preservation was 0.03x10 6 CFU ml-1.
Summarising the results of bacteriological investigation can be proposed that use of 7 th
method best blocks growing of microorganisms. The amount of microorganisms in skins
preserved by 1st and 2nd methods was higher after 28 days storage comparing with initial
amount before preservation (0.03x106 CFU ml-1). Despite of this fact, organoleptical
assessment of all preservation methods showed that after 28 days of the storage all samples
had not bad odour, the bond between hair and derma was without any changes. So, all
tested methods are suitable for short term preservation of skin.
Acknowledgement
The research was carried out according to cooperative agreement with Kaunas Tadas Ivanauskas Museum of
Zoology.
168
BIODEGRADBLE POLYMER COMPOSITES CONTAINING
NUTRIENTS FOR SLOW RELEASE FERTILISERS
J. Treinyte1, V. Grazuleviciene1, M. Gumbyte2
1
Institute of Environment and Ecology, Aleksandras Stulginskis University, Akademija, Kaunas region,
2
Laboratory of Chemical and Biochemical Research for Environmental Technology, Aleksandras Stulginskis
University, Akademija, Kaunas region, Lithuania
Composites consisting of polyvinyl alcohol (PVA), nitrogen- and phosphoruscontaining waste materials were prepared and studied as materials for encapsulation of
mineral fertilizers. By-products of biodiesel production, i.e. rapeseed cake (RC) and crude
glycerol, horn meal (HM) which is the waste product of haberdashery, and
phosphogypsum (PG), which is by-product of the production of phosphorus fertilizers,
were used as the fillers of the composites. The mass ratio of polyvinyl alcohol, filler and
glycerol was kept constant (4:6:3) in the preparation of the composites. The films of the
composites with the different amounts of nitrogen and phosphorus were prepared using
different fillers or their mixtures. Mechanical properties of the films, hygroscopicity,
solubility in water were studied. The influence of the fillers and their mixtures on the
properties of the composites was estimated. The composite films containing PG exhibited
higher elasticity than the films of the composites containing HM or RC. The films in which
the mass ratios PVA:HM, PVA:RC and PVA:PG were 4:6 exhibited the tensile strength of
10.2, 14.0 and 4.95 MPa respectively. Elongation at break of the same series of films was
found to be 5.58, 4.14, 121% respectively while the tensile modulus was 442, 432 and 152
MPa correspondingly. When the mixtures of HM and RC were used as the fillers, the mass
ratio of these components did not have any substantial effect on the mechanical properties
of the composites. The films of the composites containing PG showed lower
hygroscopicity and higher stability of dimensions than those containing HM or RC or their
mixtures as the fillers. The influence of the fillers on the stability of dimensions in the
environments with the changing moisture was also studied.
Acknowledgements.Financial support of this research by the Research Council of Lithuania (project No
MIP-057/2012) is gratefully acknowledged.
169
EFFECT OF FINISHING TREATMENT ON YARN PULLOUT
BEHAVIOUR IN TERRY FABRICS
S. Petrulytė, A. Veličkienė, D. Petrulis
Department of Textile Technology, Kaunas University of Technology, Kaunas, Lithuania,
[email protected]
The yarn pullout force in a fabric depends on the geometry of the fabric, type of yarn
and fibre as well as on fabric treatment [1]. Besides, the yarn pullout test is a suitable
method for investigating the internal mechanical properties of fabric structure performed
during weaving or knitting [2]. Terry fabrics analysed in our research were made using:
pile warp – bleached linen yarn, 50 tex; ground warp and weft – plied cotton yarn, 25 tex x
2 and cotton yarn, 50 tex, respectively. The pile height of the fabric was 6 mm. Grey fabric
was affected by finishing: industrial washing with detergent (60 min, 600C) Felosan NOG
CHT (Germany), softening (60 min, 400C) with Tubingal SMF CHT (Germany),
centrifuging and drying in air (B1) or tumbling for 30, 60, 90, 120 or 150 min (B2, B3, B4,
B5, B6, respectively). The resistance to pile loop extraction (F) was measured according to
EN 15598:2008. Factorial design was made and regression analysis was performed. It was
found that the resistance to pile loop extraction depends on finishing: for B1 fabric F
varied from 418.5 to 1190.8 mN and for other variants the resistance to pile loop extraction
was 282.5-988.3 mN, investigating 5-25 mm pulling distance (z). The changes in F
regarding tumbling period were not statistically significant analysing some tumbling
periods but the minimum values of F were received for the fabrics tumbled for 90-150 min.
The determination coefficient R2=0.9448-0.9928 indicated the existence of an excellent
relation between F and z (Fig. 1). The statistical analysis showed that the relative error of F
varied in 7.5-14.6 % except single cases then this index was higher.
1400
1300
F, mN
1190.8 ±134.2
1200
B3
y = 32.514x + 220.13
1100
R2 = 0.9588
1000
B1
y = 37.154x + 314.25
900
R2 = 0.9448
1095.4 ±112.9
988.3 ±90.1
886.7 ±89.3
861.7 ±64.7
870.8 ±118.8
800
782.3 ±103.7
743.3 ±78.3
835.8 ±111.6
745.8 ±94.0
700
713.3 ±72.7
604.2 ±88.1
600
611.7 ±87.1
500
418.5 ±86.3
400
B4
y = 27.202x + 184.47
300.8 ±67.5
200
R2 = 0.9847
475.0 ±54.0
316.7 ±45.5
300
B5
y = 27.464x + 175.36
593.3 ±85.8
479.2 ±61.9
R2 = 0.9928
282.5 ±27.4
100
5
10
15
20
25
z, mm
Fig. 1. Resistance to pile loop extraction of finished fabrics.
