Method of producing treated silica filler for silicone rubber

• US 4,985,477 A
• Filed: 08/30/1989
• Issued: 01/15/1991
• Est. Priority Date: 05/13/1988
• Status: Expired due to Term

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Cottrell, Kenneth R., Collins, Warde T., Saam, John C.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): Dean, Jr., Ralph H.
• Application Number:
  US07/401,607
• Time in Patent Office: 503 Days
• Field of Search: 527/212, 527/217, 106/490, 428/405
• US Class Current: 523/212
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/80 Compositional purity
• CPC Class Codes: C08K 9/06 with silicon-containing compounds
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09C 1/3081 Treatment with organo-silicon compounds
• CPC Class Codes: Y10T 428/2995 Silane, siloxane or silicone coating

Abstract

An improved method of producing treated silica filler for use with silicone rubber operates at ambient temperature in a short period of time. The method consists essentially of mixing reinforcing silica with a volatile treating agent of the formula R_x Si(OR'"'"')₄ -_x, wherein R is a substituted or unsubstituted, saturated or unsaturated, alkyl or aryl radical having from 1 to 6 carbon atoms, R'"'"' is an alkyl radical having from 1 to 3 carbon atoms, x is 1 or 2, and R and R'"'"' are chosed so that the vapor pressure of the alkoxysilane exceeds 10 Pa (0.0001) atmosphere) at treatment temperature, in combination with a volatile catalyst selected from the group consisting of acid A, base B, and mixtures thereof; wherein acid A is a volatile acid or acid progenitor, and base B is a silylamine or silazane, acid A and base B being chosen so that the vapor pressure of either acid A or base B exceeds 500 Pa (0.005 atmosphere) at treatment temperature, for a period of time sufficient to allow the desired amount of treating agent to be absorbed onto the surface of the particulate filler.

Claims

1. A method of rapidly treating the surface of reinforcing silica filler consisting essentially of mixing, at a temperature of from about -10°

to 130°

C.,

(A) 100 parts by weight of reinforcing silica filler, having a surface area of greater than 50 m² /g, and having from 0.5 to 6 parts by weight of absorbed moisture,

(B) from 3 to 30 parts by weight of volatile treating agent of the formula R_x Si(OR'"'"')_4-x, wherein R is a alkyl, alkenyl, or aryl radical having from 1 to 6 carbon atoms which may be substituted with halogen atoms, R'"'"' is an alkyl radical having from 1 to 3 carbon atoms, x is 1 or 2, and R and R'"'"' are chosen so that the vapor pressure of the alkoxysilane exceeds 10 Pa at treatment temperature,

(C) from 0.001 to 5.0 parts by weight of volatile catalyst selected from the group consisting of base B, and mixtures of acid A and base B, wherein acid A is a volatile acid or acid progenitor, and base B is a silylamine or silazane, acid A and base B being chosen so that the vapor pressure of either acid A or base B exceeds 500 Pa at treatment temperature, for a period of time sufficient to allow the desired amount of treating agent to be adsorbed onto the surface of the particulate filler,

to yield a filler which requires a minimum of energy to disperse rapidly into polydiorganosiloxane and which gives improved properties to cured silicone elastomers.

2. The method of claim 1 in which the mixing is in the form of a stirred or fluidized bed in a container purged with an inert gas, the treatment temperature is from about 10°

to 30°

C., and the treatment time is from 3 to 10 minutes.

3. The method of claim 2 in which R and R'"'"' are methyl radical.

4. The method of claim 1 in which base B is selected from the group consisting of (R'"'"''"'"'₃ Si)₂ NR'"'"''"'"', (R'"'"''"'"'₃ Si)₂ NH, R'"'"''"'"'₃ SiNR'"'"''"'"'₂, and R'"'"''"'"'₃ SiNHR'"'"''"'"', where R'"'"''"'"' is an alkyl radical having from 1 to 3 carbon atoms.

5. The method of claim 1 in which the volatile catalyst is admixed with the reinforcing silica filler before the mixing of the volatile treating agent.

6. The method of claim 3 in which the treating agent is Me₂ Si(OMe)₂, where Me represents methyl radical.

7. The method of claim 6 in which the catalyst is (Me₃ Si)₂ NH.

8. The method of claim 3 in which the treating agent is MeSi(OMe)₃.

9. The method of claim 8 in which the catalyst is (Me₃ Si)₂ NH.

10. The method of claim 3 in which the catalyst is a mixture of MeSiCl₃ and (Me₃ Si)₂ NH.

11. The method of claim 6 in which the catalyst is a mixture of MeSiCl₃ and (Me₃ Si)₂ NH.

12. The method of claim 8 in which the catalyst is a mixture of MeSiCl₃ and (Me₃ Si)₂ NH.

13. The method of claim 6 in which the catalyst is a mixture of Me₂ SiCl₂ and (Me₃ Si)₂ NH.

14. The method of claim 8 in which the catalyst is a mixture of Me₂ SiCl₂ and (Me₃ Si)₂ NH.

15. The method of claim 10 in which the treating agent is a mixture of MeSi(OMe)₃ and Me₂ Si(OMe)₂.

16. The method of claim 11 in which the treating agent is a mixture of MeSi(OMe)₃ and Me₂ Si(OMe)₂.

17. The method of claim 12 in which the treating agent is a mixture of MeSi(OMe)₃ and Me₂ Si(OMe)₂.

18. The treated silica produced by the method of claim 1.

19. The treated silica produced by the method of claim 10.

20. The treated silica produced by the method of claim 11.

21. The treated silica produced by the method of claim 12.

22. The treated silica produced by the method of claim 13.

23. The treated silica produced by the method of claim 14.

24. The treated silica produced by the method of claim 15.

25. Silicone elastomer containing treated silica filler produced by the method of claim 1.

26. A silicone elastomer containing the treated silica of claim 19.

27. A silicone elastomer containing the treated silica of claim 20.

28. A silicone elastomer containing the treated silica of claim 21.

29. A silicone elastomer containing the treated silica of claim 22.

30. A silicone elastomer containing the treated silica of claim 23.

31. A silicone elastomer containing the treated silica of claim 24.