CREATING TOMORROW`S SOLUTIONS
Silane-Modified Polymers (SMP)
– Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry,
PhD
– Wacker
Corporation
Silane-Modified Polymers
(SMP) – Combining
the Best of Chemical
Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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Disclaimer
The information contained in this presentation is for background purposes only and is subject to
amendment, revision and updating. Certain statements and information contained in this presentation
may relate to future expectations and other forward-looking statements that are based on management's
current views and assumptions and involve known and unknown risks and uncertainties. In addition to
statements which are forward-looking by reason of context, including without limitation, statements
referring to risk limitations, operational profitability, financial strength, performance targets, profitable
growth opportunities, and risk adequate pricing, as well as the words “may, will, should, expects, plans,
intends, anticipates, believes, estimates, predicts, or continue”, “potential, future, or further”, and similar
expressions identify forward-looking statements. By their nature, forward-looking statements involve a
number of risks, uncertainties and assumptions which could cause actual results or events to differ
materially from those expressed or implied by the forward-looking statements. These include, among
other factors, changing business or other market conditions and the prospects for growth anticipated by
the Company's management. These and other factors could adversely affect the outcome and financial
effects of the plans and events described herein. Statements contained in this presentation regarding
past trends or activities should not be taken as a representation that such trends or activities will
continue in the future. The Company does not undertake any obligation to update or revise any
statements contained in this presentation, whether as a result of new information, future events or
otherwise. In particular, you should not place undue reliance on forward-looking statements, which
speak only as of the date of this presentation.
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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What are Silane-Modified Polymer (SMP) Hybrids
SILICONES
POLYURETHANES
UV resistant
high elasticity
paintable
good mechanical properties
SMP HYBRIDS
+
easy processing
broad adhesion profile
ALPHA SMP HYBRIDS
+
fast & reliable curing
tin free formulations
long shelf-life
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
3 of 25
Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
4 of 25
Chemistry of SMP Hybrid Polymers
1. modified silicones (MS)
Traditional “MODIFIED SILICONES”
HO
HO
O
O
n
Allylchloride
OH
OH
O
O
O
Hydrosilation
only
O
n+x
MeO
MeO
C Si
HH33C−Si
eO
M
MeO
O
O
O
O
n+x
O
O
OMe
OMe
Si−CH
CH3 3
Si
e
OM
OMe
γ
• low viscosities
• good stability of the polymers
• broad adhesion profile
• low functionality
• very low reactivity, tackiness
• formulations very sensitive to moisture of
fillers
• shelf-life limited
• limited mechanical properties
• tin catalyst needed
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
5 of 25
Chemistry of SMP Hybrid Polymers
2. silane-terminated polyurethanes (SPUR/STP-U) (method 1)
Traditional SILANE-TERMINATED POLYURETHANES (SPUR)
Polymer
H
H
N=C=O +
' N
R
R´
OR
Si OR
OR
2° Aminoalkyl alkoxysilanes
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
O
O
(catalyst)
N
N
H
H
N
N
'
R
R´
OR
Si OR
OR
urea group
urea group
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Chemistry of SMP Hybrid Polymers
2. silane-terminated polyurethanes (SPUR/STP-U) (method 2)
Traditional SILANE-TERMINATED POLYURETHANES (SPUR)
O
Polymer
OH
+ O C N
O=C=N
Si
OR
OR
OR
O
(catalyst)
Isocyanatoalkyl alkoxysilanes
only
•
•
•
•
N
N
H
H
Si
OR
OR
OR
roup
ure
thane ggroup
urethane
γ
good reactivity
good crosslinking for improved elasticity
broad adhesion profile
higher strength
• very high viscosity (most polymers need
plasticizers)
• sensitive to moisture of fillers
• critical towards crosslinking upon storage
(faster skinning)
• limited possibilities in tin-free catalysis
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
7 of 25
Low viscosity of silane-terminated polyethers
low viscosity leads
to:
500
450
Viscosity (Pa s)
 easier handling in
production
Silane-terminated polyurethane:SPUR
STP-U
400
350
 better workability in
formulations
300
Silane-terminated polyether: STP-E
250
150
 plasticizer free
formulations
100
 high filler loading
200
 less scrapped
material
50
0
-10
0
10
20
30
40
50
60
70
80
 easier to gun
Temperature (°C)
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
8 of 25
Chemistry of Hybrid Polymers
3. Silane-Terminated Polyethers (STP-E)
SILANE-TERMINATED POLYETHERS (STP-E)
Polymer
+
OH
OH
O C N
O=C=N
O
O
OR
Si
(O)R
n OR
(catalyst)
Isocyanatoalkyl alkoxysilanes
α
n=1
γ
O
O
N
N
H
H
OR
Si
(O)R
n OR
urethane group
urethane
group
n=3
Benefits α & γ:
Additional benefits α:
•
•
•
•
•
•
•
•
•
•
100 % functionality
Tack-free curing
Higher strength
Low polymer content yet high performance
Cost-efficient compounding