References
1. N. Pan, M. Yoon. Text. Res. J., 63, 629-637 (1993).
2. A. Asayesh, E. Niazkhani, A. A. A. Jeddi. J. Eng. Fiber. Fabr., 7, 121-128 (2012).
170
POLYETHYLENIMINE FOR USE AS A COAGULANT FOR
EXTRACTING WOOD BIOMASS FROM WASTEWATER
S. Vitolina, G. Shulga, B. Neiberte, S. Reihmane
Latvian State Institute of
[email protected]
Wood
Chemistry,
27
Dzerbenes
Str.,
LV
1006,
Riga,
Latvia,
The wastewater of hydrothermal basins of plywood production contains wood biomass
in the form of hemicelluloses, lignin and wood extractives, which are the reason for the
high chemical oxygen demand (COD) and the enhanced degree of water colour. It is
known that the purification of wastewater combines various methods, i.e., chemical
oxidation and precipitation, aerobic and anaerobic biological treatments, use of
membranes, activated carbon adsorption and the coagulation – flocculation process. The
aim of this work was to study the efficiency of the coagulation of the model wastewater for
extracting wood biomass by a high-molecular cationic polyelectrolyte. Model wastewater
was obtained by the treatment of birch wood in a weak alkaline solution with a
hydromodulus of 1/50 at 90ºC for 4 h. As a coagulant, polyethyleneimine (PEI) with a
molecular weight of 7.5·104 was used. Optimal conditions of biomass coagulation from the
model hydrolyzate were varied in a PEI dosage interval of 7-140 mg/l and a pH range of 310. The effectiveness of coagulation was defined after a system settling time of 120 min
and filtration. The efficiency of biomass and lignin isolation from the model hydrolyzate
was evaluated in terms of the removal of biomass, lignin only, colour and the
permanganate index. The residual concentration of the biomass and lignin was defined,
using their preliminarily obtained correlation curves. COD and the colority of the filtrate
were determined by ISO 15705 and LVS EN ISO 7887, respectively. The PEI coagulation
efficiency highly depends on the pH and dosage. The total suspended biomass removal at
various PEI dosages and pH has shown that, with increasing PEI dosage, the optimal value
of the biomass coagulation pH increases. For example, at a dose of 7 mg/l, the maximal
precipitation occurs at a pH of 3.0. However, at a dose of 70 mg/l, the maximal yield of
biomass takes place at a pH of 9.0. The maximal degree of purification, i.e., 93% of total
biomass, 64% of lignin, 86% of colority and 41% of COD reduction is found to be reached
using a PEI dosage of 35 mg/l at pH 6. Under these circumstances, the charge
neutralisation mechanism between PEI and the biomass components with the formation of
polyelectrolyte complexes in the form of insoluble and colloid particles occurs. The higher
efficiency of PEI in comparison with Al-containing coagulants may be governed by
realising the complex mechanism of the biomass components’ precipitation.
Removal; %
93
100
90
81
80
64
60
60
61
49
WB
56
Lignin
40
20
pH
0
5.0
6.0
7.0
8.0
Fig. 1. Wood biomass (WB) and lignin removal from model wastewater at optimal dosage of PEI and pH
171
ELECTROPHOSPHORESCENT DIODES BASED ON Ir(Fppy)3.
D. Volyniuk1,2, P. Stakhira2, J.V. Grazulevicius1, V. Cherpak2,
J. Keruckas1,Z. Hotra2,3, M. Hladun4
1
3
4
European University, Lviv, Ukraine
2
Organic light-emitting diodes (OLEDs) have potential applications in full-colour, high
resolution, large area flat-panel displays, future flexible displays, and solid-state lighting
[1]. Phosphorescent OLEDs (PhOLEDs) are characterized by high luminous efficiency.
The triplet emitters enable an internal quantum efficiency as high as 100% converting both
singlet and triplet excitons into photons [2]. The achievable 100% internal quantum
efficiency is based on the use of the host-guest strategy with triplet emitters (guests)
dispersed homogeneously into suitable organic matrix (the host). We have fabricated and
studied blue-green PhOLEDs by simultaneous vacuum deposition of host materials, 3,6bis(indol-1-yl)-9-phenylcarbazoles (BIPCs), and of the triplet guest tris[2-(4,6difluorophenyl)pyridinato-C2,N]iridium(III) complex (Ir(Fppy)3).
The phosphorescence spectra of the films of BIPCs at 77K exhibit emission peaks that
can be attributed to a sandwich excimer of adjacent carbazole moieties. High triplet-levels
(ca. 2.7 eV) of BIPCs give a possibility of using these materials as hosts for blue
PHOLEDs. BIPCs are characterized by relatively high values ofglass-transition
temperatures (77-95 °C).
