Synpo by Jiri Vrana

BioLinX Brokerage Event in
Breda, Netherlands
16 June 2016
Content:
-Brief company profile
-Utilization of lignin and other biomaterials in various polymers
Jiří Vrána – Synpo a.s.
Company Profile
Pardubice
Czech
Republic
SYNPO, a.s.
S. K. Neumanna 1316
Zelené Předměstí
CZ - 532 07 Pardubice
The Czech Republic
www.synpo.cz
+420 466067111
SYNPO - History
 1952 - Research Institute for Synthetic Resins and Lacquers
 State-owned
 1992 - SYNPO, joint stock company
 “For-profit” company owned by shareholders
 Since 2009, 100 % shares owned by Spolchemie, a.s
3

120 employees

Quality Control Certificate ISO 9001
SYNPO - Key Activities






4
Contract R&D and product development in synthetic polymers,
coatings, composites and adhesives.
Production of coatings, paints, compounds and adhesives.
Process development and scale-up in SYNPO‟s pilot plant and
manufacturing facilities.
Custom manufacturing and tolling of various products.
Analytical and testing services in accredited laboratories.
Training of PhD and MSc students in collaboration with the
University of Pardubice and cooperation with the Academy of
Science in Prague.
SYNPO - Research and Development

R&D areas
Alkyds, polyesters and polyurethanes
 Epoxy resins, hardeners, reactive diluents
 Emulsion and solution polymers and acrylic dispersions
 Nanostructured polymers and renewable raw materials
Applications
 Paints/Coatings
 Composites
 Casting and sealing compounds
 Adhesives and putties
 Laminating resins


5
SYNPO – Production of paints and
specialties & scale-up

Standard and custom production
 Complete range of materials for coating of metals, plastics and glass.
 Custom manufacturing of special polymers, e.g. adhesives.

Applications


Scale-up & tolling

6
Coating applications in road and rail vehicles, aircrafts, sporting
goods, engineering, manufacturing of composites and coating of glass
products.
Pilot plant is equipped for transfer from laboratories to production
scale – polymerization reactors
with capacity from 20 to 300 l.
SYNPO - Analytical and Testing Services

Analysis of Polymer Materials


7
Accredited according to EN ISO/IEC 17025 for various chemical and
physical properties of products based on synthetic polymers and resins
including related materials, wastes, components, and environmental
samples.
Analysis of Products and Materials
 Determination of physical and chemical properties
 Structure / property relationships
 Characterization of polymer branching
 Raw materials analysis
 Evaluation of reproducibility of production batches
 Determination of product composition
 Study and optimization of chemical reactions
SYNPO – Analytical Services
Analytical Instruments and Equipment









8

Liquid chromatography (HPLC, LC-MS)
Gel permeation chromatography (GPC)
Gel permeation chromatography coupled with a multi-angle light
scattering photometer and a viscometer (GPC-MALS)
Asymmetric flow field flow fractionation coupled with MALS (A4F-MALS)
Gas chromatography (GC) and (GC-MS)
Infrared spectroscopy FT-IR, infrared microscopy
Atomic force microscopy (AFM), a very high-resolution type of scanning
probe microscopy (SPM),
Tensiometer
Particle size distribution (Dynamic Light Scattering)
Titration methods
Synpo – Testing Instruments
for mechanical, thermal and thermal-mechanicals tests
 DSC, DDSC
 Impact strength
 DMA
 HDT
 TMA / TGA
 Teraohmmeter
 Universal testing machines
 Accelerated weathering testers (Q-panels)
 Viscometers
 Salt spray and SO2 atmosphere testing
 Optical miscroscopy
 Climate chambers, Q-Sun
Certification - all tests are carried out according to ISO,
ASTM, and DIN standards in accredited laboratories.
Activities on the field of bio-materials

Bio-commodity refinery (BIOCORE)
Membership in consortium of an integrated project funded under the 7th FP EU, 20102014. An aim of the project was to develop an overarching biorefining concept that will form the basis
for viable industrial exploitation of lignocellulosic biomass for commodity scale production of
essential products.

BIOCOPAC project
Membership in consortium of integrated project funded under 7th FP EU, 2011 -
2013.
The goal of the project was to develop a polyester bio-lacquer for the protection of metallic food
packaging. A natural lacquer to be obtained was from industrial tomato processing byproducts (skins). The main component the biopolymer cutin was extracted from the cuticle of the fruit.

Contract research:
 Utilization and testing of bio-materials in various polymers:




10
Succinic acid
Lactic acid derivates
Adipic acid or itaconic acid
Bio solvents (methyl levulinate, lactate esters, succinate esters, etc.)
Utilization of lignin in polymers

Use our experience in preparation of various
polymeric materials containing different modifications
of lignin.

