Talk3 - Dmitry Chernyshov

EVALUATION OF SILANE TECHNOLOGIES FOR THE
APPLICATION IN A 2K WB POLYURETHANE
TOPCOAT SYSTEM ON GLASS:
Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Scope:
- Product introduction:
- CoatOSil* MP200 epoxysilane oligomer
- CoatOSil DRI polysiloxane emulsion
- CoatOSil T-Cure glycolic thiolsilane oligomer
- Application of organofunctional silanes and silicones in wb PU systems:

- Formulation examples
- Polyisocyanate modification
- Test results
- Conclusions:

*CoatOSil is a trademark of Momentive Performance Materials Inc.
Basics of Silane Chemistry:
Chemistry Typical Performance Attributes
Between Surfaces
OR - coupling
Compatibilization
pigments; fillers
Y S i OR Surface A Surface B
Men
- Amino Y X
- Epoxy R = Methyl - adhesion Bonding
coatings; laminates
- Vinyl R = Ethyl
- Isocyanato n = 1 or 0;
OR = 2 or 3
- Methacryl Between Polymers
- Ureido - cross-linking x x x
- Mercaptan Re-enforcement
PE pipes; cable;
- Polysulfide coatings

CoatOSil* MP 200 Epoxy Silane Oligomer
A New Silane for CAS Applications
CH3 CH3 TYPICAL PHYSICAL PROPERTIES:

H3CO O O O O O OCH3
Flash point: 106OC
H3CO Si Si Si Si OCH3
Active material: 98%
Epoxy (mequiv./g): 4,79
O O O O
Viscosity: 30-40 cSt/25OC
Specific gravity: 1,13 g/ml
Solubility (demi.water): not soluble
O O O O Typical properties are average data and are not to be used as or to develop specifications.
Key Feature Typical Benefits

Product contains partially hydrolyzed • Availiability of alkoxy groups for
and condensed silane further hydrolysis/condensation
• Lower VOC contribution
Availability of polyepoxide groups • Faster grafting with polymers
• Faster curing at application
Product contains oligomeric siloxane • Better stability against hydrolysis
network • Hydrophobicity
Low viscosity • Reactive diluent
100% active material • Uses in WB, SB, HS and PC systems

CoatOSil* DRI Silicone Emulsion Form - Features
Low Viscosity Emulsion of Crosslinked Siloxanes
CoatOSil
DRI
Acrylic latex
-Hydrophobic waterborne siloxane emulsion form -Cures to form elastic film at room temperature
-Anticipated Low VOC -High temperature resistance

Formulated to be VOC free in Europe - Only 40% weigh loss after pyrolysis
-Typical Emulsion Properties -Typical film Properties

- White opaque liquid - Tensile MPa(psi): 3,45(500)
- ~45% solids - Elongation: ~450%
- Low viscosity: ~20 cp - Hardness (Shore A): ~30
- pH ~11 - Elastic recovery: >90%
-Compatibility with WB latexes and dispersions -Water contact angle >90°
Typical properties are average data and are not to be used as or to develop specifications. Note: Test data. Actual results may vary.

CoatOSil* DRI Polysiloxane as Co-binder in Coating Systems:
Compatibility with Resin Systems
WB-dispersion control 1 mixed with control 1 mixed with control 1 mixed with
control 1 CoatOSil MP200 silane CoatOSil DRI siloxane commercial silicone
(1wt.-%) (10wt.-%) emulsion (10wt.-%)
WB-dispersion control 2 mixed with control 2 mixed with control 2 mixed with
control 2 CoatOSil MP200 silane CoatOSil DRI siloxane commercial silicone
(1 wt.-%) (10wt.-%) emulsion (10wt.-%)
-CoatOSil DRI siloxane emulsion demonstrated significantly higher compatibility with WB-dispersion
resins compared to commercially available silicone emulsions Note: Test data. Actual results may vary.

