Formulating with Vinyl Gums for Addition Cure HCR

Charles Olsen Jr.*1, Hans Haas1 and Claudio Diaz2,

AB Specialty Silicones, Waukegan, IL, (2) Gumena LLC, Elkhart, IN

AB Specialty Silicones │ Charles Olsen Jr │October 12, 2016

Outline

• Formulating with Vinyl Gums for Addition Cure HCR

• Differences between Peroxide cure and Addition cure
• Advantages of Addition Cure system in HCR
• Stoichiometric Chemistry
 Pictures
• Calculation
• Rational elastomer design for formulating
• Example of XL effect Graphs
• Precautions

• Summary

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Addition cure compared to Peroxide cure

Addition cure Peroxide cure

• True catalyst • Not truly a catalyst,
 Heat directly drives the  Heat decomposition of
reaction rate peroxide drives one
 Pt complex participates in crosslink
many crosslink reactions  Activator for vinyl
 Excess Pt does not speed crosslinking
cure  Properties are modified by
• No byproducts or gas changing peroxide level
generation • Always generates by-products
• Post cure usually not needed • Potential for bubbles
• Fewer confounding factors in • Formulation space is
formulating constrained by interactions

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Choices affecting properties

• Addition cure • Peroxide cure

 XL selection  Choice of vinyl polymer blend
 Choice of vinyl polymer blend  Reinforcing fillers
 Type of reinforcing filler

Addition cure offers formulator another degree of freedom

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Rational formulating

• Combination of vinyl polymer structure and hydride structure

provides versatility in formulating
 Three types of crosslinker
• Terminal hydride
• Pendant hydride
• Combination of both
 Wide range of SiH concentration along the backbone
 Backbone length from short to long
• Additional sources of vinyl can be easily incorporated
 Methyl Vinyl resins
 Organic vinyl contributors

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Basic Addition Reaction

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Vinyl Terminated Gum

Si Si Si Si Pt
Si Si Si + O
O O
O O H
D N M

Si Si Si Si
O O O

N M

Si
• Most formulations use a blend of
terminal and pendant
ADDITIONvinyl
CUREgum O
Si
O
Si

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Pendant Hydride Polydimethylsiloxanes

Si Si Si Si
O O O
H
D M

• Dimethylmethylhydrogenpolysiloxane copolymer with trimethylsiloxy terminals

(M-stopped)
• Pendant functionality - hydride functionality along the backbone of the polymer
• Very wide range of functionality: 5 to 23 hydrides per molecule
 Higher and lower available upon request
• Wide range of equivalent weights: 132 to >1,000 equivalent wt

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Example calculation

• Formulating spreadsheet makes calculations simple

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Effect of SiH excess
45
Shore A
40
35
30
E%
25
20
15
Tensile N/mm
10
5
0
300 200 100 0
• Excess vinyl%
gum remains
Excess SiH unreacted
• 60% excess is lower limit in this example
• OH including water can consume SiH

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MW and Functionality independently selected

• Range of crosslinkers evaluated

Viscosity and MW strongly correlated

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Higher functionality XL

• Same MW, Functionality effect

40 Shore A 915

35 910
30 Tear Strength
[N/mm] 905
25
900
20
895
15 Elongation
[%]

10 890

5 Tensile Strength 885

[N/mm²]
1XL 11, 10 XL 13, 2
23

Significant increase in tear

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Larger MW XL

• Same Functionality, MW effect

45 855
40 850
35 Shore A
845
30
25 840
Tear Strength [N/mm]
20 835
15
830
Elongation [%]
10
5 825
Tensile Strength [N/mm²]
0 820
XL 10, 21 XL 12,19

Dilution effect may contribute to property reduction

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Extending filler comparison

None 30 phr 30 phr

Minusil ATH
Shore A 39 37 35

Elongation [%] 911 754 699

Tensile Strength [N/mm²] 6.6 4.0 3.5

Tear Strength [N/mm] 28.9 25.8 23.3

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Reinforcing filler comparison

Tensile
Strength Tear Strength
Reinforcing filler Shore A Elongation [%] [N/mm²] [N/mm]

Andifil AS 200 39 911 6.6 28.9

Aerosil R972 32 1126 5.0 23.2

Sipernat 120 26 462 1.2 7.2

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Other considerations

• Avoid Catalyst poison

 Amines
 Peroxides
 Sulfur
• Shelf life
 Filler treatment crepe hardening
 Addition of inhibitors to extend mixed system
• Control of cure profile
 Wide choice of inhibitors to modify cure profile

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Summary

• Addition cure HCR has the potential for;

 Faster cure
 “Cleaner” parts
 More flexible formulating
 Differentiation from competitors
 Backwards integration into
compounding
• Formulating assistance is available

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• Picture credit
How I met your elastomers: from network topology to mechanical behaviours of conventional silicone materials
A. M. Stricher,ab R. G. Rinaldi,b C. Barrès,a F. Ganachaud*a and L. Chazeau*b
Show Affiliations
RSC Adv., 2015,5, 53713-53725

DOI: 10.1039/C5RA06965C
Received 17 Apr 2015, Accepted 27 May 2015

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