Claims
- 1. A method of preparing a vinyl-containing first polysilane having the general formula
- [RSi][R.sub.2 Si]
- where there are present 0 to 60 mole percent [R.sub.2 Si] units and 40 to 100 mole percent [RSi] units, where R is an alkyl radical containing 1 to 8 carbon atoms, and where the remaining bonds on silicon are attached to other silicon atoms, --R' groups, and vinyl groups, where R' is an alkyl group containing 1 to 8 carbon atoms or a phenyl group, said method consisting of reacting under anhydrous conditions in the presence of a solvent a second polysilane with chlorine or bromine endblocking groups of general formula
- [RSi][R.sub.2 Si]
- where there are present 0 to 60 mole percent [R.sub.2 Si] units and 40 to 100 mole percent [RSi] units, where R is an alkyl radical containing 1 to 8 carbon atoms, and where the remaining bonds on silicon are attached to other silicon atoms and chlorine or bromine atoms with (1) a Grignard reagent of general formula R'MgX' or an organolithium compound of general formula R'Li at a temperature of 0 to 120.degree. C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX' or vinyllithium at a temperature of 0 to 120.degree. C., followed by reaction with (3) a Grignard reagent of general formula R'MgX' or an organolithium reagent of general formula R'Li at a temperature of 0.degree. to 120.degree. C. where R' is an alkyl radical with 1 to 8 carbon atoms or a phenyl radical and X' is chlorine, bromine, or iodine and thereafter removing the solvent at a temperature of less than about 150.degree. C. to obtain the vinyl-containing first polysilane.
- 2. A method as defined in claim 1 where the remaining bonds on silicon in the second polysilane are attached to other silicon atoms and chlorine atoms and where R in both the first and second polysilanes is a methly group.
- 3. A method as defined in claim 2 where the second polysilane is reacted with (1) a Grignard reagent of general formula R'MgX, with (2) a Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX, and with (3) a Grignard reagent of general formula R'MgX.
- 4. A method as defined in claim 3 where the second polysilane is reacted with (1) a Grignard reagent of general formula (CH.sub.3)MgX, with (2) a Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX, and with (3) a Grignard reagent of general formula (CH.sub.3)MgX.
- 5. A method as defined in claim 3 where the Grignard reagent in step (1) is present in an amount sufficient to react with 10 to 40 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with 30 to 70 weight percent of the replaceable chlorine in the second polysilane, and where the Grignard reagent in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 6. A method as defined in claim 3 where the Grignard reagent in step (1) is present in an amount sufficient to react with 25 to 40 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with 40 to 60 weight percent of the replaceable chlorine in the second polysilane, and where the Grignard reagent in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 7. A method as defined in claim 3 where the Grignard reagent in step (1) is present in an amount sufficient to react with about 33 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with about 50 weight percent of the replaceable chlorine in the second polysilane, and where the Grignard reagent in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 8. A method as defined in claim 2 where the second polysilane is reacted with (1) an organolithium compound of general formula R'Li, with (2) vinyllithium, and with (3) an organolithium compound of general formula R'Li.
- 9. A method as defined in claim 8 where the second polysilane is reacted with (1) methyllithium, with (2) vinyllithium, and with (3) methyllithium.
- 10. A method as defined in claim 8 where the organolithium compound in step (1) is present in an amount sufficient to react with 10 to 40 weight percent of the replaceable chlorine in the second polysilane, where vinyllithium in step (2) is present in an amount sufficient to react with 30 to 70 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 11. A method as defined in claim 8 where the organolithium compound in step (1) is present in an amount sufficient to react with 25 to 40 weight percent of the replaceable chlorine in the second polysilane, where vinyllithium in step (2) is present in n amount sufficient to react with 40 to 60 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 12. A method as defined in claim 8 where the organolithium compound in step (1) is present in an amount sufficient to react with about 33 weight percent of the replaceable chlorine in the second polysilane, where vinyllithium in step (2) is present in an amount sufficient to react with about 50 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 13. A method as defined in claim 2 where the second polysilane is reacted with (1) an organolithium compound of general formula R'Li, with (2) a Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX, and with (3) an organolithium compound of general formula R'Li.
- 14. A method as defined in claim 13 where the second polysilane is reacted with (1) methyllithium, with (2) a Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX, and with (3) methyllithium.
- 15. A method as defined in claim 13 where the organolithium compound in step (1) is present in an amount sufficient to react with 10 to 40 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with 30 to 70 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 16. A method as defined in claim 13 where the organolithium compound in step (1) is present in an amount sufficient to react with 25 to 40 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with 40 to 60 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane reamining after steps (1) and (2).
