US4719273A
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Method for forming new preceramic polymers containing silicon
Assignee: Massachusetts Institute of Technology
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Filing: 1986-03-24
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Granted: 1988-01-12
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Expires: 2006-03-24
Abstract
Abstract A method of forming preceramic polymers by mixing (A) an organic polysilane, preferably either a methylpolysilane of the formula [(RSiH) x (RSi) y ] 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, a tri(lower)alkyl- or di(lower)alkylsilyl group x+y=1, (x and y are each >0 and also x=1, y=0), and n is an integer greater than 1) or a polycarbosilane having repeat units of the formula [R a Si(H)--(CH 2 ) q ], [R a Si(H)--CH═CH], and [R a Si(H)--C.tbd.C] (where R a is H, 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, q is an integer 1 or greater), with (B) an organic or organisilicon compound having at least two alkenyl groups and allowing the mixture to react is disclosed. Preferably, the alkenyl group is a vinyl group. The reaction is preferably initiated by the generation of reactive free radicals. Novel preceramic polymers formed by this method are also disclosed.
Inventors
- 👤 Dietmar Seyferth
- 👤 Yuan-Fu Yu
- 👤 Gudrun E. Koppetsch
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 08:48
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/60; C08L; C08L83/00; C08L83/16; G; G03; G03F; G03F7/00; G03F7/004; G03F7/075; G03F7/0757
Claims Analysis
Total Claims: 72
Claim 1
Independent Claim
68 words
A method for preparing preceramic organosilicon polymers, where the method comprises: (a) mixing an organic polysilane having a plurality of Si--H functional groups with a sufficient quantity of an organosilicon compound containing at least two alkenyl groups or a cyclic organic compound containing at least three alkenyl groups, to undergo a hydrosilylation reaction; (b) allowing the mixture of step (a) to react, thereby forming said preceramic organosilicon polymer.
Claim 2
Independent Claim
68 words
A method for preparing preceramic organosilicon polymers, where the method comprises: (a) mixing an organic polysilane having a plurality of Si--H functional groups with a sufficient quantity of an organosilicon compound containing at least two alkenyl groups or a cyclic organic compound containing at least three alkenyl groups, to undergo a hydrosilylation reaction; (b) allowing the mixture of step (a) to react, thereby forming said preceramic organosilicon polymer.
Claim 3
Independent Claim
125 words
A method for preparing preceramic organosilicon polymers, where the method comprises: (a) mixing a polycarbosilane having a multiplicity of repeat units of the formula, [R a Si(H)--(ORG) q ], where R a is H, a lower alkyl group having from 1 to about 6 carbon atoms, a cycloalkyl group having 3 to about 6 carbon atoms, or a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, (ORG) is a difunctional alkylene, alkenylene or alkynylene group, and q is an integer 1 or greater, with a predetermined quantity of an organic or organosilicon compound containing at least two alkenyl groups to undergo a hydrosilylation reaction; (b) allowing the mixture of step (a) to react, thereby forming said preceramic organosilicon polymer.
Claim 4
Independent Claim
125 words
A method for preparing preceramic organosilicon polymers, where the method comprises: (a) mixing a polycarbosilane having a multiplicity of repeat units of the formula, [R a Si(H)--(ORG) q ], where R a is H, a lower alkyl group having from 1 to about 6 carbon atoms, a cycloalkyl group having 3 to about 6 carbon atoms, or a substituted or unsubstituted lower aryl group having from 6 to about 10 carbon atoms, (ORG) is a difunctional alkylene, alkenylene or alkynylene group, and q is an integer 1 or greater, with a predetermined quantity of an organic or organosilicon compound containing at least two alkenyl groups to undergo a hydrosilylation reaction; (b) allowing the mixture of step (a) to react, thereby forming said preceramic organosilicon polymer.
Claim 5
Dependent Claim
20 words
The method of claim 2 wherein the reaction of step (b) is initiated by the generation of reactive free radicals.
Claim 6
Dependent Claim
17 words
The method of claim 3 in which an appropriate input of energy generates the reactive free radicals.
Claim 7
Dependent Claim
34 words
The method of claim 2 wherein the repeat units are selected from the group consisting of the formula [R a Si(H)--(CH 2 ) q ], [R a Si(H)--CH═CH], [R a Si(H)--C.tbd.C], and mixtures thereof.
Claim 8
Dependent Claim
19 words
The method of claim 4 wherein the energy source for the generation of free radicals is initiated by heat.
Claim 9
Dependent Claim
25 words
The method of claim 3 wherein the generation of free radicals is initiated by ultraviolet irradiation in the presence or the absence of a catalyst.
Claim 10
Dependent Claim
28 words
The method of claim 3 wherein the generation of free radicals is initiated by a free radical catalyst selected from the group consisting of peroxides and azo compounds.
Claim 11
Dependent Claim
11 words
The method of claim 8 wherein the azo compound is azobisisobutyronitrile.
Claim 12
Dependent Claim
12 words
The method of claim 8 wherein the peroxide is an organic peroxide.
