Dynasylan® Oligomers
for Challenging
Requirements in
Adhesives & Sealants
SpecialChem Webinar, January 30th 2020
Juergen Fritz,
Manager Applied Technology
Adhesives & Sealants
Evonik Resource Efficiency GmbH
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offer an advanced performance in adhesives and sealants
• Summary
• Contacts
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Evonik: Focus on Specialty Chemicals
▪ One of the global leaders in specialty chemicals
▪ Around 80 percent of our sales are generated in businesses where we
rank among the market leaders
▪ Strong integrated technology platforms
▪ Well-balanced spectrum of business activities, end-markets, and
regional presence
▪ Close collaboration with customers
▪ Market-orientated research and development
▪ All 3 business segments do sell additives and specialty products to the
Adhesives & Sealants industry
(www.evonik.com/adhesives-sealants)
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offering an advanced performance in adhesives and sealants
• Summary
• Contacts
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What are Dynasylan® Organofunctional Silanes?
Bifunctional molecules!
Representative structure of organofunctional silanes:
(n = 0, 1, 2, 3)
The organofunctional group can The hydrolyzable group can react
interact and/or react with polymers, with inorganic fillers, metals, glass
generate adhesion or modify the or undergo self-condensation.
properties of inorganic surfaces.
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Mode of Action of Organofunctional Silanes
Silanes are used as: Primer 0.05 – 5 % in water or alcohol/water (pH = 3 - 5)
Additive 0.30 – 2 % without solvent
1. Stepwise Catalyst H+(*)
Y Si(OR)3 Y Si(OH)3
hydrolysis + 3 H2O/- 3 ROH
Silanetriol
2. Bonding by Y Si(OH)3 + HO Y
- x H2O
SiO
condensation
Substrate O
3. Filmforming and interaction
with polymer matrix via Y Y SiO
Polymer Matrix O
(*)exception: aminosilanes
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Why using Dynasylan® Silanes in Adhesives & Sealants ?
Silane Effects Industries
• Adhesion Promotion
• Crosslinking
• Drying
• Polymer Modification (PU-Endcapping)
• Reinforcement
• Rheology Modification
Silane Improvements
• Wet and dry adhesion
• Mechanical properties
• Storage stability
• Resistance to heat, moisture, atmospheric factors
and solvents
• Storage, handling and easy processing
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offering an advanced performance in adhesives and sealants
• Summary
• Contacts
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Example for efficient Adhesion Promotion
Lap shear of 1 comp. PU-sealant on aluminum and glass,
with and without Dynasylan® Silanes
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Glass Aluminum
lap shear [N/mm²]
PU-sealant
2
without silane
adhesion failure cohesion failure
1
0
no silane Dynasylan®
PU-sealant with
GLYMO
Dynasylan® GLYMO
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VPS 4721
Epoxyfunctional Silane
Oligomer
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VPS 4721: Epoxyfunctional Silane Oligomer (Patent Protected)
▪ Oligomer,
with polymer status by OECD definition
▪ High molecular weight > 2000 g/mol
▪ Low monomer content < 3.0 %
▪ Reduced VOC (approx. 60 %) vs. GLYMO
▪ Advantages in labelling
Y1,2 = organofunctional group (VPS 4721 = epoxy)
OR = hydrolyzable group
[..] = repeating unit of monomer
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VPS 4721: Epoxyfunctional Silane Oligomer
▪ Excellent adhesion promoter for Adh. and Seal.
▪ Excellent color and color stability
▪ Excellent product stability also at higher T
▪ High long term stability
▪ Excellent reactivity
▪ Better stability vs. GLYMO in water based Adh. and Seal.
▪ Significant reduced VOC content
▪ Low monomer content/ improved Labelling
VPS 4721
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Better stability of VPS 4721 compared to GLYMO as Additive
in 1 Component Waterborne Acrylic Polymer Dispersions
solid
250
200
Viscosity DIN 4 cup (sec)
150
immediately
2 weeks @ RT
100 4 weeks @ RT
8 weeks @ RT
50
0
Mowilith Mowilith Mowilith Mowilith Mowilith Mowilith
LDM 7719 LDM 7719 + LDM 7719 + LDM 6119 LDM 6119 + LDM 6119 +
3% GLYMO 3% VPS 4721 3% GLYMO 3% VPS 4721
Viscosity acc. DIN ISO 2431 and a cup DIN 53211 with a jet of 4 mm at 17 – 24 °C
VPS 4721 led to much higher stability versus GLYMO in mixture with waterborne dispersion !
