High strength, extrudable silicone elastomer compositions

• US 4,162,243 A
• Filed: 05/08/1978
• Issued: 07/24/1979
• Est. Priority Date: 05/08/1978
• Status: Expired due to Term

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Maxson, Myron T., Lee, Chi-Long, Stebleton, Leo F.
• Primary Examiner(s): Jacobs, Lewis T.
• Application Number:
  US05/904,176
• Time in Patent Office: 442 Days
• Field of Search: 260/37 SB
• US Class Current: 524/847
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08K 9/06 with silicon-containing compounds
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

A composition curable to a silicone elastomer is prepared by mixing a triorganosiloxy endblocked polydimethylsiloxane fluid where the triorganosiloxy is dimethylvinylsiloxy or methylphenylvinylsiloxy, a reinforcing silica having a surface treated organosiloxane groups which contain 0.05 to 0.32 percent by weight vinyl, a fluid organohydrogensiloxane, a platinum catalyst and optionally a platinum catalyst inhibitor. The polydimethylsiloxane fluid has a major peak molecular weight of 68,000 to 135,000, a dispersity index greater than 3.8, the lowest molecular weight species between 854 and 3146 and the highest molecular weight species between 174,000 and 370,000. These compositions are readily extrudable under low pressure and cure to high strength elastomers with a high durometer.

Claims

1. A silicone elastomeric composition consisting essentially of a product obtained by mixing

(A) 100 parts by weight of a triorganosiloxy endblocked polydimethylsiloxane fluid in which the triorganosiloxy units are selected from the group consisting of dimethylvinylsiloxy and methylphenylvinylsiloxy, said fluid being a mixture of polymeric species of varying molecular weight where each species is present in an amount sufficient to collectively provide a molecular weight distribution such that there is present at least one polymeric species (1) at a concentration greater than the concentrations of adjacent polymeric species of lower and higher molecular weight where polymeric species (1) is identified as a peak molecular weight as determined by gel permeation chromatographic analysis and there being a peak molecular weight of polymeric species in the range of from 68,000 to 135,000 at a major concentration, in said fluid the molecular weight of the lowest molecular weight polymeric species being in the range of from 854 to 3146 and the molecular weight of the highest molecular weight species being in the range of from 174,000 to 370,000, the mixture of polymeric species having a molecular weight distribution such that a dispersity index has a value greater than 3.8,

(B) from 20 to 60 parts by weight of a reinforcing amorphous silica having a surface area of greater than 100 square meters per gram, the surface of the silica having silicon atoms to which are bonded organosiloxane groups selected from the group consisting of

(a) (CH₃)₃ SiO--,

(b) CH₂ ═

CH(CH₃)₂ SiO{(CH₃)₂ SiO}_x --,

(c) CH₂ ═

CH(CH₃)(C₆ H₅)SiO{(CH₃)₂ SiO}_x --, and ##STR5## in which x is an integer of 0 to 20 and y is an integer of 1 to 5, the organosiloxane groups being present in an amount such that there is from 0.05 to 0.32 percent by weight vinyl based on the weight of the silica and the organosiloxane groups being present in a mole ratio such that there is from 7 to 50 moles of (a) for each mole of (b), (c), (d) or mixtures thereof,

3. The silicone elastomeric composition according to claim 1 in which the triorganosiloxy endblocked polydimethylsiloxane fluid of (A) has a peak molecular weight in the range of 80,000 to 120,000 at a major concentration and a dispersity index in the range of 6 to 12.

4. The silicone elastomeric composition according to claim 1 in which the triorganosiloxy endblocked polydimethylsiloxane fluid of (A) contains two peak molecular weights where the peak molecular weight in the range of from 68,000 to 135,000 being at a major concentration and another peak molecular weight in the range of from 4,000 to 24,100 being at a minor concentration.

5. The silicone elastomeric composition according to claim 1 in which the triorganosiloxy unit of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (b) where x has a value of 0 to 5 inclusive, and the silica is present in an amount of from 35 to 45 parts by weight.