CoatOSil* DRI Polysiloxane as Co-binder in Coating Systems:
Compatibility with Resin Systems
Micro-compositional analysis through energy dispersive x-ray spectroscopy

showed limited silicone enrichment on resin film surface.
Characterization of Elements (Si content) of upper layer (10 nm) of a coating layer
WB dispersion film only WB dispersion+10% CoatOSil DRI

polysiloxane film
Si% wt on surface: None
Si% wt on surface: 6,4%
(vs. 4% uniform bulk distribution)
CoatOSil DRI polysiloxane demonstrated uniform distribution of Si over the coating, allowing
good film overcoatability Note: Test data. Actual results may vary.

WB Two pack Epoxy primers with Silane and Siloxane
Formulation parameters
TYPICAL PHYSICAL PROPERTIES:

CoatOSil* DRI
CoatOSil MP200 silane
polysiloxane
STRUCTURE
Reactive Siloxane emulsion
Active content 45% 100%

VOC content
(after full 0% 20 %
hydrolysis)
Function Flexibilizer and hydrophobic agent Adhesion promoter and crosslinker
Typical properties are average data and are not to be used as or to develop specifications.

CoatOSil* T-Cure: Glycolic Thiolsilane Oligomer – Value Proposition
Key features and typical benefits

-No HAPS /<1% Releasable
-Low Viscosity
-Low odor
(as opposed to typical Mercapto Silane)
-Reactive diluent behaviour
- <1% Releasable HAPS
Typical physical properties

-Density (g/cm3) : 1,105
CoatOSil T-Cure
-Viscosity at 25 0C (cPs) : ~400 Glycolic Thiolsilane
-Refractive Index at 25 0C : ~1,474 Oligomer
-Surface Tension at 25 0C(dyne/cm): ~34,65
Typical properties are average data and are not to be used as or to develop specifications.

CoatOSil* T-Cure silane: Glycolic Thiolsilane Oligomer – Hydrolysis Rate
Glycol Methanol Ethanol

CH3CH2O CH3CH2O OCH3 OCH2CH3
R Si
O
O
> R Si
O
O
> CH3O Si
OCH3
R
> H3CH2CO Si R
OCH2CH3
2-Methyl-1,3- 1,3-
propanediol Butanediol
Faster Slower
Cyclic species hydrolyze faster than methoxy- silanes
Glycolic silanes allow faster curing rates compared to

methoxy silanes
CoatOSil* T-Cure silane: Typical Performance Benefits in Coatings
CoatOSil T-Cure silane becomes incorporated into 2K PU coating via a

controlled reaction with the Isocyanate hardener.
CoatOSil T-Cure Silane Isocyanate Trimer Thiourethane Linkage
Key Features of CoatOSil T-Cure Silane Typical Performance Benefits in Coatings

-Advanced chemical resistance
-Enhanced x-linking of PU coatings
-Good hardness development
-Interaction with specific substrates
-Enhanced adhesion
-Advanced QUV stability
-Non-yellowing on outdoor exposure

2-pack WB Polyurethanes: Value Proposition
Value proposition:
-2K waterbased polyurethane coatings –
Lower VOC alternatives for traditional SB PU coatings
Advantages:
-Excellent mechanical properties and chemical resistance
-Outstanding outdoor resistance
-Highly productive systems
-Environmentally responsible
Value proposition of silanes in polyurethane finishes:

Salt-spray cabinet, ISO7253
-Advanced wet adhesion on complex surfaces
-Good corrosion resistance
-Good chemical resistance
-Enhanced weatherability for outdoor application
Control
2-pack WB Polyurethanes: Coating Chemistry
Chemistry: 2K PU cure
water-based emulsion aliphatic isocyanate
-acrylic polyol OH + O C N -hydrophilic Diffusion of
-polyester polyol -hydrophobic polyisocyanate into
-modified alkyd polyol -mix WB polyol emulsion
O C N
O H
Polyurethane is formed as a product

of polyol - isocyanate reaction

Polyisocyanate in
O=C=N-
organic solvent
Film application
Mix both
-OH
components
together Evaporation of water
Waterbased
-OH -OH polyol Control
secondary
Film formation
-OH
13 emulsion
WB 2-pack Polyurethanes: Model Formulations Used in the Studies
WHITE TINTING PASTE FUNCTIONAL BINDER

