Polythiol Presentation

Titelfolie
THIOCURE®
for Paints & Coatings,
Adhesives & Sealants
BRUNO BOCK
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Contents
Bruno Bock
Evans
Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
Contents
Bruno Bock
THIOCURE® Polythiols
Introduction
Production
Properties
Thiourethane-Systems
Epoxy-Systems
UV- and Thiol-Ene-Systems
Sealants
Product Range
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Bruno Bock
Evans
Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
©Bruno Bock
Privately owned enterprise, founded 1937
in Hamburg
Leading position worldwide in the production of
Mercaptocarboxylic Acids and their Derivatives
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Bruno Bock
Evans
Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
Acquisition of Evans Chemetics LP, USA in 2005
Commissioning of Technical Service Center for Coatings,
Adhesives and Sealants in May 2010
Approx. 100 employees in Germany, 70 in USA
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Bruno Bock
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Chemetics
THIOCURE
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EP-Systems
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THIOCURE®
Trade name for Polythiols from Bruno Bock and Evans
Chemetics
Sulfur analogs of alcohols are called thiols
More traditionally, thiols are referred to as mercaptans
The functional group of a thiol is an –SH end group bonded
to a carbon-atom
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Bruno Bock
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Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
Thiocure Polythiols are
di- up to hexafunctional
low in viscosity
solvent- and VOC-free
nearly colorless liquids
Polythiols have a high refractive index
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Chemetics
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Thiols react via polyaddition with Epoxies and Isocyanates
and via radical respectively nucleophile addition with doubleand triple-bonds
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Chemetics
THIOCURE
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Synthesis of Polythiols by esterification of Mercaptocarboxylic
Acids + polyfunctional Alcohols
3-Mercaptopropionic Acid (3-MPA)
Mercaptopropionates
and Polymeric thiols
Thioglykolic Acid (TGA)
Mercaptoacetates
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Contents
Bruno Bock
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Chemetics
THIOCURE
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Mercaptopropionates
3-Mercaptopropionic Acid
+ Pentaerythritol
THIOCURE®
PETMP
+ Trimethylolpropane
THIOCURE®
TMPMP
+ Ethylenglycol
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THIOCURE®
GDMP
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Contents
Bruno Bock
Evans
Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
Polymeric Polythiols
THIOCURE® ETTMP
THIOCURE® PCL4MP 1350 (Experimental product)
THIOCURE® PPGMP 800 und 2200 (Experimental products)
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Contents
Bruno Bock
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Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
Mercaptoacetates
Thioglycolic Acid (TGA)
+ Pentaerythritol
THIOCURE®
PETMA
+ Trimethylolpropane
THIOCURE®
TMPMA
+ Ethyleneglycol
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GDMA
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Contents
Bruno Bock
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Chemetics
THIOCURE
PU-Systems
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THIOCURE® Characteristics
Mercaptopropionates
MercaptoAcetates
Polymeric
Polythiols
PETMP, TMPMP, GDMP, 1
PETMA, TMPMA, GDMA
ETTMP, PCL4MP 1350
Reactivity
+
++
-
Hardness
+
++
-
Flexibility
-/+
-/+
++
UV-Resistance
++
+
-/+
Water miscibility
--
--
-/+
++
-
+
Odor
++ = best
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Contents
Bruno Bock
Evans
Chemetics
THIOCURE
PU-Systems
EP-Systems
UV/ThiolEne
THIOCURE® Applications
Binder for
- Thiourethanesystems
- Thiol-Ene-systems
(thermal or
UV-curing)
BRUNO BOCK
Additive for
Hardener for
- PU-systems
- Epoxy-systems
- Radiation curing
UV-systems
- Stoving systems
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Contents
Bruno Bock
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Chemetics
THIOCURE
PU-Systems
EP-Systems
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THIOCURE® for Thiourethane-Systems
The thiol group is the sulfur analog of the hydroxl group.
Since sulfur and oxygen belong to the same periodic table
group, they share some similiar chemical bonding properties.
In comparison to the OH-bond the SH-bond is weaker, that
means that the proton on the S-atom of thiols is given away
more easily in comparison to the alcohols‘ proton
higher
reactivity than Acrylates, Polyesters, Polyethers
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Bruno Bock
THIOCURE
Evans
Chemetics
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Sealants
Calculation of the hardener
In general one equivalent of NCO-groups (42 g/mol)
reacts with one equivalent of Thiol-groups (33 g/mol)
Isocyanate [g] = Amount THIOCURE [g] x SH-content [%] x 42
33 x NCO-content [%]
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
How could you influence the reactivity of Thiolurethane-systems?