The electroluminescent devices ITO/CuI/BIPCs:Ir(Fppy)3/TCz1)/Ca/Al were
fabricated by means of vacuum co-deposition of BIPCs and Ir(Fppy)3as reported earlier
[2]. Electroluminescence maxima of the devices based on BIPCs:Ir(Fppy)3 are observed
at 476 nm and 500 nm The shape of the spectra of electroluminescence is similar to that of
PL spectra of the solid films of Ir(Fppy)3. This observation confirms that
electrophosphorescence is nature of the emission of the devices. The current density –
voltage curves of the devices show minimum turn-on voltage Von of 6.8 V, and maximum
brightness of 11000 cd/m2 with current efficiency of 12.2 cd/A. CIE chromaticity
coordinates (x, y) of the devices ITO/CuI/BIPCs:Ir(Fppy)3/TCz1/Ca/Al exhibiting blueto-green colour were found to be (0.23, 0.44).
Ackowledgments. This research was supported by FP7 REGPOT-2012-2013-1 REGPOT-2012-2013-1 ICT
project CEOSeR (grant agreement No 316010). It was also supported by the Lithuanian–Ukrainian
Cooperation Programme in the Fields of Research and Technologies (project No TAP LU 01/2012)
References:
1. A. Michaleviciute, E. Gurskyte, D.Yu. Volyniuk, V.V. Cherpak, G. Sini, P.Y. Stakhira,
J.V. Grazulevicius. J. Phys. Chem. C, 116, 20769-20778 (2012).
2. D. Tomkute-Luksiene, J. Keruckas, T. Malinauskas, J. Simokaitiene, V. Getautis, J.V. Grazulevicius,
D. Volyniuk, V. Cherpak, P. Stakhira, V. Yashchuk, V. Kosach, G. Luka, J. Sidaravicius. Dyes and
Pigments, 96, 278-286 (2013).
172
NANOCOMPOSITES BASED ON POLYURETHANE AND ON
MESOPOROUS SILICON DIOXIDE MODIFIED WITH METAL
OXIDES
E.R. Volkova
Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia, [email protected]
Over last years, a trend related to the use of mesoporous materials based on silicon
dioxide (MCM) and featured by high specific surface area, by nanosized organized pores,
and by high concentration of hydroxyl groups as active fillers for polymers is actively
progressing 1. In this work, effect of MCM–48-based nano-dispersive materials
modified with Fe2O3, TiO2, ZrO2, CuO2, and NiO on the structure and properties of lowtemperature curing polyurethane composites is investigated. A polyurethane composition,
fast-curing at room temperature and based on mixtures of hydroxyl-containing oligomers
featured by different functionalities with polyisocyanate, was considered as a polymeric
matrix 2.
The effect on nanomaterials on rheological properties and curing kinetics of
polyurethane compositions is investigated. Reasoning from catalytic action and from the
effect on vitality of reaction mass, fillers are ranged as follows:
Fe2O3–SiO2 < TiO2– SiO2 < ZrO2– SiO2 < CuO– SiO2 < NiO– SiO2.
The effect on nanomaterials on physic-mechanical properties of polyurethanes is
investigated as well. It is demonstrated that upon addition of 0.5%wt. filler, strength of
polyurethane increases 1.2–1.5-fold, whereas the Young modulus increases 1.4–1.7-fold as
compared with an unfilled material. The strain increases from 12% to 18%.
Correlation between structural variations occurring in a polymer in the presence of
filler, and physic-mechanical properties of polyurethanes is detected by using the Raman
spectroscopy. The MCM–48-based fillers are «embedded» into the structure of polymer
due to formation of additional hydrogen and chemical bonds between superficial OH–
groups of filler and the polyurethane matrix. The increase in hydrogen bonds’
concentration and enhancement of intermolecular interaction lead to formation of more
regularly structured polyurethanes resulting in the increase in the strength and elastic
modulus values.
It has been ascertained that nanomaterials based on MCM–48 and modified with metal
oxides can be used as multifunctional modifiers functioning simultaneously as curing
catalysts and as reinforcing fillers in polyurethane systems based on a mixture of hydroxylcontaining oligomers and polyisocyanate.
Ackowledgments. This work was financially supported by the Department of Chemistry and Material
Sciences of the Russian Academy of Sciences “Creation of and investigation in macromolecules and
macromolecular structures of new generations” (Project 12-T-3-1002), by the Russian Foundation for Basic
Research (Project 12-03-00281).
References
1. A. Melissa, Ver Meer, Balaji Narasimhan, Brent H. Shanks, Surya K. Mallapragada. Applied Materials
& Interfaces, 2 (1), 41–47 (2010).
2. E.R. Volkova, V.V. Tereshatov, Zh.A. Vnutskikh. Rus. J. of Appl. Chem., 83 (8), 1372–1379 (2010).
173
STRUCTURE–PROPERTY RELATIONSHIPS OF POLYURETHANE
COMPOSITES SYNTHESIZED USING VARIOUS OLIGODIOLS
E.R. Volkova
Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia, [email protected]
High-strength rigid polyurethane composites based on hydroxyl-containing oligomers
of various functionalities and polyisocyanate have been obtained via successive synthesis
of the branched polymer system. The influence of molecular mass of two-functional
oligoester as a constituent of a multi-component oligomer base on the properties of a
polyurethane material quickly curable at low temperatures has been studied.