WB-acrylic dispersion 30 WB-acrylic dispersion 70
Dispersing aid 4 Dispersing aid 4
Butylglycol 4 Butylglycol 4
Water 5 water 12,4
Titanium dioxide 52 Wollastonite 3
mixing with cowless blades disperser Mica S 3
milling with Zr-beads , 45 min, at RT. Talkum 3
Grinding fineness less 15 micron CoatOSil*2812 block-co-polymer 0,1
1000 rpm mixing with cowless blades disperser
Water 5 milling with Zr-beads , 45 min, at RT.
TOTAL 100 Grinding fineness less 15 micron
1500 rpm
CoatOSil 7001E block-co-polymer 0,1
UV-HALS 0,4
TOTAL 100
Product formulations are included as illustrative examples only. Momentive makes no representation or warranty of
POLYISOCYANATE CROSSLINKER any kind with respect to any such formulations, including, without limitations, concerning the efficacy or safety of any
product manufactured using such formulations.
Aliphatic polyisocyanate 60,0
Butylglycol acetate 35
Ethyl-3-ethoxypropionate 5
TOTAL 100,0

CoatOSil CoatOSil
CoatOSil Silquest CoatOSil CoatOSil CoatOSil MP200 T-Cure
PART A control MP200 A137 DRI MP200 and DRI T-Cure w/o funct. Binder w/o funct. Binder
WHITE TINTING PASTE 43,7 43,3 43,0 41,9 41,5 41,5 49,7 47,3
FUNCTIONAL BINDER 43,7 43,3 43,0 41,9 41,5 41,5
CoatOSil*DRI polysiloxane 4,2 4,2
WB-acrylic dispersion 35,1 33,4
Silquest*A137 silane 1,6
PART B
POLYISOCYANATE 12,6 12,5 12,4 12,1 12,0 16,2 14,4 18,6
CoatOSil MP200 silane 0,8 0,8 0,8
CoatOSil T-Cure silane 0,8 0,8

TOTAL 100,0 100,0 100,0 100,0 100,0 100,0 100,0 100,0
Product formulations are included as illustrative examples only. Momentive makes no representation or warranty of any kind with respect to any such formulations, including, without limitations,
concerning the efficacy or safety of any product manufactured using such formulations.
- Silane was introduced either into the polyol part of the topcoat (Silquest A137 silane) or into
a polyisocyanate part of the formulation (CoatOSil MP200 silane) or into both (CoatOSil DRI
polysiloxane and CoatOSil MP200 silane)
- In case of CoatOSil T-Cure silane the silane was introduced into the system as a 3rd
component (due to high hydrolysis rate in water)

*CoatOSil and Silquest are trademarks of Momentive Performance Materials Inc.
WB 2-pack PU Topcoats with Silane and Siloxane: APPLICATION
Formulation: Part A and Part B are homogenized

Part A + Part B are mixed together vigorously
Thinner: Deionized water: 0 to 5% for viscosity adjustment/spray
Substrates: Glass panels
Preparation: Cleaning with xylene followed by IPA degreasing
Application: Air spray -1.4 mm nozzle gravity feed-1.5 bars
Thickness: 40 to 60 microns dft.
Flahs-off: 15 minutes
Drying: RT, 1 week before testing
Test protocol: -Dry and wet adhesion (immersion in water at 60 OC.)

-QUV-B accelerated weatherability
-impact resistance
-chemical acid etch resistance

Test Results: dry & wet adhesion
control CoatOSil* MP200 Silquest* A137

-All 2K PU TC systems
showed excellent DRY
adhesion
-WET adhesion failed

for all systems EXCEPT
CoatOSil MP200 and
CoatOSil T-Cure
-No synergies from

using CoatOSil MP200
CoatOSil DRI CoatOSil MP200 / DRI CoatOSil T-Cure and CoatOSil DRI were
observed
Note: Test data. Actual results may vary.

