Claims
- 1. A process for the production of hydrogen containing siloxanes of the formula:
- M'D.sub.x.sup.H D.sub.y M'
- where
- M'=R.sub.3-i.sup.1 H.sub.i SiO.sub.1/2 with R.sup.1 being independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals and the subscript i ranges from 0 to 3;
- D.sup.H =R.sup.2 HSiO.sub.2/2 with R.sup.2 being independently selected from the group consisting of hydrogen and one to forty carbon atom monovalent hydrocarbon radicals; and
- D=R.sub.2.sup.3 SiO.sub.2/2 where each R.sup.3 is independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals; and the subscript x ranges from 1 to 20 and the subscript y ranges from 0 to 20; comprising:
- (a) mixing a hydrogen containing siloxane selected from the group consisting of:
- i) D.sub.z.sup.H where D.sup.H is as previously defined and z varies from 3 to 8; and
- ii) M'D.sub.xx.sup.H D.sub.yy M' where M', D.sup.H, and D are as previously defined and xx is greater than 20 and yy is either 0 or greater than 20; with
- (b) an M' rich silicone compound comprising M' where M' is as previously defined, wherein when said M' rich compound additionally comprises D, T, or Q groups, D is as previously defined,
- T=R.sup.4 SiO.sub.3/2 with R.sup.4 being independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals, and Q=SiO.sub.4/2 where the molar ratio of silicon atoms in the M' groups in said M' rich silicone compound to the sum of the silicone atoms in the M', D, T, and Q groups in said M' rich silicone compound is 0.04 or greater; in the presence of a catalyst selected from the group consisting of acid washed clays, zeolites, ion exchange resins and linear phosphonitrilic halides and
- (c) heating the mixture of said hydrogen containing siloxane and said M' rich silicone compound to a temperature ranging from 20.degree. C. to 200.degree. C.
- 2. The process of claim 1 wherein said catalyst is a solid catalyst selected from the group consisting of
- 1) acid washed clays,
- 2) zeolites, and
- 3) ion exchange resins.
- 3. The process of claim 2 where the temperature ranges from 40.degree. C. to 180.degree. C.
- 4. The process of claim 3 where the catalyst is an acid washed clay.
- 5. The process of claim 3 where the catalyst is a zeolite.
- 6. The process of claim 3 where the catalyst is an ion exchange resin.
- 7. The process of claim 1 where the catalyst is a linear phosphonitrilic halide.
- 8. The process of claim 7 where the temperature ranges from 20.degree. C. to 140.degree. C.
- 9. The process of claim 8 where the linear phosphonitrilic halide is selected from the group consisting of:
- i) (PX.sub.3 (N(PX.sub.2)).sub.k NPX.sub.3).sup.+ (PX.sub.6)-- where X is halogen selected from the group consisting of fluorine, chlorine, bromine and iodine and k is an integer of one or greater;
- ii) Cl.sub.3 P(NPCl.sub.2).sub.n NPCl.sub.3.sup.+ PCl.sub.6 -- where n is an integer of from 1 to 6;
- iii) Cl.sub.3 P(NPCl.sub.2).sub.m NPCl.sub.3.sup.+ ECl.sub.p -- where E is an element having an electronegativity value of from 1.2 to 2, m is an integer of from 0 to 9 and p is an integer of from 4 to 6;
- iv) O(X).sub.2-f Y.sub.f P(NPX.sub.2).sub.g NPX.sub.3-h Y.sub.h where g is an integer ranging from 0 to 8, f is 0 or 1, h is 0 or 1, X is a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine, Y is selected from the group consisting of OH, OR' and R'CO.sub.2 where R' is alkyl or aryl; and
- v) O(X).sub.2-r Y.sub.r P(NPX.sub.2).sub.s NP(O)X.sub.2-t Y.sub.t where s is an integer ranging from 0 to 8, r is 0 or 1, t is 0 or 1, X is a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine, Y is selected from the group consisting of OH, OR' and R'CO.sub.2 where R' is alkyl or aryl.