A relationship between molecular mass of hydroxyl-containing oligomer, urethane
formation rate constant and rigidness of the material has been ascertained. The lesser
molecular mass of oligodiol is, i.e. the larger the content of OH-groups in initial oligomer
mixture is, the higher is rate constant of polyurethane formation, concentration of urethane
groups, and density of polyurethane’s chemical network. With the increase in cross-linking
frequency and in the content of hard urethane segments inhibiting conformational
transformations, the polymer becomes harder.
A decrease in diol’s molecular mass and, respectively, in the length of soft segments
located between network’s nodes, leads to a deceleration of segments’ mobility and, as a
consequence, to an increase in viscosity and to reduction of the composition’s viability.
When using of low-molecular oligodiols at polyurethane synthesis, structural changes
registered by Raman spectroscopy take place. The increase of relative intensity of the
peaks typical for rigid urethane segments with strong hydrogen bonds has been detected on
Raman spectra.
Introduction of low-molecular hydroxyl-containing oligomer into the mixture enables
to significantly raise glass transition temperature, strength and modulus of elasticity of
multi-component polyurethane materials.
Ackowledgments. This work was financially supported by the Department of Chemistry and Material
Sciences of the Russian Academy of Sciences “Creation of and investigation in macromolecules and
macromolecular structures of new generations” (Project 12-T-3-1002), by the Russian Foundation for Basic
Research (Project 12-03-00281).
174
RIGID POLYURETHANE FOAMS OBTAINED FROM BYPRODUCTS OF PET PRODUCTION
V.Zeltins1, U.Cabulis1, I.Vitkauskiene2
1
Latvian State Institute of Wood Chemistry, Dzerbenes str. 27, LV-1006, Riga, Latvia,
[email protected]
2
UAB NEO Group, Silutes str.9, Rimkai LT-95346, Dovilai sen. Klaipeda district, Lithuania
Polyurethanes (PUR) are one of the most required polymers due to their versatility.
Rigid PUR foams are applied on a large scale mainly as thermal insulating materials. Due
to dwindling petrochemical resources, the production of polymers, including PUR foams,
from renewable or recyclable resources is being actively investigated. As raw material in
current research was used polyester polyol Neopolyol®380 (OH-value = 380 mgKOH/g,
visc. = 3000 mPas) obtained from PET (polyethylene terephthalate) industry by-products
and produced in commercial scale by one of the biggest manufacturers of PET granules in
Europe - NEO Group, Lithuania (Klaipeda). Production of Neopolyol®380 based on
transesterification of PET by diethylene glycol in the presence of functional additives is the
process preserving natural resources, reducing production cost, and enabling to obtain
polyols competitive with those produced from petrochemical raw materials because of
excellent and stable quality [1]. There were developed different foam compositions with
various densities and foaming parameters, there are only one constant figure in all recipes:
ratio by vol.: Polyol comp. / Isocyanate comp. = 1 / 1. Typical rigid PUR foams
compositions are given in following table:
Neopolyol®380
Sorbitol polyether polyol
H2O
Blowing agent
Flame retardant
Catalyst
Surfactant
PMDI
Isocyanate index
Content of Neoplyol 380 in Polyol component, %
pbw.
75 – 100
0 – 25
0.5 – 2.2
7 – 35
20
0.5 – 3.5
1.5
135 – 160
115 – 120
51 - 68
There were obtained PUR foams with densities 30 – 105 kg/m3, all obtained materials
characterizes with fine cellular structure, high closed cell content (>95%), low water
absorption (<2.1 vol.%); and what is very important for thermal insulation materials, good
thermal conductivity coef. (<0.025 W/m·K) and compressive strength (>0.21 MPa);
optimum flammability class – E (EN 13501-1) and dimension stability. The rigid PUR
foam materials for wall and roof insulation with densities 35 and 55 kg/m3 respectively
were obtained in semi industrial scale and tested in real open air conditions. The obtained
systems fully comply with EU norms and standards [2], and their production is encouraged
to taking into account increasing demands for energy efficiency in construction and
refrigeration industry in Europe and in the Baltic states, especially [3].
References
1. I. Vitkauskiene, R. Makuška. Chemija, 19 (2), 29-34 (2008).
2. EN14315 „Thermal insulation products for buildings – In-situ formed sprayed rigid polyurethane (PUR)
and polyisocyanuraye (PIR) foam products”.
3. Green Paper „A 2030 framework for climate and energy policies”, Brussels, 27.3.2013.
175
MOLECULAR DYNAMICS STUDIES OF HYDRATION AND PHASE
BEHAVIOUR OF OXYETHYLATED GLYCEROL AQUEOUS
SOLUTIONS
E. Zhivotova1, V. Andrushchenko2
1
Department of Physics, National University of Pharmacy, Kharkov, Ukraine,[email protected]
Department of Molecular Spectroscopy, Institute of Organic Chemistry and Biochemistry, Academy of
Sciences, Prague, Czech Republic
2
The long-term storage of biological objects under low temperatures is of high
importance both for the purpose of transplantation and preservation of genetic material.
Since ice crystals formed during cooling and/or heating processes can result in damage or
death of biological cells, addition of cryoprotectants (substances which prevent ice crystal
formation) is necessary.