CoatOSil* MP200 silane CoatOSil T-Cure silane

-Silanes were observed to have
improved wet adhesion on glass
more effectively in case of a
coating systems which are
modified with functional fillers and
extenders:
-talcum
CoatOSil MP200 silane CoatOSil T-Cure silane -mica

W/O Fillers & Extenders W/O Fillers & Extenders -wollastonite
-kaolin
-clays
-Non-treated fillers & extenders
are typically more efficient in
enabling adhesion promotion with
silanes on glass
*CoatOSil is a trademarks of Momentive Performance Materials Inc.
Test Results: accelerate weatherability
QUV-B, gloss
95 - Improved gloss retention of silane
90
modified topcoat systems vs. control
85
topcoat
Gloss, 60'
80
Yellowing
75 4,5
70 4
delta E color change

3,5
65
3
60
0 10 20 30 40 50 60 70 2,5
Days 2
control CoatOSil MP 200 silane (0,8 wt.-%)
1,5
CoatOSil* T-Cure silane (0,8 wt.-%) Silquest*A137 silane (1,6 wt.%)
1
CoatOSil DRI polysiloxane (4 wt.-%)
0,5
0
0 10 20 30 40 50 60 70
- Improved yellowing resistance of coating
Days
systems modified with organosilicone control CoatOSil MP 200 silane (0,8 wt.-%)
CoatOSil* T-Cure silane (0,8 wt.-%) Silquest*A137 silane (1,6 wt.%)

additives (silanes and siloxanes)
CoatOSil DRI polysiloxane (4 wt.-%)

Test Results: impact Resistance and Chemical Acid Etch Resistance
Acid Etch Test: Impact Resistance Test (on steel):

-test is carried out by exposing a CC to 30, 60 and
90 min. etch attack of 0,5M H2SO4 (at 50 OC)
-ranking: R10 - best to R1 – worst
30 min.
60 min. impact DIRECT impact REVERSE

(A) 2K PU Control OK OK
(B) CoatOSil*M P 200 silane OK OK
(C) CoatOSil T-Cure silane OK OK
(D) CoatOSil DRI polysiloxane OK OK
90 min.
R 30 min. R 60 min R 90 min SUM (R)

-good flexibility of Si- modified topcoat systems
(A) 2K PU Control 6 0 0 6
(B) CoatOSil*M P 200 silane 8 6 4 18 -improved chemical etch resistance of Si-modified
(C) CoatOSil T-Cure silane 8 6 4 18 topcoat systems
(D) CoatOSil DRI polysiloxane 8 2 2 12

*CoatOSil is a trademarks of Momentive Performance Materials Inc.
WB 2-pack Polyurethanes: Silane Modifcation of Polyisocyanate Crosslinker
SILANIZATION 30% 10% 5%

POLYISOCYANATE 38 50 55
Butylglycolacetate 35 35 35
Ethylethoxypropionate 5 5 5
Coating Systems:102K WB
Silquest*Y-9627 silane 22 5 PU with Si-modified polyisocyanates
total (in gr.) 100 100 100
Solids% 60 60 60
NCO-Number% 6,3 10,6 12,7 3
-Universal and robust approach allowing

incorporation of different aminosilanes 3
into the polyisocyante structure; 3

-Alkoxysilane-modified polyisocyante
adduct, stable across wide variety of
silanization levels;
-Si(OR)x moiety typically improves

solubility in water due to the polarity of 3 3
Si-OH groups formed upon hydrolysis.