Dispersion of lignin in polyol or oil
–
–
–
11
PUR casting resin (flexible and rigid)
PUR foams (flexible and rigid)
modification of soya based alkyd resin for wood
protection
Example of incorporation of lignin into polyurethane
R-NCO + HO-R„ → R-NH-CO-O-R„
Lignin
Energy
Polyol
Dispersion
Moisture
Polyol system
preparation
> 0.1 mbar
Vacuum drying
Blowing
agents,
surfactants
Additives,
catalysts
Mixing
Isocyanate
Polymerization
Mixing
~ 70 °C
Post Curing
Heat
Rigid polyurethane foams
12
Polyurethane casting resin
Energy,
compressed
air
Liquified organosolv lignin
o Propoxylated organosolv lignin
CH3
OH
CH
CH2
O
O
CH3
CH
C H 3O
OH
CH3
O
CH
O
CH2
O
C H 3O
CH2
O
O
O CH3
O CH3
OH
HO
OH
O
CH3
O CH3
CH
CH3
O
O
C H2
CH2
CH2
O
CH
CH3
CH
HO
CH3
CH
O CH3 CH2
O
CH2
O
CH
CH2
CH
CH3
OH
Solid lignin
13
CH3
OH
Liquified lignin
Polyurethane elastomers with lignin
AFM scan
Casted sheets
Standard
Veropal 3B
(PU cast resin
of Synpo)
Propoxylated lignin as reactive
compound (OHV ~ 100)
14
AFM (Atomic Force Microscopy)
Scan 2 µm
Aggregates: 300 nm – 1.2 µm
Lignin as
biofiller
(OHV = 0)
Polyurethane elastomers – comparison of properties
2K PU cast resin Veropal 3B modified by lignin used as reactive compound and biofiller
600
500
Relative units [-]
400
300
0 wt.% of lignin
15 wt.% of lignin (teor. OH = 100 mg KOH/g)
15 wt.% of lignin (teor. OH = 0 mg KOH/g)
200
100
0
Tensile
Elongation [%] Modulus [MPa] Work to break
strength [MPa]
[N/mm2]
15
Hardness
[Shore A]
Water
absorbtion in 1
week [%]
Polyurethane elastomers – changes in viscosity
Measured 3 hours at 25 °C
With biofiller
With reactive compound
Neat system
16
Flexible PU modified with propoxylated lignin
Multilayer sandwich
•
•
•
Used dried powdered organosolv lignin
Lignin with theoretical OHV = 100 mg KOH/g
Three-roll mill dispersion
o
•
Modification of flexible casting resin Veropal 3B
o
o
o
•
•
17
castor oil/lignin = 1/1
0 wt. % of lignin
7.5 wt. % of lignin
13.6 wt. % of lignin
Top black layer – PU with lignin
Cured by polymeric MDI (Suprasec 2651, NCO = 32.6 %)
Casted sheets 20 x 10 x 0.4 cm
0 wt. % of lignin
7.5 wt. % of lignin
13.6 wt. % of lignin
Flexible PU modified by lignin - properties
300.0
250.0
0 % 7.5 % 13.6 %
of lignin
relative units [-]
200.0
150.0
100.0
50.0
0.0
Tensile strength [MPa]
18
Elongation [%]
Modulus [Mpa]
Work to break [MPa]
Hardness [Shore A]
Rigid PU modified by propoxylated lignin
•
•
•
•
Dried powdered organosolv lignin (theoretical OH# = 100 mg KOH/g)
Lupranol 3422 polyether polyol OH# = 390 mg KOH/g
Three-roll mill dispersion (Lupranol 3422/lignin = 2/1)
Modification of rigid casting resin
o
o
o
•
•
19
0 wt. % of lignin
8.3 wt. % of lignin
15.0 wt. % of lignin
Cured by polymeric MDI (Suprasec 2651, NCO = 32.6 %)
Casted sheets 20 x 10 x 0.4 cm
0 wt. % of lignin
8.3 wt. % of lignin
15.0 wt. % of lignin
Rigid PU modified by lignin - properties
120.0
0 % 7.5 % 13.6 %
of lignin
100.0
80.0
60.0
40.0
20.0
0.0
Tensile strength [MPa]
20
Elongation [%]
Modulus [Mpa]
Work to break [MPa]
Hardness [Shore A]
Rigid polyurethane foams
standard
21
0.5 wt. % of lignin
1 wt. % of lignin
2 wt. % of lignin
AFM analysis of rigid PU foams
scan 3 µm, adhesion map, primary particles 70 - 90 nm
scan 3 µm, adhesion map, primary particles 70 - 80 nm
Rigid PU foams modified by lignin
22
scan 5 µm, adhesion map, primary particles 90 and
170 nm
scan 5 µm, adhesion map, primary particles 70 - 90
nm and agglomerates 650 nm
Flexible polyurethane foams
standard
23
1 wt.% of lignin
2 wt.% of lignin
Flexible polyurethane foams - properties
Flexible polyurethane foams modified with lignin
170
160
Relative units
150
0 wt.% of lignin
140
0,5 wt.% of lignin
130
1 wt.% of lignin
1,5 wt.% of lignin
120
2 wt.% of lignin
110
100
90
Foam density [kg/m3]
Foam rise time [s]
IFD 25 [N]
IFD 65 [N]
IFD = Indentation Force Deflection - ASTM D3574 B1, values are
generated at 25 and 65 percent of initial foam height
High IFD test results imply increased hardness.
24
Comments of results obtained with tested