Long shelf-life
Very high reactivity & fast strength-build-up
Improved mechanical properties
Crystal clear formulations
Tin-free curing
Additional benefits γ:
•
•
Trimethoxy reaction  faster than MS
Good recovery  sealants
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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Rate of skin forming time of different endcapped SMP polymers
α-STP-E
OMe
H
N
O
2h
8h
C
Si
O
OMe
CH3
H
N
O
C
Si
O
OMe
O
OMe
C
Si
CH3
O
OMe
OMe
30 min
5 min
H
N
OMe
H
N
O
1 min
OMe
C
Si
O
OMe
OMe
γ-STP-E
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
10 of 25
Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
11 of 25
The GENIOSIL® “toolbox” of polymers provides many options
GENIOSIL® XT
 Polymer range for
very strong and
elastic adhesives
and coatings
GENIOSIL® STP-E
 Standard polymer
range for elastic
adhesives &
sealants
GENIOSIL® XB
 Polymer range for
strong and hard
adhesives and
coatings
GENIOSIL® WP
 Polymer range for
waterproofing
liquid membranes
GENIOSIL® XM
 Polymer range for adhesion
and elongation
 Most important of all – all polymers can be blended to achieve state-of-the-art products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
12 of 25
Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
13 of 25
Compounding with GENIOSIL® SMP’s
Typical One-Component Formulation and Compounding Steps
 10 - 40%
 10 - 20%
 1 - 2%
silane-modified polymer
plasticizer
water scavenger
pre-mix liquids
 40 - 60%
 2 - 4%
 1%
fillers, typically calcium carbonates
pyrogenic silica
stabilizer package
disperse solids
homogenously
 0.1 - 1%
catalyst/adhesion = Aminosilane
activate and evacuate bubbles
screening recipe
scale-up in lab
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
transfer to production
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Calcium carbonate selection impacts various properties
Hardness
Strength
Body
Elasticity
Calcium
Carbonate Type
Shear Strength
Rheology/Body
Elasticity
GC
High
Low
Low
GCC
Low
Low
High
PCC
High
High
High
GC = Ground Calcium Carbonate | GCC = Ground Coated Calcium Carbonate | PCC = Precipitated Coated Calcium Carbonate
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
15 of 25
Influence of formulation by plasticizers
Shore
hardness
Viscosity
Adhesion
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
Through
cure
Skin
formation
time
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Pyrogenic Silica impact on mechanics
Rheology
Tensile
Strength
HDK
Property
BET
Rheology/Body
QTY
Tensile Strength
BET
Elasticity
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
17 of 25
Stabilizer impact on product stability
UV-Stability
Temperature
Stability
Shelf-Life
Durability
Stabilizer
Influence
Antioxidant
Temperature
UV-Absorber
Radiation
HALS*
Temperature & Radiation
* Hindered Amine Light Stabilizers
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
18 of 25
α-Effect: fast without special catalysts
Polymers cured with different catalytic systems
Skin-formation-time (23°C/50 % r.h.)
250
>360
>360
Alpha
skin-formation-time [min]
Gamma
200
150
100
20
• no tin-catalyst required
15
• easy formulation
10
• improved storage stability
5
0
50
Benefits α-effect:
1.0% GF 96 0.25 %
DBTL
• no degradation via
secondary reactions with tin
0
2.0% GF 96
1.0% GF 96
1.0% GF 96 1.0% GF 96
0.05 % DBTL 0.25 % DBTL
GENIOSIL® GF 96 – Aminopropyltrimethoxysilane
DBTL – Dibutyltin-dilaurate
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
19 of 25
Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
20 of 25
Formulating approach with GENIOSIL® SMP
aaaa
• Step 1: Charge
mixing vessel
Compounding Benefits at a Glance
• No heat activation in vessel
• No pre-drying of fillers
• No moisture monitoring during
mixing
• Step 2: Mixing
Total time is 1-2 hours
before filling step
• No specific compounding
parameters
• No special raw materials
• No hazardous ingredients
 Fast and Easy Production Process
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
21 of 25
Agenda
 Introduction
 Chemistry
 GENIOSIL® SMP product line
 Formulating
 Manufacturing
 Performance in end-user products
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
22 of 25
SMP are capable of being formulated with performance from low
modulus sealants to high performance adhesives
Bonding
CA = Cyanoacrylate
PU = Polyurethane
1K / 2K = one / two component
SMP = Silane-Modified Polymers
Shear strength (psi)
Epoxy
CA
1450
GENIOSIL®
XB 502
Acrylic
2k-PU
GENIOSIL® XT
Sealing
1k-PU
PU, SMP
Silicone, PU, SMP
100
200
300
Elongation (%)
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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GENIOSIL® SMP
The Bridge Between Silicones and Polyurethanes
Wood Flooring Adhesives
Joint Sealer
Façade Sealer
Bus, Truck, Rail
Assembly Adhesives
High-end Adhesives
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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Thank you for your attention!
Silane-Modified Polymers (SMP) – Combining the Best of Silicone & Organic Polymers
International Silicone Conference – May 17, 2016
Michael Austerberry, PhD – Wacker Chemical Corporation
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