*Silquest is a trademarks of Momentive Performance Materials Inc.
control, only control only Silquest A137 CoatOSil DRI

with silane modified with Silquest* A137 with silane modified with silane modified
PART A polyisocyanate std. polyisocyanate polyisocyanate polyisocyanate
WHITE TINTING PASTE 40,60 42,9 39,9 37,2
FUNCTIONAL BINDER 40,60 42,9 39,9 37,2
CoatOSil* DRI polysiloxane 8,3
Silquest A137 silane 1,6 1,6

PART B
POLYISOCYANATE 12,5
POLYISOCYANATE modified
with 15% Silquest Y-9627 silane 18,80 18,5 17,2
TOTAL 100,0 100,0 100,0 100,0
-Combining silane adhesion promoter in the polyol part of the formulation with the silane-
modified polyisocyanate
-Examples of other silane applicable for polyisocyanate modification: Silquest A-Link 15 silane;
Silquest A-Link600 silane (only 5% silanization max.); CoatOSil T-Cure silane (only 1% silanization
max.)

Silquest* Y-9627 silane modified Silquest A137 silane modified

polyisocyanate, ONLY polyol, ONLY
-Modification of
polyisocyanate activator
alone did not yield
formulations with improved
wet adhesion on glass
Silquest Y-9627 silane modified Silquest Y-9627 silane modified

polyisocyanate and CoatOSil* DRI polyisocyanate and Silquest A137 -Simultaneous application of
polysiloxane modified polyol silane modified polyol
silane (siloxane) modified
polyol and silane-modified
polyisocyante yielded
improved wet adhesion on
glass substrate
Copyright © 2019 Momentive Performance Materials Inc. All rights reserved. Note: Test data. Actual results may vary.
CONCLUSIONS:
1. Oligomer epoxysilane technology and glycolic thiol-silane technology has

shown to help improve wet adhesion of 2K WB Polyurethane coating systems on
glass substrates
2. Optimum adhesion promotion effect of the silane technology is observed in the

case of coating formulations containing special inorganic fillers and extenders
3. To increase wet adhesion on glass one can utilize synergies between

incorporation of silane adhesion promoters into the paint formulation and
application of polyisocyanate crosslinkers chemically modified with silanes
DISCLAIMER
DISCLAIMER: THE MATERIALS, PRODUCTS AND SERVICES OF MOMENTIVE PERFORMANCE MATERIALS INC. AND ITS SUBSIDIARIES AND AFFILIATES DOING BUSINESS
IN LOCAL JURISDICTIONS (COLLECTIVELY “SUPPLIERS”) ARE SOLD BY THE RESPECTIVE LEGAL ENTITY OF THE SUPPLIER SUBJECT TO SUPPLIERS’ STANDARD CONDITIONS
OF SALE, WHICH ARE INCLUDED IN THE APPLICABLE DISTRIBUTOR OR OTHER SALES AGREEMENT, PRINTED ON THE BACK OF ORDER ACKNOWLEDGMENTS AND
INVOICES, AND AVAILABLE UPON REQUEST. ALTHOUGH ANY INFORMATION, RECOMMENDATIONS, OR ADVICE CONTAINED HEREIN IS GIVEN IN GOOD FAITH,
SUPPLIERS MAKE NO WARRANTY OR GUARANTEE, EXPRESS OR IMPLIED, (I) THAT THE RESULTS DESCRIBED HEREIN WILL BE OBTAINED UNDER END-USE CONDITIONS,
OR (II) AS TO THE EFFECTIVENESS OR SAFETY OF ANY DESIGN INCORPORATING SUPPLIERS’ PRODUCTS, MATERIALS, SERVICES, RECOMMENDATIONS OR ADVICE.
AFOREMENTIONED EXCLUSIONS OR LIMITATION OF LIABILITY ARE NOT APPLICABLE TO THE EXTENT THAT THE END-USE CONDITIONS AND/OR INCORPORATION
CONDITIONS CORRESPOND TO THE RECOMMENDED CONDITIONS OF USE AND/OR OF INCORPORATION AS DESCRIBED BY SUPPLIER IN ITS PRODUCT DATA SHEET
AND/OR PRODUCT SPECIFICATIONS. EXCEPT AS PROVIDED IN SUPPLIERS’ STANDARD CONDITIONS OF SALE, SUPPLIERS AND THEIR REPRESENTATIVES SHALL IN NO
EVENT BE RESPONSIBLE FOR ANY LOSS RESULTING FROM ANY USE OF ITS MATERIALS, PRODUCTS OR SERVICES DESCRIBED HEREIN. Each user bears full responsibility
for making its own determination as to the suitability of Suppliers’ materials, services, recommendations, or advice for its own particular use. Each user must
identify and perform all tests and analyses necessary to assure that its finished parts incorporating Suppliers’ products, materials, or services will be safe and
suitable for use under end-use conditions. Nothing in this or any other document, nor any oral recommendation or advice, shall be deemed to alter, vary,
supersede, or waive any provision of Suppliers’ Standard Conditions of Sale or this Disclaimer, unless any such modification is specifically agreed to in a writing
signed by Suppliers. No statement contained herein concerning a possible or suggested use of any material, product, service or design is intended, or should
be construed, to grant any license under any patent or other intellectual property right of Suppliers or any of its subsidiaries or affiliates covering such use or
design, or as a recommendation for the use of such material, product, service or design in the infringement of any patent or other intellectual property right.
Momentive and the Momentive logo are trademarks of Momentive Performance Materials Inc.

