US4705837A
Expired / Lapsed
US
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Method for converting Si-H containing polysiloxanes to new and useful preceramic polymers and ceramic materials
Assignee: Massachusetts Institute of Technology
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Filing: 1986-04-08
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Granted: 1987-11-10
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Expires: 2006-04-08
Abstract
Abstract A method of forming preceramic polymers using a polysiloxane having repeat units of the formula [RSi(H)O] n (where R is a lower alkyl group having from 1 to about 6 carbon atoms, a cycloalkyl group having from 3 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, n is an integer 1 or greater), by reacting it with a (poly)silylamide is disclosed. Preferably, the poly(silylamide) is a polymeric alkali metal silylamide of the formula [(R 1 SiHNH) a (R 1 SiN) b (R 1 SiHNM) c ] m where a+b+c=1; R 1 is a lower alkyl group having from 1 to about 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 2 to about 6 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, a tri(lower)alkyl- or di(lower)alkylsilyl group or a di(lower)alkylamino group; M is an alkali metal or one-half equivalent of an alkaline earth metal; and m is an integer greater than 1. Preferably, a weight ratio of polysiloxane:silylamide of 15:1 to 1:15 is used. Novel preceramic polymers formed by this method are also disclosed.
Inventors
- 👤 Dietmar Seyferth
- 👤 Yuan-Fu Yu
- 👤 Tom S. Targos
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 22:49
CPC Classifications
C; C08; C08L; C08L83/00; C08L83/16; C04; C04B; C04B35/00; C04B35/515; C04B35/56; C04B35/565; C04B35/571; C04B35/58; C04B35/584; C04B35/589; C08G; C08G77/00; C08G77/48; C08G77/54
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
90 words
A method for preparing organosilicon polymers, wherein the method comprises: (a) admixing a poly(silylamide) in an organic solvent with a polysiloxane having a plurality of repeat units of the formula [RSi(H)O] n where R is a lower alkyl group having from 1 to about 6 carbon atoms, a cycloalkyl group having 3 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, and n is an integer 1 or greater; and (b) allowing the admixture of step (a) to react.
Claim 2
Independent Claim
90 words
A method for preparing organosilicon polymers, wherein the method comprises: (a) admixing a poly(silylamide) in an organic solvent with a polysiloxane having a plurality of repeat units of the formula [RSi(H)O] n where R is a lower alkyl group having from 1 to about 6 carbon atoms, a cycloalkyl group having 3 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, and n is an integer 1 or greater; and (b) allowing the admixture of step (a) to react.
Claim 3
Dependent Claim
21 words
The method of claim 1 wherein said method further comprises quenching the reaction mixture of step (b) with a reactive electrophile.
Claim 4
Dependent Claim
115 words
The method of claim 2, wherein the poly(silylamide) has the formula [(R 1 SiHNH) a (R 1 SiN) b (R 1 SiHNM) c] m , where a+b+C=1, R 1 is a lower alkyl group having from 1 to about 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 3 to about 6 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, a tri(lower)alkyl- or di(lower)alkylsilyl group or a di(lower)alkylamino group; M is an alkali metal or one-half equivalent of an alkaline earth metal; and m is an integer greater than 1.
Claim 5
Dependent Claim
12 words
The method of claim 1, wherein R is the lower alkyl group.
Claim 6
Dependent Claim
11 words
The method of claim 4, wherein R is CH 3 .
Claim 7
Dependent Claim
13 words
The method of claim 3, wherein R 1 is the lower alkyl group.
Claim 8
Dependent Claim
12 words
The method of claim 6, wherein R is the lower alkyl group.
Claim 9
Dependent Claim
15 words
The method of claim 7, wherein both R and R 1 are CH 3 .
Claim 10
Dependent Claim
18 words
The method of claim 1 wherein the weight ratio of polysiloxane: poly(silylamide) is from about 15:1 to 1:15.
Claim 11
Dependent Claim
19 words
The method of claim 3 wherein the ratio of polysiloxane to alkali metal poly(silylamide) is about 5:1 to 1:5.
Claim 12
Dependent Claim
11 words
The method of claim 10 wherein the ratio is about 1:1.
Claim 13
Dependent Claim
40 words
The method of claim 2, wherein the reactive electrophile has the formula E-X, wherein E is selected from the group consisting of lower alkyl and silyl groups and X is selected from the group consisting of halogens, sulfates and sulfonates.