Low molecular weight polymers can serve as cryoprotectants. One of them is
oxyethylated glycerol (OEG) of polymerization degree from 5 to 30. Such important
properties of any cryoprotectant-containing aqueous solutions as phase behaviour and
glass-forming tendency were investigated for OEG solutions by differential scanning
calorimetry, IR-spectroscopy and cryomicroscopy. [1, 2]
In order to rationalize and better understand the experimentally obtained results, in the
current study we performed molecular dynamics simulations of OEG aqueous solutions at
different cryoprotectant concentration. The hydration of OEG molecules and its
dependence on the concentration was determined. Variations in the density of the OEGwater system were obtained and compared with the experimental phase diagrams. The
results of molecular modeling confirmed the earlier obtained experimental conclusions
[1, 2] that OEG could be a promising cryoprotectant.
References
1. E. N. Zhivotova , A. V. Zinchenko , L. G. Kuleshova, et al. Cryoletters., 28, 261-70 (2007)
2. E. N. Zhivotova , A. V. Zinchenko , L. G. Kuleshova, et al. Molecular Physics., 106, 1751-1759 (2008)
176
THE EFFECT OF UNIAXIAL PRETENSION UPON MULTILAYER
TEXTILE SYSTEMS BIAXIAL STRENGTH PARAMETERS
D. Zubauskiene, E. Strazdiene, V. Urbelis
Department of Clothing and Polymer Products Technology, KaunasUniversity of Technology, Kaunas,
The variety of upholstery materials differ by their strength properties and
deformational behavior in longitudinal and transverse directions. It means that mechanical
characteristics of each applied material must be taken into the account individually. The
research presents special method for the investigation of the effect of uniaxial pretension
values upon multilayered textile systems biaxial strength.
For the investigations of the effect of separate materials structure upon the variations
of flexible multilayer systems spatial shape 100 % cotton fabric of plain weave was used as
basic layer. For the second layer five types of 100 % PES fusing interlinings of woven,
knitted and nonwoven structures were applied. Two textile layers were bonded together by
the third layer of polymeric PU adhesive. Adhesive density was 52 and 76 dots/cm2.
Uniaxial testing results show that high anisotropy is characteristic for basic cotton material
and woven interlinings, low anisotropy - for nonwoven and knitted interlinings. Meantime
tension characteristics after adhesive bonding became anisotropic and very close for all
tested systems.
It must be noted that in uniaxial testing two-layer adhesive bonded systems with
woven and knitted interlinings show the second and the third breaking points which are
higher compared to the first one.The first peak point is related with the breaking of basic
material, the second – with the breaking of interlining material and the third – with the
breaking of the last threads of both layers.
Analysing the effect of specimens pretention level upon strains and stresses
distributions it can be seen that in longitudinal pretention the threads of multilayer systems
stronger longitudinal direction break first after which punching process does not stop due
to friction between the punch and the material. Because of this, punching load translocates
on weaker and more deformable transverse direction, which becomes the main load
carrying direction. Thus, the second breaking locates here. The most important role here
plays the friction between the specimen and the punch. Only because of it, the torn
specimen does not slip from the surface of the punch and punching process proceeds.
It was interesting to observe that irrespective to the pretention in transverse direction,
the first breaking appeared in longitudinal direction again. The rest of the process was
going as it was in the previously described case of longitudinal pretention. It means that at
low levels of pretention, e.g. 2.1 % it is possible to control the height of punching, i.e.
deformation level, but not to change the location of critical stresses.
References
1. D. Zubauskiene, E. Strazdiene, V. Urbelis, V. Saceviciene. Material Science, 18 (4), 367-372 (2012).
2. P. Potluri, V. S. Thammandra. Composite Structures, 77, 405-418 (2007).
3. K. Vanclooster, A. Eshghyar, S. V. Lomov. The 14th Int. ESAFORM Conf. on Material Forming, 907912 (2011).
4. K. H. Leong, O. A. Khondker, I. Herszberg. Conference ICCM-12 (1999).
5. K. Ancutiene, E. Strazdiene. Material Science and Applied Chemistry, 21, 45-50 (2010).
177
HIGHLY EFFICIENT INTRINSIC PHOSPHORESCENCE
FROM A σ-CONJUGATED POLYSILANE POLYMER
A. Kadashchuk1,2, Yu. Skryshevski1, S. Toliautas3, J. Sulskus3, L. Valkunas3, S. Nespurek4
1
Institute of Physics, National Academy of Sciences of Ukraine, 03028 Kyiv, Ukraine, [email protected]
Polymer and Molecular Electronics Department, IMEC, B-3001, Leuven, Belgium
3
Faculty of Physics, Vilnius University, LT-10222 Vilnius, Lithuania
4
Institute of Macromolecular Chemistry, Academy of Sciences of Czech Republic, Prague, Czech Republic
2
The interest to phosphorescence (Ph) phenomena in organic semiconducting materials
has greatly increased in last decade due to creation of highly efficient phosphorescent
OLEDs with internal quantum efficiency close to 100% which was achieved by using
organometallic complexes as dopants in organic host. In conventional conjugated polymers
the reported intrinsic Ph quantum yield is usually very small (~10-5) or not detectable at all.
The combination of a low intersystem crossing (ISC) rate implying a low population of the
triplet state, a low radiative rate and a high non-radiative decay results in an extremely low
Ph yield for conjugated polymers devoid of heavy atoms.