Claim 13
Dependent Claim
12 words
The method of claim 10 wherein the organic peroxide is benzoyl peroxide.
Claim 14
Dependent Claim
25 words
The method of claim 3 which further comprises adding a transition metal catalyst which is effective in hydrosilylation reactions to the mixture of step (a).
Claim 15
Dependent Claim
18 words
The method of claim 12 wherein the transition metal catalyst is H 2 PtCl 6 .6H 2 O.
Claim 16
Dependent Claim
28 words
The method of claim 2 wherein the polycarbosilane has at least about 25 mole % of repeat units of the formula [R a Si(H)--(CH 2 ) q ].
Claim 17
Dependent Claim
13 words
The method of claim 6 wherein the mixture is heated to 70°-90° C.
Claim 18
Dependent Claim
25 words
The method of claim 3 wherein the alkenyl group of the alkenyl containing compound is a lower alkenyl group having 2 to 6 carbon atoms.
Claim 19
Dependent Claim
13 words
The method of claim 16 wherein the alkenyl group is CH 2 ═CH.
Claim 20
Dependent Claim
14 words
The method of claim 1 wherein the organic polysilane contains a lower alkyl group.
Claim 21
Dependent Claim
13 words
The method of claim 2, wherein R a is the lower alkyl group.
Claim 22
Dependent Claim
13 words
The method of claim 16, wherein R a is the lower alkyl group.
Claim 23
Dependent Claim
12 words
The method of claim 19, wherein R a is CH 3 .
Claim 24
Dependent Claim
12 words
The method of claim 20, wherein R a is CH 3 .
Claim 25
Dependent Claim
11 words
The method of claim 2 where q is 3 to 1.
Claim 26
Dependent Claim
9 words
The method of claim 2 where q is 1.
Claim 27
Dependent Claim
208 words
The method of claim 20 wherein the organosilicon compound is selected from the group consisting of [R 1 2 (A)Si] 2 Y, [R 1 (A) 2 Si] 2 Y, [(A) 3 Si] 2 Y, [R 1 ASiY] n , R 1 n (A) 3-n Si--Si(A) 3-q R 1 q , (A) 4 Si, and cyclo-[(A) 2 SiY 1 ] m where Y=O, S, NH, NR 2 , CH 2 , CH═CH, C.tbd.C CH 2 CH 2 , ##STR6## and other organic bridges; n and q are 0, 1 or 2, except where it causes the compound to be non-existant, n may be the same or different than q; Y 1 =O, S, NH, NR 2 , CH 2 , CH═CH, C.tbd.C, m is 2 or greater when Y 1 is NH, NR 2 , S, CH 2 , CH═CH and C.tbd.C, and m is 3 or greater when Y 1 is O; R 1 is a substituted or unsubstituted lower alkyl group having 1-6 carbon atoms, or a substituted or unsubstituted lower aryl group having 6-10 carbon atoms, R 2 is defined as R 1 and can be the same or different and A is a substituted or unsubstituted vinyl group or a substituted or unsubstituted allyl group.
Claim 28
Dependent Claim
18 words
The method of claim 25 wherein [R 1 ASiY] n is cyclo-[R 1 (A)SiY 1 ] m .
Claim 29
Dependent Claim
9 words
The method of claim 25 wherein A is vinyl.
Claim 30
Dependent Claim
82 words
The method of claim 21 wherein the organosilicon compound is selected from the group consisting of cyclo-[(CH 3 )(CH 2 ═CH)SiO] 4 , cyclo-[(CH 3 )(CH 2 ═CH)SiO] 5 , cyclo-[(CH 3 )(CH 2 ═CH)SiO] 6 , combinations of cyclo-[(CH 3 )(CH 2 ═CH)SiO] n , n=at least, 4, cyclo-[(CH 3 )(CH 2 ═CH)SiS] 3 , cyclo-[(CH 3 )(CH 2 ═CH)SiNH] 3 cyclo-[(CH 3 )(CH 2 ═CH)SiNH] 4 , and combinations of cyclo-[(CH 3 )(CH 2 ═CH)SiNH] n , n=at least 3.
Claim 31
Dependent Claim
83 words
The method of claim 2 wherein an organopolysilane of the formula [(RSiH) x (RSi) y ] n , where x+y=1, n is an integer greater than 1, R is a lower alkyl group having from about 1 to about 6 carbon atoms, a lower 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 or a tri(lower)alkyl- or di(lower)alkylsilyl group is added to create a ternary preceramic polymer.
Claim 32
Dependent Claim
52 words
The method of claim 29 wherein the organopolysilane is added in sufficient quantity so that the excess silicon obtained on pyrolysis of the organopolysilane can react with excess carbon from the pyrolysis of the polycarbosilane and the alkenyl containing organic or organosilicon compound, thereby minimizing the amount of free carbon or silicon.
Claim 33
Dependent Claim
12 words
The method of claim 30 wherein R is the lower alkyl group.
Claim 34
Dependent Claim
11 words
The method of claim 31 wherein R is CH 3 .
Claim 35
Dependent Claim
22 words
The method of claim 30 wherein the organic substituents in the silicon compound other than the alkenyl groups are CH 3 .