Claim 14
Dependent Claim
27 words
The method of claim 12 wherein the reactive electrophile is selected from the group consisting of lower alkyl halides, lower alkyl sulfates, lower alkyl sulfonates, and halosilanes.
Claim 15
Dependent Claim
14 words
The method of claim 13 wherein the reactive electrophile is the lower alkyl halide.
Claim 16
Dependent Claim
14 words
The method of claim 14 wherein the lower alkyl halide is CH 3 I.
Claim 17
Dependent Claim
11 words
The method of claim 13 wherein the halosilane is a chlorosilane.
Claim 18
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 1.
Claim 19
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 3.
Claim 20
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 11.
Claim 21
Dependent Claim
12 words
The method of claim 1 wherein R is the lower aryl group.
Claim 22
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 8.
Claim 23
Independent Claim
239 words
A method for preparing an organosilicon polymer, wherein the method comprises: (a) generating an alkali metal poly (silylamide) in the presence of a polysiloxane having a plurality of repeat units of the formula: [RSi(H)O] n , where n is an interger 1 or greater; R is a lower alkyl group having from 1 to about 6 carbon atoms, a lower cycloalkyl group having from 3 to about 6 carbon atoms, or a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, wherein the poly(silylamide) is generated by reacting the ammonolysis product of an R 1 SiHX 2 , where R 1 is a lower alkyl group having from 1 to about 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to about 6 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, a tri(lower)alkyl- or di(lower)alkylsilyl group or a di(lower)alkylamino group and X is a halogen, in the presence of a basic catalyst capable of deprotonating the hydrogen from a nitrogen atom adjacent to a silicon atom to generate the poly(silylamide) in situ: (b) allowing the in situ generated poly(silylamide) and the polysiloxane sufficient time to react with each other at room temperature; and (c) quenching the mixture with an organic halide or halosilane to produce the organosilicon preceramic polymer.
Claim 24
Independent Claim
239 words
A method for preparing an organosilicon polymer, wherein the method comprises: (a) generating an alkali metal poly (silylamide) in the presence of a polysiloxane having a plurality of repeat units of the formula: [RSi(H)O] n , where n is an interger 1 or greater; R is a lower alkyl group having from 1 to about 6 carbon atoms, a lower cycloalkyl group having from 3 to about 6 carbon atoms, or a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, wherein the poly(silylamide) is generated by reacting the ammonolysis product of an R 1 SiHX 2 , where R 1 is a lower alkyl group having from 1 to about 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to about 6 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to about 6 carbon atoms, a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, a tri(lower)alkyl- or di(lower)alkylsilyl group or a di(lower)alkylamino group and X is a halogen, in the presence of a basic catalyst capable of deprotonating the hydrogen from a nitrogen atom adjacent to a silicon atom to generate the poly(silylamide) in situ: (b) allowing the in situ generated poly(silylamide) and the polysiloxane sufficient time to react with each other at room temperature; and (c) quenching the mixture with an organic halide or halosilane to produce the organosilicon preceramic polymer.
Claim 25
Dependent Claim
20 words
The method of claim 22 wherein the ratio of polysiloxane: in situ generated poly(silylamide) is from about 15:1 to 1:15.
Claim 26
Dependent Claim
20 words
The method of claim 23 wherein the ratio of polysiloxane: in situ generated poly(silylamide) is from about 5:1 to 1:5.
Claim 27
Dependent Claim
17 words
The method of claim 24 wherein the ratio of polysiloxane: in situ generated poly(silylamide) is about 1:1.
Claim 28
Dependent Claim
16 words
The method of claim 24 wherein R amd R 1 are each the lower alkyl groups.
Claim 29
Dependent Claim
14 words
The method of claim 24 wherein R and R 1 are CH 3 .
Claim 30
Dependent Claim
14 words
The method of claim 25 wherein R and R 1 are CH 3 .
Claim 31
Dependent Claim
10 words
The preceramic polymer formed by the method of claim 27.
Claim 32
Dependent Claim
10 words
The preceramic polymer formed by the method of claim 28.
References Cited (Backward Citations)
US3108985A
Cited
US3853567A
Cited
US3892583A
Cited
US4310651A
Cited
US4404153A
Cited
US4312970A
Cited
US4395460A
Cited
US4482669A
Cited
US4611035A
Cited
US4645807A
Cited
US4639501A
Cited
US4650837A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-11-09 | 1991-05-11 | 1991-11-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-11-09 | 1995-05-11 | 1995-11-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-11-09 | 1999-05-11 | 1999-11-10 | $7700.00 | Window Closed / Lapsed |