In this study we report on a surprisingly highly efficient intrinsic Ph we found in a neat
poly[biphenyl(methyl)silylene] (PBMSi) σ-conjugated polymer featuring quantum yield as
large as ~10% in solid films and 20% in a diluted frozen solution, that is unusually large as
for conjugated polymers devoid of heavy atoms and is comparable to that of
organometallic polymers. The Ph and delayed fluorescence (DF) in this polymer were
studied by time-resolved PL techniques and it was shown that Ph is due to the radiative
decay of triplets on biphenyl side group under excitation of the σ-conjugated polymer
backbone, i. e. with energy well below the lowest singlet state of the biphenyl group, and
the DF comes from polymer backbone as a result of triplet-triplet annihilation. Efficient
triplet energy transfer in the polymer films has been revealed by PL quenching method
using the polymer films doped with different triplet acceptors and organometallic
complexes. We argue that the exceptionally strong Ph in this polymer results mostly from a
greatly increased ISC rate in this polymer between S1 and T1 states of different parts of the
macromolecule.
To clarify the nature of the excited states in PBMSi, we calculated the structure and
electronic spectra of this polymer using Gaussian09 package, choosing DFT/ TDDFT with
B3LYP functional and 6-31G(d,p) Pople basis set. Transition moment calculations
(including spin-orbit coupling) were carried out using GAMESS-US program, at the level
of GMC-QDPT theory. The calculations yield qualitatively well the energy level positions
and wave-function character of electronic excited states in PBMSi. It was found that: (i)
the lowest singlet excited state is of a charge-transfer (CT) character due to (-)
transition between Si-chain and biphenyl group and responsible for the fluorescence of this
polymer; (ii) it is located well below the - transition of the polymer Si-backbone;
(ii) the - transition has the largest oscillator strength and thus dominates the first
absorption band of this polymer; (iii) the lowest triplet state T1 responsible for the
phosphorescence of PBMSi was confirmed to be due to - transition in biphenyl group
and it is populated via ISC transition mainly from the singlet CT state. Finally, we discuss
the reason of the greatly increased ISC rate in PBMSi and demonstrate that this polymer
could be promising for application as host material in white-light emitting OLEDs due to
rather high intrinsic triplet level.
Acknowledgements. The research was supported by the DKNII of Ukraine under the bilateral UkrainianLithuanian project М/318-2013.
178
JSC „NEO GROUP“ is one of the biggest manufacturers of polyethylene terephthalate (PET) granules
in Europe, located in Lithuania near the Klaipeda port. Over 308 thousand tons, which compose 12 per
cent of the European production, are manufactured and sold during a year. “NEO GROUP” provides
its production for the biggest manufacturers of soft drinks, mineral water, beer, food, domestic
chemicals and other manufacturers of plastic packages.
In 2011 „NEO GROUP“ starts new activity – chemical recycling of industrial PET waste into aromatic
polyester polyols. Annual capacity 4.500 tons per year. New product – NEOPOLYOL – is raw material
for manufacturing of Polyurethane (PU) and Polyisocynaurate (PIR) insulation foams.
JSC „NEO GROUP” is the member of multinational packaging company – RETAL GROUP, that
produces PET preforms, HDPE closures, PET resins for plastic packaging and PET films. The major
RETAL GROUP company's clientele include international and local producers of soft drinks, beer and
carbonated beverages. The company plants are located in European Union, Russia, Ukraine,
Kazakhstan and Georgia.