PU compositions
• Fine powder lignin (up to 15 wt. %) is suitable for preparation of
flexible PU elastomers because it improves:
• Tensile strength
• Toughness
• Electrical resistance
• Lignin in polyol can be used in PU casting resins in electrical
engineering industry
• Improvement of thermo-mechanical properties and electric resistance
• A drawback is an increase of moisture absorption
• Powdered lignin added into rigid PU systems (up to 15
decreases:
wt. %)
• Mechanical properties
• Organosolv lignin liquified by propoxylation shortens pot life and
causes undesirable bubbling. Lignin must be chemically treated
prior to its application in polyurethanes.
25
• Propoxylated lignin reacted with MDI leads to very brittle casting
resins. But it can be modified.
POLYESTER RESINS BASED ON
BIO-SUCCINIC ACID
• CASE STUDY of the influence of bio-succinic acid (SA) in solvent borne coil
and can coatings. Preparation of resins based on isophthalic acid and adipic
acid, NPG and EG. SA was used as replacement of AA or replacement of both
IA and AA.
Bio-succinic acid replaced entire AA and partly IA. Total content of SA was up to
12 wt. % on solid components.
The polyester resin solutions were cured using hexamethoxy melamine
resulting in an excellent polymer network.
Outcomes:
-SA instead of AA: higher solid and solution viscosity, higher Tg and coating
hardness
-SA instead of IA: lower solid and solution viscosity, lower Tg and coating
hardness
-Resins with SA after QUV exposure: lower loss of gloss and lower Db* value
-(difference in red-green axis)
-Higher SA content: faster increase of coating hardness over time
26
Ref: Paint&Coating Industry, May 2016, Vol.32, No.5, p. 26-31
ALKYD RESINS BASED ON
BIO-SUCCINIC ACID
 CASE STUDY: Use of bio-succinic acid (SA) as a replacement of phthalic anhydride
(PA) in short, medium and long soybean oil alkyds  preparation of alkyd resins
with high bio-content.
 Experimental work was fisnished with interesting results, however, they were
published only in internal reports so far.
27
SWOT analysis to bio-materials
in polymers
Internal
factors
28
Success factors
Failure factors
Strength
Weaknesses
Opportunity to valorise so far
hardly used bio-mass and biomaterials.
In some cases an additional
chemical modification of biomaterials is not required.
Developed technological
processes can be solvent free.
Conventional production lines can
be utilized.
Addition of bio-mass and biomaterials increases the renewable
content in a new polymer.
Reactivity with e.g. isocyanates in solvent
free system is still not well understood.
Chemical structure of a new polymer
undefined.
In some cases, an addition of certain biomaterials, e.g. lignin, requires an extra
step in production of modified polymers .
Bio-materials may cause undesirable
increase viscosity of the reaction mixture
or deterioration of some properties.
Long term storage stability of e.g. lignin
or lactides is limited.
Colour changes can be an issue, lignin
containing polymers are dark brown.
SWOT analysis – Part 2
Success factors
External
Opportunities
factors
Carbon footprint of final products
can be significantly lowered.
New polymers containing biomaterials can provide interesting
properties.
Polymers can be even 100 % biobased.
Bio-materials can contribute to
price reduction of a final product.
Polymers with bio-materials can
extend the specialties product
portfolio.
Failure factors
Threats
Potential shortage of original bio-mass,
e.g. for lignin production.
Limited production capacity.
Variations in properties of bio-materials.
Lower acceptance among endusers for
non-standard products different from
conventional materials.
Synpo is interested in testing diverse bio-materials in various polymers,
especially those with reactive groups enabling chemical bonding and
thus possibly resulting in enhanced final properties.
29
Our cooperating partners and customers
30
Thank you for your
attention
www.synpo.cz
www.akrylmetal.cz
+420 466067111