CoatOSil and Silquest are trademarks of Momentive Performance Materials Inc.

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EVALUATION OF SILANE TECHNOLOGIES FOR THE

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

- Application of organofunctional silanes and silicones in wb PU systems:

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Chemistry Typical Performance Attributes

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

CH3 CH3 TYPICAL PHYSICAL PROPERTIES:

Key Feature Typical Benefits

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

-Anticipated Low VOC -High temperature resistance

-Typical Emulsion Properties -Typical film Properties

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Micro-compositional analysis through energy dispersive x-ray spectroscopy

WB dispersion film only WB dispersion+10% CoatOSil DRI

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

TYPICAL PHYSICAL PROPERTIES:

Reactive Siloxane emulsion

Active content 45% 100%

Function Flexibilizer and hydrophobic agent Adhesion promoter and crosslinker

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Key features and typical benefits

Typical physical properties

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Glycol Methanol Ethanol

Cyclic species hydrolyze faster than methoxy- silanes

Glycolic silanes allow faster curing rates compared to

CoatOSil T-Cure silane becomes incorporated into 2K PU coating via a

CoatOSil T-Cure Silane Isocyanate Trimer Thiourethane Linkage

Key Features of CoatOSil T-Cure Silane Typical Performance Benefits in Coatings

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Value proposition of silanes in polyurethane finishes:

Polyurethane is formed as a product

Salt-spray cabinet, ISO7253

WHITE TINTING PASTE FUNCTIONAL BINDER

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

CoatOSil T-Cure silane 0,8 0,8

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Formulation: Part A and Part B are homogenized

Test protocol: -Dry and wet adhesion (immersion in water at 60 OC.)

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

control CoatOSil* MP200 Silquest* A137

-WET adhesion failed

-No synergies from

Note: Test data. Actual results may vary.

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

CoatOSil* MP200 silane CoatOSil T-Cure silane

CoatOSil MP200 silane CoatOSil T-Cure silane -mica

delta E color change

CoatOSil* T-Cure silane (0,8 wt.-%) Silquest*A137 silane (1,6 wt.%)

Note: Test data. Actual results may vary.

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

Acid Etch Test: Impact Resistance Test (on steel):

60 min. impact DIRECT impact REVERSE

R 30 min. R 60 min R 90 min SUM (R)

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.

SILANIZATION 30% 10% 5%

-Universal and robust approach allowing

into the polyisocyante structure; 3

Salt-spray cabinet, ISO7253

-Si(OR)x moiety typically improves

Si-OH groups formed upon hydrolysis.

Copyright © 2019 Momentive Performance Materials Inc. All rights reserved.