For more details please visit our website: www.neogroup.eu
179
180
INDEX OF AUTHORS
Abraitienė A. 161
Alaburdaitė R. 90, 168
Alonso J. 158
Ancutienė I. 84
Andreyeva O. 146
Andrushchenko V. 176
Aniskevich A. 120
Arshanitsa A. 113, 152
Auzins E. 137
Babushkina M. A.88
Badia J.D. 158, 159
Bakanas R. 64
Bakeev N.F. 80
Ball S. 58
Barabash M.Yu. 65
Baronaitė M. 66
Barsukov V. 40
Barylo G. 108
Baskakov A. 71
Batueva T. 130
Bekampienė P. 161, 167
Beleška K. 168
Belkova L. 121
Bereznev S. 122
Bermejo M. 156
Bernava A. 124
Berzina R. 61, 125, 134
Bezugla T. 48, 67
Bezuglyi M. 48, 67
Birska I. 56
Bitenieks J. 53, 134
Bobokalonov J.T.123
Bockovs I. 125
Bočkuvienė A. 68
Bogomolova O. E. 50
Bol’shakova A.V. 80
Borisova A. 62
Borisova A. 120
Boroznjak R. 126
Bouclé J. 42
Brovkina J. 163
Brzęczek A. 49
Budriene S. 145, 166
Busilienė G. 127
Butkutė R. 69
Cabulis U. 11, 60, 152, 165, 175
Čekavičiūtė M. 70
Chate A. 140
Chen L.-Y. 39
Chernikova E. 71, 77, 106, 114
Chernyavskaya S. 56
Cherpak V. 108,172
Chumachenko V. 67
ChuprinaN.G. 74
Churkina V.Ya. 76
Ciuta G. 72
Claesson P. M. 25, 26
Clarke P. 59
Crudu A. 128
Crudu M. 128
Dainyte A. 73
Data P. 28, 46, 47, 49, 50
Daugela P. 153
DavidenkoI.I. 74
Davidenko N.A. 74
Dedinaite A. 25, 26
Degbia M. 42
Denina I. 121
Domagala W. 28
Dulko A. 166
Dunér G. 25
Dutschk V. 133
Dzenis M. 162
Dzyazko Y. 151
Efimova A.A. 80
Elksnite I. 149
Fedorov D.P. 76
Fernandez P. 157
Flak T. 37
Fleancu M. 129
Frolov A. N. 51, 104
Gabor J. 37
Gaidau C. 128, 129
Galkin J. 55
Gerasimcik I. 145
Getmanchuk Yu.P. 74
Gil-Castell O. 156, 157, 158, 159
Giškonis E. 96
Glaskova T. 20
Glibowski P. 142
Golba S. 37
Gorbunova M. 130, 131
Gostev A. 77, 93, 106
Grabis J. 132
Grazuleviciene V. 169
Gražulevičius J. V. 42, 44, 45, 63, 66, 69,
70, 73, 81, 83, 91, 95, 102, 105, 107, 108,
109, 110, 119, 139, 172
Grigalevicius S. 78, 79, 117
Grigalovica A. 132
Grinfelds U. 121
Griniene R. 78
Grishko V. 131
Grobelny Z. 37
181
Grokhovskaya T. E. 80
Gromadzki D. 32
Grynko D.A. 65
Gudeika D. 63, 73, 81, 119
Gudkova V. 82
Gumbyte M. 169
Gurevits J. 122
Gurskyte E 42
Gustaite S. 133
Hinrichs K. 29, 41
Hladun M. 172
Hotra Z. 108, 172
Huang S.-H. 39
Ionescu M. 128, 129
Ivanauskaitė A. 83
Ivanauskas A. 84
Ivanauskas R. 84
Ivanova T. 53, 134, 149
Jafarzadeh S. 25
Janickis V. 99
Janietz S. 29
Jankauskaitė V. 54, 64, 96, 136, 167
Jankauskas V. 64, 95
Japins G. 61
Jaruseviciute I. 153
Jelinska N. 137, 140
Jonikaitė-Švėgždienė J. 85
Joskaudas T. 85
Jou J.H. 34, 78
Juodzbalys G. 153
Jursenas S. 81
Kajaks J. 138
Kalkis V. 61, 134, 149
Kallavus U. 87
Kalniņš K. 138
Kalnins M. 137, 149
Kampars V. 30
Kanno S. 36, 86
Kärner K. 87
Kašėtaitė S. 139
Kasimova G.F. 123
Kazlauske J. 133
Kers J. 160
Keruckas J. 63, 172
Ketleriute S. 72
Khizhnyak S. 38
Khomenko V. 40
Khotina I. A. 88
Kirpluks M. 60, 135, 165
Kirsnytė M. 111
Kiseļeva T. 57
Kishilov S. 71
Klimkevičius V. 89
Knerelman E.I. 76
Kochane T. 145, 166
Kois J. 122
Kokars V. 30
Komarov P. 38
Konoval V.P. 141
Korichenska O. 48
Kostina Yu. 71
Kostjuk S. V. 51, 100, 104, 112
Kovalev A. I. 88
Kovalovs A. 137, 140
Kozar O.P. 141
Krainova G. 131
Kramarenko E.Yu. 94
Krastins J. 125
Krivorotova T. 85, 142
Krivosheeva O. 25
Krucaite G. 78
Krumme A. 31, 82
Krylova V. 90, 118
Kukhta A. 52
Kukhta N. 44, 51, 108
Kulebyakina A.I. 80
Kuncēvičs J. 57
Kunitskaya L.R. 74, 143
Kus N. 108
Kushakova N. S. 88
Kutsevol N. 48, 67
Kuzhir P. 52, 53
Laiveniece L. 144
Laka M. 56
Lamberty T. 157
Łapkowski M. 28, 43, 49
Laurinavičiūtė J. 155
Laurinavičiūtė R. 91
Lenartowicz K. 43
Łężniak M. 37
Liesiene J. 55, 123, 133, 153
Liimand K. 160
Lisauskaitė A. 136, 164
Litmanovich E. 92
Liu L. 79, 117
Liu X. 26
Livcha S. 162, 163
Logunova A. 93
Lygaitis R. 69, 83
Lysenko E. A. 94
Maciulyte S. 145
Maistrenko L. 146
Makhaev V.D.