- 17. A method as defined in claim 13 where the organolithium compound in step (1) is present in an amount sufficient to react with about 33 weight percent of the replaceable chlorine in the second polysilane, where the Grignard reagent in step (2) is present in an amount sufficient to react with about 50 weight percent of the replaceable chlorine in the second polysilane, and where the organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine in the second polysilane remaining after steps (1) and (2).
- 18. A method of preparing a vinyl-containing first polysilane having the general formula
- [RSi][R.sub.2 Si][R"Si]
- where there are present 0 to 40 mole percent [R.sub.2 Si] units, 0.1 to 99.9 mole percent [RSi] units, and 0.1 to 99.9 mole percent [R"Si] units, where R is an alkyl radical containing 1 to 8 carbon atoms, where R" is selected from the group consisting of alkyl radicals containing at least six carbon atoms, phenyl radicals, and radicals of the formula
- A.sub.y X.sub.(3-y) Si(CH.sub.2).sub.z --
- where A is a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, y is an integer equal to 0 to 3, X is chlorine or bromine, and z is an integer greater than or equal to 1, and where the remaining groups on silicon are attached to other silicon atoms, --R' groups, and vinyl groups, where R' is an alkyl group containing 1 to 8 carbon atoms or a phenyl group, said method consisting of reacting under anhydrous conditions in the presence of a solvent a second polysilane with chlorine or bromine endblocking groups of general formula
- [RSi][R.sub.2 Si][R"Si]
- where there are present 0 to 40 mole percent [R.sub.2 Si] units, 0.1 to 99.9 mole percent [RSi] units, and 0.1 to 99.9 mole percent [R"Si] units, where R is an alkyl radical containing 1 to 8 carbon atoms, where R" is selected from the group consisting of alkyl radicals containing at lease six carbon atoms, phenyl radicals, and radicals of the formula
- A.sub.y X.sub.(3-y) Si(CH.sub.2).sub.z --
- where A is a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, y is an integer equal to 0 to 3, X is chlorine or bromine, and z is an integer greater than or equal to 1, and where the remaining bonds on silicon are attached to other silicon atoms and chlorine or bromine atoms with (1) a Grignard reagent of general formula R'MgX' or an organolithium compound of general formula R'Li at a temperature of 0.degree. to 120.degree. C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH.sub.2 .dbd.CH)MgX' or vinyllithium at a temperature of 0.degree. to 120.degree. C., followed by reaction with (3) a Grignard reagent of general formula R'MgX' or an organolithium reagent of general formula R'Li at a temperature of 0.degree. to 120.degree. C. where R' is an alkyl radical with 1 to 8 carbon atoms or a phenyl radical and X' is chlorine, bromine, or iodine and thereafter removing the solvent at a temperature of less than about 150.degree. C. to obtain the vinyl-containing first polysilane.
- 19. A method as defined in claim 18 where the first polysilane and the second polysilane each contain 0 to 40 mole percent of [R.sub.2 Si] units, 40 to 99 mole percent [RSi] units, and 1 to 30 mole percent [R"Si] units.
- 20. A method as defined in claim 19 where the first polysilane and the second polysilane each contain 0 to 10 mole percent of [R.sub.2 Si] units, 80 to 99 mole percent [RSi] units, and 1 to 20 mole percent [R"Si] units.
- 21. A method as defined in claim 19 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with 10 to 40 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with 30 to 70 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
- 22. A method as defined in claim 20 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with 10 to 40 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with 30 to 70 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
- 23. A method as defined in claim 21 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with 25 to 40 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with 40 to 60 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
- 24. A method as defined in claim 22 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with 25 to 40 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with 40 to 60 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
- 25. A method as defined in claim 23 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with about 33 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with about 50 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
- 26. A method as defined in claim 24 where the Grignard reagent or organolithium compound in step (1) is present in an amount sufficient to react with about 33 weight percent of the replaceable chlorine or bromine in the second polysilane, where the Grignard reagent or vinyllithium in step (2) is present in an amount sufficient to react with about 50 weight percent of the replaceable chlorine or bromine in the second polysilane, and where the Grignard reagent or organolithium compound in step (3) is present in an amount in excess of that required to react with any replaceable chlorine or bromine in the second polysilane remaining after steps (1) and (2).
STATEMENT OF GOVERNMENT RIGHTS
The United States Government has rights in this invention pursuant to Contract Number F33615-83-C-5006 awarded by the United States Air Force.
US Referenced Citations (8)
Non-Patent Literature Citations (2)
Entry |
Baney, et al.; "Methylchloropolysilane & Derivatives Prepared from the Redistribution of Methylchlorodisilates"; 1983, 2, 859; ORGANOMETALLICS. |
West et al.; "Polysilane High Polymers as Precursors to Silicon Carbide"; (1984), 25, 4,; POLYM. PREPR. |