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BRUNO BOCK THIOCHEMICALS
Bruno Bock PU-Systems UV/ThiolEneContents
Contents
� Bruno Bock
� THIOCURE® Polythiols
� Introduction
� Production
� Properties
� Thiourethane-Systems
� Epoxy-Systems
� UV- and Thiol-Ene-Systems
� Sealants
� Product Range
Evans Chemetics EP-Systems
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THIOCURE
BRUNO BOCK THIOCHEMICALS
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� Privately owned enterprise, founded 1937
in Hamburg
� Leading position worldwide in the production of
Mercaptocarboxylic Acids and their Derivatives
©Bruno Bock
Bruno Bock PU-Systems UV/ThiolEneContents Evans Chemetics EP-SystemsTHIOCURE
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� 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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THIOCURE®
Bruno Bock PU-Systems UV/ThiolEneContents Evans Chemetics EP-SystemsTHIOCURE
� 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 PU-Systems UV/ThiolEneContents Evans Chemetics EP-SystemsTHIOCURE
� Polythiols have a high refractive index
� Thiocure Polythiols are
� di- up to hexafunctional
� low in viscosity
� solvent- and VOC-free
� nearly colorless liquids
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� Thiols react via polyaddition with Epoxies and Isocyanates
and via radical respectively nucleophile addition with double-
and triple-bonds
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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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+ Pentaerythritol THIOCURE®
PETMP
THIOCURE®
TMPMP+ Trimethylolpropane
+ Ethylenglycol THIOCURE®
GDMP
Mercaptopropionates
3-Mercaptopropionic Acid
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Polymeric Polythiols
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THIOCURE® ETTMP
THIOCURE® PPGMP 800 und 2200 (Experimental products)
THIOCURE® PCL4MP 1350 (Experimental product)
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+ Pentaerythritol THIOCURE®
PETMA
THIOCURE®
TMPMA
+ Trimethylolpropane
+ Ethyleneglycol THIOCURE®
GDMA
Mercaptoacetates
Thioglycolic Acid (TGA)
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THIOCURE® Characteristics
Mercapto-
propionatesPETMP, TMPMP, GDMP, 1
Mercapto-
AcetatesPETMA, TMPMA, GDMA
Polymeric
PolythiolsETTMP, PCL4MP 1350
Reactivity + ++ -
Hardness + ++ -
Flexibility -/+ -/+ ++
UV-Resistance ++ + -/+
Water miscibility -- -- -/+
Odor ++ - +
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++ = best
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THIOCURE® Applications
Binder for
- Thiourethane-
systems
- Thiol-Ene-systems
(thermal or
UV-curing)
Hardener for
- Epoxy-systems
Additive for
- PU-systems
- Radiation curing
UV-systems
- Stoving systems
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Bruno Bock PU-Systems UV/ThiolEneContents Evans Chemetics EP-SystemsTHIOCURE
� 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
THIOCURE® for Thiourethane-Systems
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� 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 [%]
THIOCURE EP-Systems SealantsBruno Bock Evans Chemetics UV/ThiolEnePU-Systems
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� How could you influence the reactivity of Thiol-
urethane-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/NCO-
reaction (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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� Examples for reaction inhibitors are
Phosphoric acid ester (Dibutyl phospate) or
boric acid ester (Tributyl borate)
� Beware! Reactivity of comparable polyisocyanates
could differ according to their producer
0
50
100
150
200
14
GeltimePETMP + D'dur N 75
Control 1% 0,1%
Tributyl Dibutyl
borate phosphate
[min]
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� 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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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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� 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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� Use of an activator like tertiary amine is necessary
THIOCURE EP-Systems SealantsBruno Bock Evans Chemetics UV/ThiolEnePU-Systems
The resulting thiolate anion is highly nucleophilic and
quickly added to the epoxideSource: „Formulierung von Kleb- und Dichtstoffen“ (Bodo Müller / Walter Rath)
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� With respect to type and concentration of
amine very fast systems can be formulated
100 g Bisphenol A-
Standard EP- Resin +
65.2 g PETMP
Catalyst: TEDA Triethylene-
diamine (DABCO® LV 33 /
Addocat® 105 ,
calculated on EP-resin)
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21 8 40
50
100
150
200
250
300
350
0,10% 0,25% 0,50% 1,00%
Geltime][min.]
