US4761458A — Preceramic polycarbosilane derivatives

Claim 1

Independent Claim 40 words

A halogenated polycarbosilane consisting essentially of ##STR8## units where each R is independently an alkyl group containing 1 to 4 carbon atoms, where X is chlorine or bromine, and where X is present at about 0.1 to 80 weight percent.

Claim 2

Dependent Claim 40 words

A halogenated polycarbosilane consisting essentially of ##STR8## units where each R is independently an alkyl group containing 1 to 4 carbon atoms, where X is chlorine or bromine, and where X is present at about 0.1 to 80 weight percent.

Claim 3

Dependent Claim 26 words

A halogenated polycarbosilane as defined in claim 1 where R is methyl, X is chlorine, and X is present at about 0.5 to 35 weight percent.

Claim 4

Dependent Claim 26 words

A halogenated polycarbosilane as defined in claim 1 where R is methyl, X is bromine, and X is present at about 0.5 to 55 weight percent.

Claim 5

Independent Claim 101 words

A method of preparing a halogenating polycarbosilane, which method comprises reacting a polycarbosilane with a halogenating agent selected from the group consisting of chlorine, bromine, PCl 5 , PBr 5 , SbCl 5 , N-chlorosuccinimide, N-bromosuccinimide, SOCl 2 , and mixtures of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine, where the polycarbosilane contains at least 0.1 weight percent Si-H groups, and thereafter separating the halogenated polycarbosilane; where the halogenated polycarbosilane contains 0.1 to 80 weight percent halogen.

Claim 6

Independent Claim 101 words

A method of preparing a halogenating polycarbosilane, which method comprises reacting a polycarbosilane with a halogenating agent selected from the group consisting of chlorine, bromine, PCl 5 , PBr 5 , SbCl 5 , N-chlorosuccinimide, N-bromosuccinimide, SOCl 2 , and mixtures of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine, where the polycarbosilane contains at least 0.1 weight percent Si-H groups, and thereafter separating the halogenated polycarbosilane; where the halogenated polycarbosilane contains 0.1 to 80 weight percent halogen.

Claim 7

Dependent Claim 35 words

A method as defined in claim 4 where the halogenating agent is chlorine, where the treatment temperature is less than about 50° C., and where the halogenated polycarbosilane containing 0.5 to 35 weight percent chlorine.

Claim 8

Dependent Claim 17 words

A method as defined in claim 5 where the treatment temperature is less than about 5° C.

Claim 9

Dependent Claim 24 words

A method as defined in claim 4 where the halogenating agent is bromine and the halogenated polycarbosilane contains 0.5 to 55 weight percent bromine.

Claim 10

Dependent Claim 17 words

A method as defined in claim 7 where the treatment temperature is less than about 5° C.

Claim 11

Dependent Claim 25 words

A method as defined in claim 4 where the halogenating agent is sulfonyl chloride and the halogenated polycarbosilane contains 0.5 to 35 weight percent chlorine.

Claim 12

Dependent Claim 45 words

A method as defined in claim 4 where the halogenating agent is PCl 5 or PBr 5 and the halogenated polycarbosilane contains 0.5 to 35 weight percent chlorine if the halogen is chlorine or 0.5 to 55 weight percent bromine if the halogen is bromine.

Claim 13

Dependent Claim 25 words

A method as defined in claim 4 where the halogenating agent is SbCl 5 and the halogenated polycarbosilane contains 0.5 to 35 weight percent chlorine.

Claim 14

Dependent Claim 43 words

A method as defined in claim 4 where the halogenating agent is N-chlorosuccinimide or N-bromosuccinimide and the halogenated polycarbosilane contains 0.5 to 35 weight percent chlorine if the halogen is chlorine or 0.5 to 55 weight percent bromine if the halogen is bromine.

Claim 15

Dependent Claim 74 words

A method as defined in claim 4 where the halogenating agent is a mixture of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine and the halogenated polycarbosilanes contains 0.5 to 35 weight percent chlorine if the halogen is chlorine or 0.5 to 55 weight percent bromine if the halogen is bromine.