Claim 36
Dependent Claim
20 words
The method of claim 29 wherein the organopolysilane is [(CH 3 SiH) x (CH 3 Si) y ] n .
Claim 37
Dependent Claim
20 words
The method of claim 33 wherein the organopolysilane is [(CH 3 SiH) x (CH 3 Si) y ] n .
Claim 38
Dependent Claim
13 words
The method of claim 30 wherein all non-alkenyl substituents are CH 3 .
Claim 39
Dependent Claim
20 words
The method of claim 31 wherein the organopolysilane is [(CH 3 SiH) x (CH 3 Si) y ] n .
Claim 40
Dependent Claim
13 words
The method of claim 37 wherein the mixture is heated to 70°-90° C.
Claim 41
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 1.
Claim 42
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 2.
Claim 43
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 5.
Claim 44
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 14.
Claim 45
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 21.
Claim 46
Dependent Claim
88 words
The method of claim 3 wherein an organopolysilane of the formula [(R a SiH) x (R a Si) y ] n , where x+y=1, n is an integer greater than 1, R a is a lower alkyl group having from about 1 to about 6 carbon atoms, a lower 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 or a tri(lower)alkyl- or di(lower)alkylsilyl group is added to create a ternary preceramic polymer.
Claim 47
Dependent Claim
51 words
The method of claim 44 wherein the organopolysilane is added in sufficient quantity so that the excess silicon obtained on pyrolysis of the organopolysilane can react with excess carbon from the pyrolysis of the polycarbosilane and the alkenyl-containing organic or organosilicon compound, thereby minimizing the amount of free carbon or silicon.
Claim 48
Dependent Claim
13 words
The method of claim 45 wherein R a is the lower alkyl group.
Claim 49
Dependent Claim
12 words
The method of claim 46 wherein R a is CH 3 .
Claim 50
Dependent Claim
12 words
The method of claim 46 wherein R is a lower alkyl group.
Claim 51
Dependent Claim
12 words
The method of claim 47 wherein R is a lower alkyl group.
Claim 52
Dependent Claim
11 words
The method of claim 46 wherein R is CH 3 .
Claim 53
Dependent Claim
14 words
The method of claim 48 wherein all non alkenyl substituents are CH 3 .
Claim 54
Dependent Claim
14 words
The method of claim 49 wherein all non alkenyl substituents are CH 3 .
Claim 55
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 45.
Claim 56
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 47.
Claim 57
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 48.
Claim 58
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 49.
Claim 59
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 51.
Claim 60
Dependent Claim
10 words
A preceramic polymer formed by the method of claim 52.
Claim 61
Dependent Claim
29 words
The method of claim 3 wherein the polycarbosilane polymer has at least about 35 mole % of repeat units of the formula [R a Si(H)--(CH 2 ) q ].
Claim 62
Dependent Claim
29 words
The method of claim 3 wherein the polycarbosilane polymer has at least about 50 mole % of repeat units of the formula [R a Si(H)--(CH 2 ) q ].
Claim 63
Dependent Claim
13 words
The method of claim 20 wherein the organic compound is a polyalkenyl compound.
Claim 64
Dependent Claim
61 words
The method of claim 3 wherein the organic or organosilicon compound is a compound of the formula --[--R 1 (Un)SiC.tbd.C--]-- n , where R 1 is a substituted or unsubstituted lower alkyl having 1-6 carbon atoms or a substituted or unsubstituted lower aryl group having 6-10 carbon atoms, Un is an unsaturated moiety, and n is an integer 1 or greater.
Claim 65
Dependent Claim
39 words
The method of claim 3 wherein at least about 25 mole % of the repeat units of the polycarbosilane are selected from the group consisting of [R a Si(H)--(CH 2 ) q ], [R a Si(H)--CH═CH], and [RaSi(H)--C C].
Claim 66
Dependent Claim
24 words
The method of claim 63 wherein the polycarbosilane contains at least about 25 mole % of repeat units of the formula [R a Si(H)--C.tbd.C].
Claim 67
Dependent Claim
24 words
The method of claim 61 wherein the polycarbosilane contans at least about 25 mole % of repeat units of the formula [R a Si(H)--CH═CH].
Claim 68
Dependent Claim
17 words
The method of claim 62 where R 1 is CH 3 and Un is (CH 2 ═CH).
Claim 69
Dependent Claim
25 words
The method of claim 3 wherein the polycarbosilane polymer has at least about 35 mole % of repeat units of the formula [R a Si(H)--C.tbd.C].
Claim 70
Dependent Claim
25 words
The method of claim 3 wherein the polycarbosilane polymer has at least about 35 mole % of repeat units of the formula [R a Si(H)--CH═CH].
Claim 71
Dependent Claim
24 words
The method of claim 63 wherein the polycarbosilane contains at least about 35 mole % of repeat units of the formula [R a Si(H)--CH═CH].
Claim 72
Dependent Claim
24 words
The method of claim 69 wherein the polycarbosilane contains at least about 50 mole % of repeat units of the formula [R a Si(H)--CH═CH].
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