7. The silicone elastomeric composition according to claim 1 in which the triorganosiloxy of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (d) where y has a value of 1 to 5 inclusive, and the silica is present in an amount of from 35 to 45 parts by weight.

9. The silicone elastomeric composition according to claim 3 in which the triorganosiloxy unit of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (b) where x has a value of 0 to 5 inclusive, and the silica is present in an amount of from 35 to 45 parts by weight.

10. The silicone elastomeric composition according to claim 3 in which the triorganosiloxy unit of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (d) where y has a value of 1 to 5 inclusive and the silica is present in an amount of from 35 to 45 parts by weight.

11. The silicone elastomeric composition according to claim 3 in which the peak molecular weight at the major concentration is in the range of 80,000 to 120,000 and the peak molecular weight at the minor concentration is in the range of 7,000 to 15,000.

13. The silicone elastomeric composition according to claim 9 in which the peak molecular weight at the major concentration is in the range of 80,000 to 120,000 and the peak molecular weight at the minor concentration is in the range of 7,000 to 15,000.

14. The silicone elastomeric composition according to claim 1 in which there is also present an amount of a platinum catalyst inhibitor sufficient to extend the shelf life at ambient temperature.

15. The silicone elastomeric composition according to claim 13 in which the platinum catalyst inhibitor is an acetylenic alcohol.

16. The silicone elastomer composition according to claim 14 in which the acetylenic alcohol is 3,5-dimethyl-1-hexyn-3-ol.

17. The silicone elastomeric composition according to claim 7 in which there is also present an amount of a platinum catalyst inhibitor sufficient to extend the shelf life at ambient temperature.

18. The silicone elastomeric composition according to claim 16 in which the platinum catalyst inhibitor is an acetylenic alcohol.

19. The silicone elastomeric composition according to claim 17 in which the acetylenic alcohol is 3,5-dimethyl-1-hexyn-3-ol.

20. The silicone elastomeric composition according to claim 11 in which there is also present a platinum catalyst inhibitor sufficient to extend the shelf life at ambient temperature.

21. The silicone elastomeric composition according to claim 19 in which the platinum catalyst inhibitor is an acetylenic alcohol.

22. The silicone elastomeric composition according to claim 20 in which the acetylenic alcohol is 3,5-dimethyl-1-hexyn-3-ol.

2. (C) an amount of a fluid organohydrogensiloxane sufficient to provide from 1 to 3 inclusive silicon-bonded hydrogen atoms per vinyl radical in (A) and (B) combined, said organohydrogensilxoane having an average of at least three silicon-bonded hydrogen atoms per molecule and consisting essentially of units selected from a group consisting of methylhydrogensiloxane, dimethylsiloxane, dimethylhydrogensiloxy, trimethylsiloxy and SiO₂ units, and

(D) an amount of a platinum catalyst sufficient to provide at least one part by weight platinum per one million parts by weight of (A), said platinum catalyst being soluble in (A), the silicone elastomer composition having a viscosity such that at least 45 grams per minute of the composition can be extruded through a 3.175 millimeter orifice under a pressure of 620 kilopascals.

6. The silicone elastomeric composition according to claim 2 in which the triorganosiloxy of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (b) where x has a value of 0 to 5 inclusive, and the silica is present in an amount of from 35 to 45 parts by weight.

8. The silicone elastomeric composition according to claim 2 in which the triorganosiloxy of (A) is methylphenylvinylsiloxy and the silica of (B) has a surface area of 120 to 600 square meters per gram, the organosiloxane groups are (a) and (d) where y has a value of 1 to 5 inclusive, and the silica is present in an amount of from 35 to 45 parts by weight.

12. The silicone elastomeric composition according to claim 8 in which the peak molecular weight at the major concentration is in the range of 80,000 to 120,000 and the peak molecular weight at the minor concentration is in the range of 7,000 to 15,000.