Claim 16

Dependent Claim 23 words

A method as defined in claim 13 where CH e X f is CCl 4 and the free radical initiator is benzoyl peroxide.

Claim 17

Independent Claim 107 words

A method of preparing a R' radical-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with a reagent or mixture of reagents selected from the group consisting of Grignard reagents having the general formula R'MgX' and organolithium compounds having the general formula R'Li where X' is chlorine, bromine, or iodine and R' is an alkyl radical containing 1 to 20 carbon atoms, a vinyl radical, or a phenyl radical, at a temperature of 0° to 120° C., in a solvent in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R' radical-containing polycarbosilane.

Claim 18

Independent Claim 107 words

A method of preparing a R' radical-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with a reagent or mixture of reagents selected from the group consisting of Grignard reagents having the general formula R'MgX' and organolithium compounds having the general formula R'Li where X' is chlorine, bromine, or iodine and R' is an alkyl radical containing 1 to 20 carbon atoms, a vinyl radical, or a phenyl radical, at a temperature of 0° to 120° C., in a solvent in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R' radical-containing polycarbosilane.

Claim 19

Dependent Claim 117 words

A method as defined in claim 15 where the halogenated polycarbosilane is prepared by treating a polycarbosilane with a halogenating agent selected from the group consisting of chlorine, bromine, PCl 5 , PBr 5 , SbCl 5 , N-chlorosuccinimide, N-bromosuccinimide, SOCl 2 , and mixture of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine, where the polycarbosilane contains at least 0.1 weight percent Si-H groups, and where the halogenated polycarbosilane contains 0.5 to 35 weight percent halogen if the halogen is chlorine or 0.5 to 55 weight percent halogen if the halogen is bromine.

Claim 20

Dependent Claim 13 words

A method as defined in claim 16 where R' is a methyl radical.

Claim 21

Dependent Claim 13 words

A method as defined in claim 16 where R' is a vinyl radical.

Claim 22

Dependent Claim 13 words

A method as defined in claim 16 where R' is a phenyl radical.

Claim 23

Dependent Claim 37 words

A method as defined in claim 16 where the halogenated polycarbosilane is reacted with a mixture of reagents where R' in one reagent is a methyl radical and in a second reagent R' is a vinyl radical.

Claim 24

Dependent Claim 37 words

A method as defined in claim 16 where the halogenated polycarbosilane is reacted with a mixture of reagents where R' in one reagent is a vinyl radical and in a second reagent R' is a n-octyl radical.

Claim 25

Dependent Claim 37 words

A method as defined in claim 16 where the halogenated polycarbosilane is reacted with a mixture of reagents where R' in one reagent is a vinyl radical and in a second reagent R' is a n-dodecyl radical.

Claim 26

Dependent Claim 12 words

A R' radical-containing polycarbosilane as prepared by the method of claim 17.

Claim 27

Dependent Claim 12 words

A R' radical-containing polycarbosilane as prepared by the method of claim 20.

Claim 28

Dependent Claim 12 words

A R' radical-containing polycarbosilane as prepared by the method of claim 22.

Claim 29

Independent Claim 123 words

A method of preparing a R"O-- or RO-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with a reagent selected from the group consisting of (i) carbinols having the general formula R"OH, (ii) alcoholates having the general formula R"OM, and (iii) alkyl orthoformates having the general formula (RO) 3 CH wherein R" is a alkyl radical containing 1 to 4 carbon atoms or a phenyl radical, R is an alkyl radical containing 1 to 4 carbon atoms, and M is sodium, potassium, or lithium, at a temperature of 0° to 110° C., in a solvent, in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R"O-- or RO-containing polycarbosilane.

