Silane Terminated

Polyurethanes

Edition: September 2009

Content
Comparison PUR and STP chemistry

Crosslinking mechanism

Design of PUR polymers

Design of STP polymers

Properties of STPs
Synthetic routes to STPs

Aminosilane route

NCO-silane Route

Comparison aminosilane route vs. NCO-silane route
Comparison STPs vs. MS-Polymers

Chemical Differentiation

Advantages of STPs
Product range and formulation examples

Product portfolio STPs

Formulation portfolio and application range

Formulation process

Dr. Beate Baumbach • 2009-09-07 • Seite 2

Comparison of PUR and STP Chemistry
Crosslinking Mechanism

PUR
PUR STP
STP

OCH3
NCO + H2O Si OCH3
OCH3
- CO2
CH3O
CH3O Si
NH2 CH3O
+
+ H2O
OCN - HOCH3

OCH3 OCH3
O Si O Si
=

C CH3O
N N OCH3
H H

Dr. Beate Baumbach • 2009-09-07 • Seite 3

 Comparison of PUR and STP Chemistry
Design of PUR Polymers

Polyurethane Polymers (moisture curing)

HO 4k-polyether OH HO 6k-polyether OH

OH

OCN NCO

OCN NCO

R-NCO + OCN-R
OCN NCO
- CO2 + H2O

=
R-N N-R
H H
NCO

Dr. Beate Baumbach • 2009-09-07 • Seite 4

 Comparison of PUR and STP Chemistry
Design of PUR Polymers

Polyurethane Polymers (moisture curing)

HO 4k-polyether
OH HO OH 6k-polyether
••PUR
PUR prepolymer approachallows
prepolymer approach allowsto
touse
uselow
lowviscosity
viscositypolymers
polymers
and
andto
toadjust
adjustfinal
finalcrosslinking
OH
crosslinking density
densityby
bythe
theratio
ratioof
ofbi-
bi-and
and
trifunctional polyethers
trifunctionalOCN NCO
polyethers

••Soft
Softelastic
elasticPUR
PURprepolymers
prepolymers mainly
mainlybuild
buildup
uplinear
linearmolecular
molecular
OCN NCO

OCN
weight
weight!! NCO
R-NCO + OCN-R

- CO2 + H2O

=
R-N N-R
H H
NCO

Dr. Beate Baumbach • 2009-09-07 • Seite 5

 Comparison of PUR and STP Chemistry
Design of STP Polymers

Silane-Terminated Polyurethane Polymers

HO Acclaim Polyether OH OCN NCO

OMe
H2N Si OMe

OMe

MeO OMe

MeO Si Si OMe

MeO OMe

OCH3 CH3O OCH3 CH3O

+ H2O
Si OCH3 + CH3O Si Si O Si
OCH3 CH3O - HOCH3 OCH3 CH3O
= Si-O-Si Cluster

Dr. Beate Baumbach • 2009-09-07 • Seite 6

 Comparison of PUR and STP Chemistry
Design of STP Polymers

Silane-Terminated Polyurethane Polymers

HO Acclaim Polyether OH OCN NCO

••STPs
STPsare
aremultifunctional,
multifunctional,they
theycrosslink
crosslinkby
bycuring
curingand
andcannot
cannot
OMe
build
buildup
uplinear
linear molecular
H N molecular
Si OMe
weight
weight
2

OMe
••Polymer
MeOPolymerchain
chainlength
lengthdetermines
determines
OMe the
thedistance
distancebetween
betweentwo
two
MeO Si Si OMe
crosslinking points
MeOcrosslinking points OMe

••Therefore
Thereforeproducts
productsfor
for„soft“
„soft“applications
applicationshave
haveaahigh
highviscosity
viscosity
OCH3 CH3O OCH3 CH3O
+ H2O
Si OCH3 + CH3O Si Si O Si
OCH3 CH3O - HOCH3 OCH3 CH3O
= Si-O-Si Cluster

