US4824918A
Expired / Lapsed
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Method of producing silicon carbide preceramic vinyl-containing polymers
Assignee: Dow Silicones Corp
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Filing: 1987-09-04
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Granted: 1989-04-25
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Expires: 2007-09-04
Abstract
Abstract Vinyl-containing polysilanes are described wherein the vinyl groups are attached to endblocking sites of intermediate reactivity. These vinyl-containing polysilanes are prepared by reacting a halogen-endblocked polysilane with, first, a non-vinyl-containing Grignard reagent or a non-vinyl organolithium compound whereby the most reactive halogen endblocking groups are replaced; then, second, reacting the resulting polysilane with vinyl Grignard reagent or vinyllithium whereby the halogen endblocking groups of intermediate reactivity are replaced; and, third, reacting the resulting polysilane with a non-vinyl-containing Grignard reagent or a non-vinyl organolithium compound whereby the least reactive halogen endblocking groups are replaced. The vinyl-containing polysilanes can be coverted to ceramic materials, including ceramic fibers, by pyrolysis.
Inventors
- 👤 Duane R. Bujalski
- 👤 Gary E. Legrow
- 👤 Jonathan Lipowitz
- 👤 Thomas F. Lim
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 18:24
CPC Classifications
C; C04; C04B; C04B35/00; C04B35/515; C04B35/56; C04B35/565; C04B35/571; C08; C08G; C08G77/00; C08G77/60
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
281 words
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 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 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° C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH 2 ═CH)MgX' or vinyllithium at a temperature of 0 to 120° 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° to 120° 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° C. to obtain the vinyl-containing first polysilane.
Claim 2
Independent Claim
281 words
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 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 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° C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH 2 ═CH)MgX' or vinyllithium at a temperature of 0 to 120° 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° to 120° 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° C. to obtain the vinyl-containing first polysilane.
Claim 3
Dependent Claim
40 words
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.
Claim 4
Dependent Claim
43 words
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 2 ═CH)MgX, and with (3) a Grignard reagent of general formula R'MgX.
Claim 5
Dependent Claim
47 words
A method as defined in claim 3 where the second polysilane is reacted with (1) a Grignard reagent of general formula (CH 3 )MgX, with (2) a Grignard reagent of general formula (CH 2 ═CH)MgX, and with (3) a Grignard reagent of general formula (CH 3 )MgX.
Claim 6
Dependent Claim
99 words
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).
Claim 7
Dependent Claim
99 words
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).
Claim 8
Dependent Claim
97 words
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).
Claim 9
Dependent Claim
35 words
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.
Claim 10
Dependent Claim
23 words
A method as defined in claim 8 where the second polysilane is reacted with (1) methyllithium, with (2) vinyllithium, and with (3) methyllithium.
Claim 11
Dependent Claim
97 words
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).
Claim 12
Dependent Claim
97 words
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).
Claim 13
Dependent Claim
95 words
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).
Claim 14
Dependent Claim
43 words
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 2 ═CH)MgX, and with (3) an organolithium compound of general formula R'Li.
Claim 15
Dependent Claim
31 words
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 2 ═CH)MgX, and with (3) methyllithium.
Claim 16
Dependent Claim
99 words
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).
Claim 17
Dependent Claim
99 words
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).
Claim 18
Dependent Claim
97 words
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).
Claim 19
Independent Claim
433 words
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 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 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° to 120° C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH 2 ═CH)MgX' or vinyllithium at a temperature of 0° to 120° 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° to 120° 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° C. to obtain the vinyl-containing first polysilane.
Claim 20
Independent Claim
433 words
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 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 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° to 120° C., followed by reaction with (2) a vinyl-containing Grignard reagent of general formula (CH 2 ═CH)MgX' or vinyllithium at a temperature of 0° to 120° 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° to 120° 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° C. to obtain the vinyl-containing first polysilane.
Claim 21
Dependent Claim
42 words
A method as defined in claim 18 where the first polysilane and the second polysilane each contain 0 to 40 mole percent of [R 2 Si] units, 40 to 99 mole percent [RSi] units, and 1 to 30 mole percent [R"Si] units.
Claim 22
Dependent Claim
42 words
A method as defined in claim 19 where the first polysilane and the second polysilane each contain 0 to 10 mole percent of [R 2 Si] units, 80 to 99 mole percent [RSi] units, and 1 to 20 mole percent [R"Si] units.
Claim 23
Dependent Claim
113 words
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).
Claim 24
Dependent Claim
113 words
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).
Claim 25
Dependent Claim
113 words
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).
Claim 26
Dependent Claim
113 words
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).
Claim 27
Dependent Claim
111 words
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).
Claim 28
Dependent Claim
111 words
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).
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