Add catalyst if the reactivity is too slow,
for example metall catalysts like K-Kat® 5218 or
quarternary ammonium salts (BYK® -ES 80)
DBTL is not effective in catalyzing the SH/NCOreaction (at roomtemperature)
Use THIOCURE® PETMP sl or PETMP cs
instead of PETMP standard to slow down
the reaction
Add slow polyols or reaction inhibitors if the
reactivity is too high
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
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Examples for reaction inhibitors are
Phosphoric acid ester (Dibutyl phospate) or
boric acid ester (Tributyl borate)
Geltime
PETMP + D'dur N 75
[min]
200
150
100
50
0
14
Control
1%
Tributyl
borate
0,1%
Dibutyl
phosphate
Beware! Reactivity of comparable polyisocyanates
could differ according to their producer
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
Lower CO2-formation in comparison to the
NCO-OH reaction
17-32 THIOCURE® ETTMP 700 + Desmodur® E 29
17-29 Polyetherpolyol + Desmodur® E 29
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
THIOCURE® for Epoxy-Systems
as hardener or blend-hardener
for solvent based and solvent free coating
systems, castings, floorings, adhesives,
sealants, plaster / mortar
imparts rapid-cure / low-temperature-cure
as hardener for epoxy-termininated polysulfides
suitable
less, respectively no color compared to amine
hardeners
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
Calculation of Hardener
In general one equivalent of Epoxy-groups reacts
with one equivalent of Thiol-groups (33 g/mol)
THIOCURE [g] = Amount Epoxyresin [g] x 33 [g/mol] x 100
SH-content [%] x EEW [g/mol]
or
THIOCURE [g] = Epoxide Value x H-Equivalent of hardener
EEW = Epoxy Equivalent Weight
Epoxide Value = 100/EEW
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
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Sealants
Use of an activator like tertiary amine is necessary
The resulting thiolate anion is highly nucleophilic and
quickly added to the epoxide
Source: „Formulierung von Kleb- und Dichtstoffen“ (Bodo Müller / Walter Rath)
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THIOCURE
Bruno Bock
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
With respect to type and concentration of
amine very fast systems can be formulated
Geltime]
[min.]
350
331
300
250
200
150
100
50
21
0
0,10%
0,25%
8
0,50%
4
1,00%
100 g Bisphenol AStandard EP- Resin +
65.2 g PETMP
Catalyst: TEDA Triethylenediamine (DABCO® LV 33 /
Addocat® 105 ,
calculated on EP-resin)
However, mixtures of tertiary amines and polythiols
are not storage-stable
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Bruno Bock
THIOCURE
Evans
Chemetics
PU-Systems
EP-Systems
UV/ThiolEne
Sealants
Phosphonium Salts show also catalytic effect and
can be premixed with THIOCURE
[h]
Geltime
12
10
8
100 g Bisphenol A-standard EP- resin
+ 65.2 g PETMP
Catalyst: TributylhexadecylPhosphoniumbromide (Cyphos® 3472,
calculated on EP-resin)
6
4
2
0
0,3
0,5
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0,65
0,8
1
1,25
1,5
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Bruno Bock
THIOCURE
Evans
Chemetics
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THIOCURE® - Application Examples
Floorings in parking garages and cold stores
Concrete road repairs / repair mortars
„5-minutes“ consumer adhesives
Adhesives for electronic applications
©Pixelio
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
THIOCURE® for Radiation Curing Systems
Ultraviolet Light / Electron Beam
Free Radical
Process
Dual-Cure /
Hybrid Cure
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Cationic
Process
Thiol-EneReaction
Anionic Catalyzed Polyaddition
Process with photolatent Base
MichaelAddition
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
THIOCURE® for Thiol-Ene Systems
The thiol-ene reaction is simply the coupling of thiol-groups
with double bonds forming a thioether
The thiol-ene reaction is a so called „click“ reaction and can
take place as radical-mediated addition reaction or as base/
nucleophile-initiated Michael-addition
Initiation occurs by radical initiators photochemically or
thermically
As combination partner can be used: acrylate, vinylether,
propenylether, allylether, low molecular polybutadiene
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
Advantages:
no oxygen inhibition!!!
low volume shrinkage
high conversion of the double bonds
THIOCURE® - Application Examples
Wood Impregnation
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Doming-Labels
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
THIOCURE® for Free Radical UV-Curing Systems
Already 1 to 10 w/w% thiol as additive in acrylate-systems
are sufficient to reduce oxygen inhibition, even in thin films
The presence of thiol retards the gelpoint and reduces
volume shrinkage
Building of homogenous polymer networks
Lower concentration of photoinitiator necessary
Replacement of amine synergists in LED-curing systems
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
THIOCURE® for Sealants
As modifier for sealants based on polysulfide
to increase the crosslinking density
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THIOCURE
PU-Systems
THIOCURE®
Chemical Description
Evans
Chemetics
EP-Systems
PETMP
PETMP l.o.