Dr. Beate Baumbach • 2009-09-07 • Seite 7

Comparison of PUR and STP Chemistry
Properties of STPs

STPs combine positive properties of PUR …

 Tailored systems by use of PU building blocks
 Good cohesion
 Paintability

… and Silicones:
 Bubble free curing (even in thick layers)
 Good adhesion
 Free of isocyanates

Dr. Beate Baumbach • 2009-09-07 • Seite 8

 Synthetic Routes to STPs
Aminosilane Route

P o ly e th e r
HO OH • Broad molecular
weight distribution
OCN R NCO
• Strong hydrogen
bridges
OCN P o ly u r e th a n e NCO

OMe
HRN Si OMe
OMe

O O
MeO OMe
MeO Si N N P o ly u re th a n e N N Si OMe
H H
MeO R R OMe

Dr. Beate Baumbach • 2009-09-07 • Seite 9

 Synthetic Routes to STPs
NCO-silane Route

HO Polyether OH • Narrow molecular

weight distribution
OMe
• Weak hydrogen
OCN Si OMe
OMe
bridges

O O
MeO OMe
MeO Si N O Polyether O N Si OMe
MeO H H OMe

Dr. Beate Baumbach • 2009-09-07 • Seite 10

Synthetic Routes to STPs
Comparison Aminosilane Route vs. NCO-silane Route

The two routes to STPs give different product properties:

a) Aminosilane route:
 Higher viscosity (dispersity / H-bridges)
 Higher modulus (H-bridges)

b) NCO-silane route:
 Lower viscosity
 Lower modulus

Dr. Beate Baumbach • 2009-09-07 • Seite 11

 Comparison STPs vs. MS-Polymers
Chemical Differentiation

Silane terminated Polyurethanes

R R
- Polyurethane backbone
R Si Polyurethane Backbone Si R
- 3 reactive goups at each end
R R

Silane terminated Polyols (MS-Polymer)

CH 3 CH 3
- Polyether backbone
R Si Polyether Backbone Si R
- 2 reactive groups at each end
R R
R = OCH3

Dr. Beate Baumbach • 2009-09-07 • Seite 12

Comparison STPs vs. MS-Polymers
Advantages of STPs

• Polyurethane backbone vs. polyether backbone

 Better mechanical properties
Higher elastic recovery / better creep resistance
• Trifunctional silanes vs. difunctional silanes
 Faster cure
Lower catalyst level needed
Use of amine instead of tin catalyst possible !!!
• Polyurethane backbone + silicone endcapping
 Improved adhesion
• Big variety of building blocks and synthetic routs
 More freedom in polymer design & range of applications
Taylor-made products (molecular weight, functionality, type of PIC)
Low and medium modulus range, sealants & adhesives

Dr. Beate Baumbach • 2009-09-07 • Seite 13

Product Range and Formulation Examples
Product Portfolio STPs

Molecular
Viscosity at 23 °C
weight
[mPas]
Product Delivery form [kg/mol] Remarks

STP with high viscosity, for „hard“ formulations with high

Desmoseal S XP 2458 90 % in Mesamoll 30,000 - 40,000 approx. 20 modulus and medium elongation

STP with high viscosity, for „soft" formulations with low

Desmoseal S XP 2636 100% 32,000 - 42,000 approx. 24 modulus and high elongation

STP with low viscosity, for „hard" formulations with high

Desmoseal S XP 2749 100% approx. 5,000 approx. 13 modulus and low elongation

Desmoseal S XP 2636
Desmoseal S XP 2458
Desmoseal S XP 2749

Dr. Beate Baumbach • 2009-09-07 • Seite 14

Product Range and Formulation Examples
Formulation Portfolio and Application Range

Technical Sealant Structural Adhesive

Construction Sealant Elastic Adhesive

< 30 40 50 60 70
Shore A

Dr. Beate Baumbach • 2009-09-07 • Seite 15

Product Range and Formulation Examples
Formulation Portfolio and Application Range