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offer an advanced performance in adhesives and sealants
• Summary
• Contacts
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Silane Oligomers from Evonik
for Adhesives and Sealants
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Oligomers
Simplified structure model: Properties
Y = organofunctional
group • low viscous
OR = hydrolyzable • liquid
group • colorless to yellow
[..] = repeating unit of • reduced VOC
monomer content
• multifunctional in
selected cases
• typically sensitive to
hydrolysis
Oligomeric silanes consist of complex structures of • polymer status
various siloxanes which are formed via condensation according to OECD
of monomeric silanes.
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Dynasylan® Silane Oligomers from Evonik for Adhesives and Sealants
Overview & Application Fields
Superior, low yellowing adhesion promoter
for glass, metals and diverse plastics
➔ No labeling required
Dynasylan®
1146
Adhesion promoter for glass,
Epoxy functional adhesion
metals and diverse plastics VPS SIVO
➔No labeling required VPS 4721 promoter for 1 and 2 K PU ,
324-1 Rubber, epoxy systems etc.
➔Ethanol release
Evonik‘s
oligomeric
systems
Adhesion promoter for Higher-boiling adhesion promoter
difficult to adhere plastics
VPS SIVO Dynasylan® vs. Dynasylan® VTMO
especially on PC and metals 260 6490 Coupling agent for PE and EVA
VPS SIVO
280
Adhesion promoter for difficult to adhere
plastics especially on PMMA and metals
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Released amount of Methanol, Monomeric versus Oligomeric Amino Silanes
Released amount of methanol after complete hydrolysis [g methanol/ 100 g silane]
Dynasylan® AMMO 53.5
Dynasylan® 1146 30.0
VPS SIVO 260 15.0
VPS SIVO 280 12.0
Oligomeric silanes offer crucial reduction of VOC-release
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CLP Labeling of Important Silanes
Classification Concentration in the mixture [%]
Product GHS-Pictograms Signal Word Hazard Statement
>= 10 %: H315 with Pictogram GHS07
(Exclamation mark)
>= 3 %: H318 with Pictogram GHS05 (Corrosion)
>= 1 % and < 3%: H319 with Pictogram GHS07
H315 = Causes skin irritation (Exclamation mark)
Dynasylan® AMMO GHS05 = Corrosion Danger H318 = Causes serious eye damage < 1 % no classification of AMMO in the mixture
<= 33 %: no classification
> 33 %: H319 with pictogram GHS07
VPS SIVO 260 GHS07 = Exclamation Mark Warning H319 = Causes serious eye irritation (exclamation mark)
Not a hazardous substance
according to Regulation (EC) No.
Dynasylan® 1146 not classified - 1272/2008 No concentration limit
<= 3,3 %: no classification
H317 = May cause an allergic skin reaction > 3,3 %: H319 with pictogram GHS07
VPS SIVO 280 GHS07 = Exclamation Mark Warning H319 = Causes serious eye irritation (exclamation mark)
Both VPS SIVO products – and especially Dynasylan® 1146 – help to avoid labeling
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Dynasylan® 1146
in RTV-1 Alkoxy Silicones
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Higher strengths of cured Alkoxy Silicone Sealant Dogbones
Strength [N/mm²]
0.0 0.5 1.0 1.5
Dynasylan® 1146
Standard aminosilane Tensile strength
Tear strength
Silane dosage: 2.0 %
Dynasylan® 1146 gives significantly higher mechanical properties compared to standard
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Primerless adhesion to Metals and Plastics in alkoxy silicones
Lap Shear [N/mm²]
0.0 1.0 2.0
Dynasylan® 1146
Standard aminosilane Aluminium
Polycarbonate
Silane dosage: 2.0 %
Dynasylan® 1146 shows improved adhesion on Aluminium and Polycarbonate !