Molecular Weight [g/mol]
PETMP sl
„low odor“
Odorless
version
„slow“
Controlled
reactivity,
recommended
for PU-Systems
PETMP cs*
Controlled
reactivity,
recommended
for PU- and
Thiol-EneSystems
488.6
125-128
SH-content [%w/w]
~ 26
Brookfield ISO 2555, 21°C
Types
4
H-active-Equivalent
Viscosity
Sealants
Pentaerythritoltetra(3-mercapto-propionate)
Standardtype
SH-functionality
UV/ThiolEne
~ 400 mPa.s
*Experimental Product
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
THIOCURE®
TMPMP
GDMP
PETMA
TMPMA
GDMA
Chemical
Description
Trimethylolpropanetri
(3-mercaptopropionate)
Glykoldi
(3-mercaptopropionate)
Pentaerythritoltetramercaptoacetate
Trimethylolpropanetrimercaptoacetate
Glykoldimercaptoacetate
3
2
4
3
2
398.6
238.3
432.5
356.5
210.2
H-activeEquivalent
136-140
122-125
111-114
122-125
107-108
SH-content
[%w/w]
~ 24
~ 26.8
~ 29.5
~ 26.5
~ 30.5
~10 mPa.s
~400 mPa.s
Cristallize at
RT
~120 mPa.s
~10 mPa.s
SH-functionality
Molecular Weight
[g/mol]
Viscosity
Brookfield ISO 2555,
21°C
~150 mPa.s
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THIOCURE
PU-Systems
Evans
Chemetics
EP-Systems
THIOCURE®
UV/ThiolEne
Sealants
Types
Di-PETMP
Di-TMPMP*
Di-Pentaerythritolhexakis
(3-mercaptopropionate)
Di-Trimethylolpropanetetra
(3-mercaptopropionate)
6
4
783.0
602.8
H-active-Equivalent
135 – 139
154 – 158
SH-content [%w/w]
~ 24.1
~ 20.8
~ 2000 mPa.s
~ 450 mPa.s
Chemical
Description
SH-functionality
Molecular Weight
[g/mol]
Viscosity
Brookfield ISO 2555,
21°C
*Experimental Product
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THIOCURE
PU-Systems
THIOCURE®
Chemical
Description
Evans
Chemetics
EP-Systems
Einsatz
UV/ThiolEne
Sealants
Types
TEMPIC
Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate
Formula
SH-functionality
Molecular Weight
SH-content [%w/w]
Viscosity
Brookfield ISO 2555,
21°C
BRUNO BOCK
3
525.6 g/mol
18 %
~8000 mPas
THIOCHEMICALS
32
THIOCURE
PU-Systems
THIOCURE®
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
ETTMP 700
ETTMP 1300
Ethoxylated
Trimethylpropan-tri(3mercapto-propionate)
Ethoxylated Trimethylpropantri(3-mercapto-propionate)
3
3
4
~700
~1300
~1350
H-active-Equivalent
236-262
435-448
348-375
SH-content [%w/w]
~ 13.5
~ 7.1
~ 9.1
~200 mPa.s
~400 mPa.s
~1000 mPa.s
Chemical
Description
SH-functionality
Molecular Weight
[g/mol]
PCL4MP 1350*
Polycaprolactone tetra
3-mercaptopropionate
Viscosity
Brookfield ISO 2555, 21°C
*Experimental Product
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THIOCURE
PU-Systems
THIOCURE®
Chemical
Description
Evans
Chemetics
EP-Systems
UV/ThiolEne
Sealants
Types
DMPT
DMDS
2,3-Di((2-mercaptoethyl)thio)-1-propanethiol
Dimercaptodiethylsulfide
3
2
260.5
154.3
min. 36.2
min. 40.7
< 10 mPa.s
< 10 mPa.s
1.63
1.60
Formula
SH-functionality
Molecular Weight
[g/mol]
SH-content [%w/w]
Viscosity
Brookfield ISO 2555, 21°C
Refractive Index
Remark
DMPT and DMDS are very smelly! Both may cause sensitization.
Use only in closed applications!
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Einsatz
© Bruno Bock
BRUNO BOCK Chemische Fabrik GmbH & Co. KG
Eichholzer Str. 23, D-21436 Marschacht, Tel. +49-4176-9098-0 Fax: +49-4176-1396, www.brunobock.de
Contact
Sales
Jens P. Jensen
Technical Service Center Elvira Schlatter
Development
Dr. Matthias Rehfeld
+49-(0)4176-9098-13
+49-(0)4176-9098-27
+49-(0)4176-9098-21
[email protected]
[email protected]
[email protected]
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BRUNO BOCK
THIOCHEMICALS
08-2014