Desmoseal S XP 2636 Desmoseal S XP 2458 Desmoseal S XP 2749

→ Shore A 20 - A 70 → Shore A 40 - A 80 → Shore A 65 - 80
- 1K SEA - 1K SEA Sprayable - 1K ADH
- 1K SEA Sprayable - 1K ADH - 1K ADH Flooring
- 1K ADH - 1K ADH Flooring
- 1K ADH Flooring - 1K ADH Transparent
- 1K ADH Transparent - 2K ADH

Technical Sealant Structural Adhesive

Construction Sealant Elastic Adhesive

< 30 40 50 60 70
Shore A

Dr. Beate Baumbach • 2009-09-07 • Seite 16

Product Range and Formulation Examples
Formulation Portfolio and Application Range

Property range of sealants and elastic adhesives:

 Tensile strength 2.0 – 6.5 MPa
 Elongation at break 100 – 1,000 %
 Shore A 20 - 80
 Modulus@100% 0.3 – 3.0 MPa

STPs provide superior properties compared to

difunctional hybrid polymers

Dr. Beate Baumbach • 2009-09-07 • Seite 17

Product Range and Formulation Examples
Formulation Process

Polymer Formulation Application

Parquet Adhesive

Sealant

Seam Sealer

Elastic Adhesive

Dr. Beate Baumbach • 2009-09-07 • Seite 18

Product Range and Formulation Examples
General Remarks Formulation Process

For the production of all formulations a double-walled vacuum dispenser with

side scraper is recommended.

Process 1: Physical pre-drying of fillers (preferred method)

• Use physically pre-dried fillers (e.g. 16 h at 100 °C)
• Add low amount of water scavanger to obtain storage stability
→ Low VOC content

Process 2: Chemical drying of the formulation

• Use of fillers which are not pre-dried
• Add higher amount of water scavanger to obtain storage stability
→ High emissions of methanol possible

Dr. Beate Baumbach • 2009-09-07 • Seite 19

Product Range and Formulation Examples
Formulation Process for 1 kg Batches

Step 1:
The vessel is filled with binder, plasticizer, additives (e.g. antioxidants),
pigments and thixotropic agent . The filler is added under stirring in 2 - 3
portions. Catalyst and water scavenger are added together with the last one.
Then the premix is dispersed under stirring and cooling (temperature: < 60 °C)
and static vacuum (< 200 mbar) for:
- 10 minutes at 3,000 rpm and
- 10 minutes at 1,000 rpm
Finally the water content of the premix should be < 200 ppm.

Dr. Beate Baumbach • 2009-09-07 • Seite 20

Product Range and Formulation Examples
Formulation Process for 1 kg Batches

Step 2:
The adhesion promotors (e.g. amino silanes) are added to the premix under
stirring and cooling (temperature: < 60 °C) for:
-10 minutes under static vacuum (< 200 mbar) at 1,000 rpm and
- 5 minutes under dynamic vacuum at 1,000 rpm
The final mixture is filled into plastic cartridges or inside coated aluminium
cartridges.

Dr. Beate Baumbach • 2009-09-07 • Seite 21

Product Range and Formulation Examples
General Remarks Formulation Process

Important points:

• A temperature of 70°C should not be exceeded, othe rwise a negative

impact on the final properties can be noticed

• The amount of water is crucial for the storage stability of the

formulation

• The water scavanger (e.g. vinyltrimethoxysilane) has a low boiling

point and might evaporate during the process

→ Use of vacuum needs to be controlled

Dr. Beate Baumbach • 2009-09-07 • Seite 22

Product Range and Formulation Examples
Summary Formulation Process

Mechanical properties: Viscosity / Rheology:

• Polymer • Thixotropic agent
• Plasticiser • Plasticiser
• Filler • Filler
• Aminosilanes • Solvents

Adhesion properties: Storage stability:

• Aminosilanes • Moisture content
• Plasticiser • Amount of water scavanger
• Amount of catalyst • Aminosilanes
• Light stabilisers

Dr. Beate Baumbach • 2009-07-07 • Seite 23

Thank you for your attention

Dr. Beate Baumbach • 2009-09-07 • Seite 24