Process for the production of silicone resins

• US 4,387,196 A
• Filed: 02/18/1982
• Issued: 06/07/1983
• Est. Priority Date: 07/27/1977
• Status: Expired due to Fees

• Current Assignee: Raychem Limited (TE Connectivity Limited)
• Original Assignee: Raychem Limited (TE Connectivity Limited)
• Inventors: Pithouse, Kenneth B., Bonnet, Jean-Claude
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/350,067
• Time in Patent Office: 474 Days
• Field of Search: 525/477, 525/478, 528/10, 528/12, 528/14, 528/21, 528/34, 528/43
• US Class Current: 525/477
• CPC Class Codes: C08G 77/06 Preparatory processes C08G77/045 takes precedence
• CPC Class Codes: C08G 77/10 Equilibration processes
• CPC Class Codes: C08K 5/10 Esters; Ether-esters
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08K 5/34 Heterocyclic compounds having nitrogen in the ring
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

The invention relates to a novel process for the production of a thermoplastic, high softening point polysiloxane resin which comprises reacting a solvent-soluble partially condensed organosiloxane with a silane capping agent. The resins so produced are useful as electrical insulator material and also as hold out agents for heat recoverable articles.

Claims

1. A process for the production of a thermoplastic, high softening point polysiloxane resin which comprises the steps of:

(a) reacting a solvent-soluble partially condensed organosiloxane having the unit formula;

space="preserve" listing-type="equation">(RSiO.sub.1.5).sub.a (R'"'"'R"SiO).sub.b

wherein R and R'"'"' are each independently hydrogen or an organic group, at least 85% of the R groups in the RSiO₁.5 units being organic groups, R" is an organic group,

a is from 0.6 to 1,

b is 0 to 0.4, and a+b=1,

and wherein the organosiloxane comprises Si-OH groups capable of further condensation, the percentage by weight, based on the weight of the resin, of said hydroxyl groups being from 1 to 10, with a silane capping agent so as to cap some of the Si--OH groups, and

(b) equilibrating the product of step (a) to produce a product having a softening point in excess of 50°

C.

2. The process of claim 1, in which the step of equilibrating comprises heating the product of step (a) in the presence of an equilibration catalyst.

3. The process of claim 1, in which R is a substituted or unsubstituted hydrocarbon group.

4. The process of claim 3, in which R is a methyl group or a phenyl group.

5. The process of claim 1 in which the groups R'"'"',R" are hydrocarbon groups or substituted hydrocarbon groups.

6. The process of claim 5, in which the groups R'"'"',R" are each independently methyl or phenyl groups.

7. The process of claim 1, in which the organic groups of the partially condensed organosiloxane are methyl groups.

8. The process of claim 6, in which up to 80% of the groups R are phenyl groups.

9. The process of claim 1, in which the partially condensed organosiloxane is a monoorganosiloxane.

10. The process of claim 9, in which the partially condensed organosiloxane is a monomethylpolysiloxane.

11. The process of claim 9, in which the partially condensed organosiloxane is a monophenylpolysiloxane.

12. The process of claim 9, in which the partially condensed organosiloxane is a monomethylmonophenylpolysiloxane in which the ratio of methyl to phenyl groups on a molar basis is from 1:

4 to 4;

1.

13. The process of claim 1, in which the partially condensed organosiloxane is one that has been prepared by hydrolysis of a hydrolysable organosilane or mixture of silanes.

14. The process of claim 13, in which the hydrolysable organosilane is a monoorganosilane.

15. The process of claim 14, in which the monoorganosilane has the formula RSiCl₃, RSi(OAlk)₃ or RSi (OCOAlk)₃ where Alk represents an alkyl group and R is as previously defined.

16. The process of claim 13, in which the hydrolysis is effected by adding a solution of the organosilane in an organic solvent to water.

17. The process of claim 16, in which a co-solvent for both the water and the organic solvent is added to maintain the hydrolysis mixture substantially homogeneous.

18. The process of claim 17, in which the co-solvent is mixed with the water and the organic solvent solution of the silane added thereto.

19. The process of claim 18, in which excess organic solvent is added to the mixture of water and co-solvent.

20. The process of claim 1, in which the silane capping agent is a monofunctional organosilane.

21. The process of claim 20, in which the silane capping agent is an organosilane of formula R₁ R₂ R₃ SiCl, R₁ R₂ R₃ Si(OAlk) or R₁ R₂ R₃ Si (OCOAlk), where R₁, R₂ and R₃ are each independently hydrogen or organic groups, and Alk represents an alkyl group.

22. The process of claim 21, in which R₁,R₂ and R₃ are each independently methyl or phenyl groups.

23. The process of claim 1, in which the step of reacting is carried out at a temperature of from 20°

to 150°

C.

24. The process of claim 2, in which the step of equilibrating comprises heating the product of step (a) at a temperature of from 60°

to 150°

C. for a period of from 5 to 120 minutes.

25. The process of claim 24, in which the product of step (a) is heated in a solution in an organic solvent for from 30 to 60 minutes.

26. The process of claim 2, in which the catalyst is an acid, an alkali, a metal soap, or kieselguhr.

27. The process of claim 1, including the additional step of subsequently cross-linking the resulting polysiloxane resin.

28. The process of claim 27, in which the resulting polysiloxane resin has substituents comprising olefinically unsaturated groups capable of undergoing cross-linking reactions.

29. The process of claim 28, in which the olefinically unsaturated groups are vinyl or allyl groups.

30. The process of claim 28, in which the olefinically unsaturated groups are present in an amount of up to 2% on a molar basis.

31. A thermoplastic, high softening point, polysiloxane resin produced by a process according to claim 1.

32. An article which is heat-recoverable, which can be rendered heat-recoverable or which is heat-recovered, made from the polysiloxane resin of claim 1, in non-crosslinked or crosslinked form.

33. Electrical insulation made from the polysiloxane resin of claim 1, in non-crosslinked or crosslinked form.