However, mixtures of tertiary amines and polythiols
are not storage-stable
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� Phosphonium Salts show also catalytic effect and
can be premixed with THIOCURE
0,3 0,5 0,65 0,8 1 1,25 1,5
0
2
4
6
8
10
12
Geltime[h]
100 g Bisphenol A-standard EP- resin
+ 65.2 g PETMP
Catalyst: Tributylhexadecyl-
Phosphoniumbromide (Cyphos® 3472,
calculated on EP-resin)
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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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PU-Systems TypesTHIOCURE Evans Chemetics SealantsEP-Systems UV/ThiolEne
Ultraviolet Light / Electron Beam
Free Radical
Process
Cationic
Process
Dual-Cure /
Hybrid Cure
Thiol-Ene-
Reaction
Anionic
Process
THIOCURE® for Radiation Curing Systems
Michael-
Addition
Catalyzed Polyaddition
with photolatent Base
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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
PU-Systems TypesTHIOCURE Evans Chemetics SealantsEP-Systems UV/ThiolEne
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� Advantages:
no oxygen inhibition!!!
low volume shrinkage
high conversion of the double bonds
THIOCURE® - Application Examples
� Wood Impregnation � Doming-Labels
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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® for Sealants
� As modifier for sealants based on polysulfide
to increase the crosslinking density
PU-Systems TypesTHIOCURE Evans Chemetics SealantsEP-Systems UV/ThiolEne
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THIOCURE® PETMP PETMP l.o. PETMP sl PETMP cs*
Chemical Description Pentaerythritoltetra(3-mercapto-propionate)
Standard-
type
„low odor“
Odorless
version
„slow“
Controlled
reactivity,
recommended
for PU-Systems
Controlled
reactivity,
recommended
for PU- and
Thiol-Ene-
Systems
SH-functionality 4
Molecular Weight [g/mol] 488.6
H-active-Equivalent 125-128
SH-content [%w/w] ~ 26
ViscosityBrookfield ISO 2555, 21°C
~ 400 mPa.s
*Experimental Product
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THIOCURE® TMPMP GDMP PETMA TMPMA GDMA
Chemical
Description
Trimethylol-
propanetri
(3-mercapto-
propionate)
Glykoldi
(3-mercapto-
propionate)
Pentaerythri-
toltetramer-
captoacetate
Trimethylol-
propanetri-
mercaptoacetate
Glykoldi-
mercaptoacetate
SH-functionality 3 2 4 3 2
Molecular Weight
[g/mol]398.6 238.3 432.5 356.5 210.2
H-active-
Equivalent136-140 122-125 111-114 122-125 107-108
SH-content
[%w/w]~ 24 ~ 26.8 ~ 29.5 ~ 26.5 ~ 30.5
ViscosityBrookfield ISO 2555,
21°C~150 mPa.s ~10 mPa.s
~400 mPa.s
Cristallize at
RT
~120 mPa.s ~10 mPa.s
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*Experimental Product
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THIOCURE® Di-PETMP Di-TMPMP*
Chemical
DescriptionDi-Pentaerythritolhexakis
(3-mercaptopropionate)
Di-Trimethylolpropanetetra
(3-mercaptopropionate)
SH-functionality 6 4
Molecular Weight
[g/mol]783.0 602.8
H-active-Equivalent 135 – 139 154 – 158
SH-content [%w/w] ~ 24.1 ~ 20.8
ViscosityBrookfield ISO 2555,
21°C
~ 2000 mPa.s ~ 450 mPa.s
BRUNO BOCK THIOCHEMICALS
Einsatz
THIOCURE® TEMPIC
Chemical
DescriptionTris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate
Formula
SH-functionality 3
Molecular Weight 525.6 g/mol
SH-content [%w/w] 18 %
ViscosityBrookfield ISO 2555,
21°C
~8000 mPas
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THIOCURE® ETTMP 700 ETTMP 1300 PCL4MP 1350*
Chemical
Description
Ethoxylated
Trimethylpropan-tri(3-
mercapto-propionate)
Ethoxylated Trimethylpropan-
tri(3-mercapto-propionate)Polycaprolactone tetra
3-mercaptopropionate
SH-functionality 3 3 4
Molecular Weight
[g/mol]~700 ~1300 ~1350
H-active-Equivalent 236-262 435-448 348-375
SH-content [%w/w] ~ 13.5 ~ 7.1 ~ 9.1
ViscosityBrookfield ISO 2555, 21°C ~200 mPa.s ~400 mPa.s ~1000 mPa.s
*Experimental Product
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PU-Systems TypesTHIOCURE Evans Chemetics SealantsEP-Systems UV/ThiolEne
THIOCURE® DMPT DMDS
Chemical
Description2,3-Di((2-mercaptoethyl)thio)-1-propane-
thiolDimercaptodiethylsulfide
Formula
SH-functionality 3 2
Molecular Weight
[g/mol]260.5 154.3
SH-content [%w/w] min. 36.2 min. 40.7
ViscosityBrookfield ISO 2555, 21°C
< 10 mPa.s < 10 mPa.s
Refractive Index 1.63 1.60
RemarkDMPT and DMDS are very smelly! Both may cause sensitization.
Use only in closed applications!
BRUNO BOCK THIOCHEMICALS
08-2014
Einsatz
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 +49-(0)4176-9098-13 j.jensen@brunobock.de
Technical Service Center Elvira Schlatter +49-(0)4176-9098-27 e.schlatter@brunobock.de
Development Dr. Matthias Rehfeld +49-(0)4176-9098-21 m.rehfeld@brunobock.de
© Bruno Bock
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