Maksimenko S. 53
Makuska R. 26, 72, 85, 89, 115
Malašauskienė J. 147
Malers L. 148
Malinauskas A. 27
Maminskas J. 153
Martínez-Felipe A. 156, 157, 158, 159
Märtson T. 82
Matulaitis T. 45
182
Mažonienė E.56
Mellikov E. 122
Merijs Meri R. 53, 61, 125, 132, 134, 149
Meseguer F. 156
Miasojedovas A. 81
Michaleviciute A. 42
Mickevičienė A. 150
Milašius R. 147
Mimaitė V. 45, 63, 95
Mocioiu A.M. 129
Mokrinskaya E.V. 74
Mokrousova O. 141, 151
Moliner-Estopiñán C. 159
Moran C. 158
Morozovs A. 144
Mukhidinov Z.K. 123
Narmontas P. 54, 64, 96
Nasiri Boroumand M. 133
Nasriddinov A.S. 123
Neiberte B. 163, 171
Netopilík M. 35
Nicholls M. 58
Novoskoltseva O.A. 97
Olivier S. 58
Öpik A. 41, 122, 126
Ostrauskaite J. 44, 91, 107, 139
Ovchinnikov M. 38
Paberza A. 152
Pakhomov P. 38
Pamedytytė V. 111
Pan J. 25
Pander P. 46, 47
Panova T. V. 98
Parilova E. 77
Pavlov V.A. 74
Petica A. 129
Petrašauskienė N. 99
Petrauskaite O. 153
Petrulis D. 170
Petrulytė S. 170
Piskun Yu.A. 100, 112
Plavan V. 154
Plesuma R. 148
Plutalova A. 71
Poltimäe T. 160
Popescu M. 128
Pothecary M.58
Prosyčevas I. 54, 96, 161
Pruchkina E. 116
Puckyte G. 42
Pudlauskaitė J. 54, 96
Pyatnikova D.A. 75
Pyshkina O. 101
Ragauskienė D. 155
Rappich J. 29, 41
Rasymaite D. 78
Razumiene J. 145, 166
Reihmane S. 62, 124, 171
Reinholds I. 61
Repeshova I. 160
Reut J. 29, 41, 126
Ribes-Greus A. 156, 157, 158, 159
Rikko M. 82
Rodrigez I. 156
Rogacheva V.B. 97
Rosado-Gil M. 156, 157, 158, 159
Rösicke F. 29
Rumyantsev A.M. 94
Rutkis M. 30
Rutland M. 26
Saar K. 160
Sababi M. 25
Sakinyte I. 145, 166
Samardokas L. 84
Samulionytė G. 102
Sánchez-Ballester S. 156, 157, 158, 159
Sankauskaitė A. 161
Santonja- Blasco L.
Savelyeva A. A. 51
Savickaite M. 72
Schmaltz B. 42
Schmitt M. 156
Sedov I.V. 76
Semjonovs P. 121
Sendrea C. 129
Senyk I. 40
Senyn E. 40
Sereikaite J. 142
Sergeyev V. 51, 101
Serra A. 33, 103
Sevastyanova I. 135
Shakels V. 162, 163
Shiman D. I. 51, 104
Shulga G.162, 163, 171
Sidorovs E. 138
Šimkus G. 105
Simokaitiene J. 44, 66, 70, 102, 107, 109
Sini G. 63
Širvaitienė A. 167
Širvaitytė J. 168
Sivtsov E. 77, 93, 106
Skrockienė V. 164
Songaila J. 107
Soria V. 157
Stakhira P. 108, 172
Stanislovaitytė E. 109
Stiebra L. 57, 165
Stokienė R. 99
Strakšys A. 166
Strazdiene E. 127, 177
Studzinsky S.L. 74
Stumbras A. 153
183
Sun G. 29
Šutaitė J. 110
Swinarew A.S. 37
Swinarew B. 37
Swist A. 47
Syritski V. 29, 41, 126
Talviste R. 87
Tarassova E. 82
Tavgeniene D. 78
Telysheva. G. 113
Teruel-Juanes R. 156, 157, 158, 159
Thormann E. 25, 26
Tolmacheva I. 131
Tomkevičienė A. 42, 105, 110, 119
Tran Van F. 42
Treigienė R. 150
Treimane R. 121
Treimanis A. 56, 121
Treinyte J. 169
Tretjakov A. 41, 126
Tumėnienė M. D. 161
Tverdokhleb V. 40
Urbelis V. 127, 177
Valeika V. 128, 168
Valeikienė V. 168
Valungeviciute G. 145
Vareikis A .68, 111
Varnaitė-Žuravliova S. 161
Vasilenko I. V. 51, 100, 104, 112
Veličkienė A. 170
Veraksa Y. A. 51
Verovkins A. 163
Vevere L. 113
Viipsi K. 87
Viirsalu M. 82
Vikele L. 56
Vilsone D. 135
Vinkevičiūtė I. 68
Vishnevetsky D. 114
Visnevskij C. 26, 72, 115
Vitkauskiene I. 165
Vitolina S. 163, 171
Vlasova E. 116
Vlaykov G.G. 65
Volchek B. 116
Volkova E.R. 173, 174
Volosova N. 101
Volyniuk D. 66, 7, 108, 172
Volynskii A.L. 80
Walczak K. 49
Williams A. 59
Xie Z. 79, 117
Yakushin V. 135
Yaroslavov A.A. 75
Zacharovas S. 64
Zaitsev K.V. 100, 112
Zaleckas E. 79, 117
Žalenkienė S. 99,118
Zalite I. 125
Zeltins V. 175
Zezin A. B. 94, 97, 98
Zhang B. 79
Zhang F. 25
Zhang X. 29
Zhang Y. 41
Zheltonozhskaya T. 143
Zhivotova E. 176
Zicans J. 53, 61, 125, 132, 134, 149
Zilinskaite V. 119
Zlobinskiy Yu.I. 76
Zoldners J. 57
Zostautiene R. 79, 117
Zubauskiene D. 177
Žukienė K. 164
184

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