- 10. The process of claim 9 where the catalyst is (PX.sub.3 (N(PX.sub.2)).sub.k NPX.sub.3).sup.+ (PX.sub.6).sup.-.
- 11. The process of claim 9 where the catalyst is Cl.sub.3 P(NPCl.sub.2).sub.n NPCl.sub.3.sup.+ PCl.sub.6.sup.-.
- 12. The process of claim 9 where the catalyst is Cl.sub.3 P(NPCl.sub.2).sub.m NPCl.sub.3.sup.+ ECl.sub.p.sup.-.
- 13. The process of claim 9 where the catalyst is
- O(X).sub.2-f Y.sub.f P(NPX.sub.2).sub.g NPX.sub.3-h Y.sub.h.
- 14. The process of claim 9 where the catalyst is
- O(X).sub.2-r Y.sub.r P(NPX.sub.2).sub.s NP(O)X.sub.2-t Y.sub.t.
- 15. The process of claim 9 further comprising deactivating said linear phosphonitrilic halide catalyst by heating to a temperature above 140.degree. C.
- 16. The process of claim 15 where the amount of said linear phosphonitrilic halide catalyst ranges from 1 to 1,000 parts per million by weight of the reaction mixture.
- 17. The process of claim 1 where i=0 and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each methyl.
- 18. The process of claim 1 where i=1 and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each methyl.
- 19. The process of claim 1 where i=0, yy=0 and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each methyl and the catalyst is an acid washed clay.
- 20. A process for the production of hydrogen containing siloxanes of the formula:
- M'D.sub.x.sup.H D.sub.y M'
- where
- M'=R.sub.3-i.sup.1 H.sub.i SiO.sub.1/2 with R.sup.1 being independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals and the subscript i ranges from 0 to 3;
- D.sup.H =R.sub.2.sup.3 SiO.sub.2/2 with R.sup.2 being independently selected from the group consisting of hydrogen and one to forty carbon atom monovalent hydrocarbon radicals; and
- D=R.sub.2.sup.3 SiO.sub.2/2 where each R.sup.3 is independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals; and the subscript x ranges from 1 to 20 and the subscript y ranges from 0 to 20; consisting essentially of:
- (a) mixing a hydrogen containing siloxane selected from the group consisting of:
- (i) D.sub.z.sup.H where D.sup.H is as previously defined and z varies from 3 to 8; and
- (ii) M'D.sub.xx.sup.H D.sub.yy M' where M', D.sup.H, and D are as previously defined and xx is greater than 20 and yy is either 0 or greater than 20; with
- (b) an M' rich silicone compound comprising M' where M' is as previously defined, wherein when said M' rich compound additionally comprises D, T, or Q groups, D is as previously defined,
- T=R.sup.4 SiO.sub.3/2 with R.sup.4 being independently selected from the group of one to forty carbon atom monovalent hydrocarbon radicals, and Q=SiO.sub.4/2 where the molar ratio of silicon atoms in the M' groups in said M' rich silicone compound to the sum of the silicone atoms in the M', D, T, and Q groups in said M' rich silicone compound is 0.04 or greater; in the presence of a catalyst selected from the group consisting of acid washed clays, zeolites, ion exchange resins and linear phosphonitrilic halides and
- (c) heating the mixture of said hydrogen containing siloxane and said M' rich silicone compound to a temperature ranging from 20.degree. C. to 200.degree. C.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 08/294,808 filed on Aug. 25, 1994, U.S. Pat. No. 5,510,441.
US Referenced Citations (13)
Foreign Referenced Citations (1)
Number |
Date |
Country |
2 252 969 |
Aug 1992 |
GBX |
Continuation in Parts (1)
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Number |
Date |
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Parent |
294808 |
Aug 1994 |
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