THIOCURE for Paints & Coatings, Adhesives & · PDF fileBRUNO BOCK THIOCHEMICALS Titelfolie THIOCURE® for Paints & Coatings, Adhesives & Sealants

BRUNO BOCK THIOCHEMICALS

Titelfolie

THIOCURE®

for Paints & Coatings,

Adhesives & Sealants


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

1

THIOCURE


2

� 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


3

� 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



4

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


5


� Polythiols have a high refractive index

� Thiocure Polythiols are

� di- up to hexafunctional

� low in viscosity

� solvent- and VOC-free

� nearly colorless liquids


6

� Thiols react via polyaddition with Epoxies and Isocyanates

and via radical respectively nucleophile addition with double-

and triple-bonds



7

� Synthesis of Polythiols by esterification of Mercaptocarboxylic

Acids + polyfunctional Alcohols

� 3-Mercaptopropionic Acid (3-MPA) Mercaptopropionates

and Polymeric thiols

� Thioglykolic Acid (TGA) Mercaptoacetates



8

+ Pentaerythritol THIOCURE®

PETMP

THIOCURE®

TMPMP+ Trimethylolpropane

+ Ethylenglycol THIOCURE®

GDMP

Mercaptopropionates

3-Mercaptopropionic Acid



9

Polymeric Polythiols


THIOCURE® ETTMP

THIOCURE® PPGMP 800 und 2200 (Experimental products)

THIOCURE® PCL4MP 1350 (Experimental product)


10

+ Pentaerythritol THIOCURE®

PETMA

THIOCURE®

TMPMA

+ Trimethylolpropane

+ Ethyleneglycol THIOCURE®

GDMA

Mercaptoacetates

Thioglycolic Acid (TGA)



11

THIOCURE® Characteristics

Mercapto-

propionatesPETMP, TMPMP, GDMP, 1

Mercapto-

AcetatesPETMA, TMPMA, GDMA

Polymeric

PolythiolsETTMP, PCL4MP 1350

Reactivity + ++ -

Hardness + ++ -

Flexibility -/+ -/+ ++

UV-Resistance ++ + -/+

Water miscibility -- -- -/+

Odor ++ - +


++ = best


12

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



13


� 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


14

� 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


15

� 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



16

� 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]



17

� Lower CO2-formation in comparison to the

NCO-OH reaction

17-32 THIOCURE® ETTMP 700 + Desmodur® E 29

17-29 Polyetherpolyol + Desmodur® E 29



18

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



19

� 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



20

� Use of an activator like tertiary amine is necessary


The resulting thiolate anion is highly nucleophilic and

quickly added to the epoxideSource: „Formulierung von Kleb- und Dichtstoffen“ (Bodo Müller / Walter Rath)


21

� 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)


331

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


22

� 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)



23

THIOCURE® - Application Examples

� Floorings in parking garages and cold stores

� Concrete road repairs / repair mortars

� „5-minutes“ consumer adhesives

� Adhesives for electronic applications

©Pixelio



24

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


25

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



26

� Advantages:

no oxygen inhibition!!!

low volume shrinkage

high conversion of the double bonds

THIOCURE® - Application Examples

� Wood Impregnation � Doming-Labels



27

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



28

THIOCURE® for Sealants

� As modifier for sealants based on polysulfide

to increase the crosslinking density



29

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



30

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



31



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


21°C

~ 2000 mPa.s ~ 450 mPa.s


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 %


21°C

~8000 mPas

32



33

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




34


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!


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 [email protected]

Technical Service Center Elvira Schlatter +49-(0)4176-9098-27 [email protected]

Development Dr. Matthias Rehfeld +49-(0)4176-9098-21 [email protected]

© Bruno Bock

We advise our customers to the best of our knowledge and information available to us. No freedom from any patent owned by Seller or others is to be inferred. Because conditions of use and

applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are

appropriate for Customer’s use and for ensuring that Customer’s workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes

no obligation or liability for the information in this document.

NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED.

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THIOCURE for Paints & Coatings, Adhesives & · PDF fileBRUNO BOCK THIOCHEMICALS Titelfolie THIOCURE® for Paints & Coatings, Adhesives & Sealants