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VPS 324-1
Ethoxy based adhesion promoter
Alkyl-amino-co-oligomer
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Influence of Special Silanes as adhesion promoters in filled STPU-adhesive
Elongation at Break
Elongation at break [index %]
0 50 100
Dynasylan® 1146
VPS SIVO 324-1
Filled STPU incl. 1.11 % adh. promoter
VPS SIVO 324-1 helps to improve the flexibility of STPU-adhesives
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Influence of Special Silanes as adhesion promoter in filled STPU-adhesive
Strength Properties
Strength [N/mm²]
0.0 1.0 2.0
Dynasylan® 1146
VPS SIVO 324-1 Tensile strength
Tear strength
Filled STPU incl. 1.11 % adh. promoter
VPS SIVO 324-1 and Dynasylan® 1146 display high strengths in STPU-adhesive
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Influence of Special Silanes as adhesion promoter in filled STPU-adhesive,
Lap Shear Adhesion
Lap shear adhesion [index %]
0 20 40 60 80 100
Aluminium
PVC
Dynasylan® 1146 PMMA
VPS SIVO 324-1
Filled STPU incl. 1.11 % adh. promoter
VPS SIVO 324-1 shows a lower adhesion performance vs. high performance Dynasylan® 1146,
but VPS SIVO 324-1 is an option for the up-coming methoxy free systems
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VPS SIVO 324-1 gives outstanding Water Repellency (STPU Sealant)
4.5
4.0 Water uptake [%] over time [d]
AMEO
3.5
3.0
2.5
VPS SIVO 324-1
2.0
1.5
1.0
0.5
0.0
0 10 20 30 40 50 Filled STPU incl. 1.11 % adh. promoter
VPS SIVO 324-1 strongly improves hydrophobicity, thus minimizes water uptake !
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VPS SIVO 260 and
VPS SIVO 280
Multifunctional
Silane SystemsTM
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VPS SIVO 260: Outstanding adhesion on Polycarbonate
CF
VPS SIVO 260
MF
Standard amino silane
2 2,2 2,4 2,6 2,8 3 3,2 3,4
Silane addition:1,1 %
Lap Shear [N/mm²] on Polycarbonate
VPS SIVO 260 shows excellent adhesion on PC !
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VPS SIVO 280: Outstanding adhesion on PMMA
VPS SIVO 280 CF
Standard amino silane AF
0 0,5 1 1,5 2 2,5 3 3,5
Lap Shear [N/mm²] on PMMA Silane addition:1,1 %
VPS SIVO 280 shows excellent adhesion on PMMA !
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offer an advanced performance in adhesives and sealants
• Summary
• Contacts
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Summary
▪ Oligomeric silanes help to reduce the VOC-formation and help to avoid
negative impact on labeling of Adhesives and Sealants
▪ VPS 4721 is an excellent adhesion promoter for PU, EP, Acrylic, Rubber
adhesives and sealants with improved color stability of the final products
▪ Moreover VPS 4721 shows an improved stability in waterbased Adh. & Seal.
▪ VPS SIVO 324-1 is highly recommended as ethanol-releasing adhesion
promoter for SMP and Silicones, offering excellent flexibilities of final films
▪ Dynasylan® 1146 imparts SMP and Silicone Adhesives and Sealants with
excellent overall performance in adhesion, mechanical properties etc.
▪ For an improved adhesion on critical substrates, the special oligomers
Dynasylan® 1146, VPS SIVO 280 and SIVO 260 are highly recommended
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Agenda
• Company profile
• Organofunctional silanes: structure & chemistry
• Special epoxy functional silanes as adhesion promoter in adhesives and sealants
• Dynasylan® Oligomers offer an advanced performance in adhesives and sealants
• Summary
• Contacts
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CONTACTS Dynasylan® & AEROSIL® in Adhesives & Sealants
Reiner Wartusch Juergen Fritz Dr. Thomas Schlosser
Evonik Resource Evonik Resource Evonik Resource
Efficiency GmbH Efficiency GmbH Efficiency GmbH
Marketing Director Manager Applied Technology Director Applied Technology
Industry Segment Resins & Adh. & Sealants Adh. & Sealants
FS-Marketsegment A&S Silanes and Silica Silanes and Silica
Rodenbacher Chaussee 4 Untere Kanalstrasse 3 Untere Kanalstrasse 3
D-63457 Hanau D-79618 Rheinfelden D-79618 Rheinfelden
phone: +49 6181 59-13476
fax: +49 6181 59-713476 phone: +49 7623 91-8592 phone: +49 7623 91-8392
Cell: +49 (0)151 120 28 984 fax: +49 7623 91-8571 fax: +49 7623 91-8571
[email protected] [email protected] [email protected]34
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