Claim 30

Independent Claim 123 words

A method of preparing a R"O-- or RO-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with a reagent selected from the group consisting of (i) carbinols having the general formula R"OH, (ii) alcoholates having the general formula R"OM, and (iii) alkyl orthoformates having the general formula (RO) 3 CH wherein R" is a alkyl radical containing 1 to 4 carbon atoms or a phenyl radical, R is an alkyl radical containing 1 to 4 carbon atoms, and M is sodium, potassium, or lithium, at a temperature of 0° to 110° C., in a solvent, in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R"O-- or RO-containing polycarbosilane.

Claim 31

Dependent Claim 117 words

A method as defined in claim 26 where the halogenated polycarbosilane is prepared by reacting a polycarbosilane with a halogenating agent selected from the group consisting of chlorine, bromine, PCl 5 , PBr 5 , SbCl 5 , N-chlorosuccinimide, N-bromosuccinimide, SOCl 2 , and mixtures of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine, where the polycarbosilane contains at least 0.1 weight percent Si-H groups, and where the halogenated polycarbosilane contains 0.5 to 35 weight percent halogen if the halogen is chlorine or 0.5 to 55 weight percent halogen if the halogen is bromine.

Claim 32

Dependent Claim 14 words

A method as defined in claim 27 where R" and R are methyl radicals.

Claim 33

Dependent Claim 13 words

A R"O-- or RO-containing polycarbosilane as prepared by the method of claim 26.

Claim 34

Dependent Claim 13 words

A R"O-- or RO-containing polycarbosilane as prepared by the method of claim 28.

Claim 35

Independent Claim 108 words

A method of preparing a R'" 2 N-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with an aminolysis reagent having the general formula NHR'" 2 wherein R'" is hydrogen, an alkyl radical containing 1 to 4 carbon atoms, a phenyl radical or a --SiR iv 3 radical wherein R iv is an alkyl radical containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, at a temperature of from 25° to 100° C., in a solvent in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R'" 2 N-containing polycarbosilane.

Claim 36

Independent Claim 108 words

A method of preparing a R'" 2 N-containing polycarbosilane, which method consists of reacting under anhydrous conditions, a halogenated polycarbosilane with an aminolysis reagent having the general formula NHR'" 2 wherein R'" is hydrogen, an alkyl radical containing 1 to 4 carbon atoms, a phenyl radical or a --SiR iv 3 radical wherein R iv is an alkyl radical containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, at a temperature of from 25° to 100° C., in a solvent in which the halogenated polycarbosilane is soluble and which does not react with the halogenated polycarbosilane, and thereafter recovering the R'" 2 N-containing polycarbosilane.

Claim 37

Dependent Claim 117 words

A method as defined in claim 31 where the halogenated polycarbosilane is prepared by reacting a polycarbosilane with a halogenating agent selected from the group consisting of chlorine, bromine, PCl 5 , PBr 5 , SbCl 5 , N-chlorosuccinimide, N-bromosuccinimide, SOCl 2 , and mixtures of CH e X f and a free radical initiator where e is 0 or 1, f is 3 or 4, the sum (e+f) is 4, and X is chlorine or bromine, where the polycarbosilane contains at least 0.1 weight percent Si-H groups, and where the halogenated polycarbosilane contains 0.5 to 35 weight percent halogen if the halogen is chlorine or 0.5 to 55 weight percent halogen if the halogen is bromine.

Claim 38

Dependent Claim 15 words

A method as defined in claim 32 where the aminolysis reagent is NH 3 .

Claim 39

Dependent Claim 17 words

A method as defined in claim 32 where the aminolysis reagent is CH 3 NH 2 .

Claim 40

Dependent Claim 13 words

A R'" 2 N-containing polycarbosilane as prepared by the method of claim 31.

Claim 41

Dependent Claim 13 words

A R'" 2 N-containing polycarbosilane as prepared by the method of claim 33.

Claim 42

Dependent Claim 13 words

A CH 3 NH-containing polycarbosilane as prepared by the method of claim 34.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1991-08-02	1992-02-01	1992-08-02	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1995-08-02	1996-02-01	1996-08-02	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1999-08-02	2000-02-01	2000-08-02	$7700.00	Window Closed / Lapsed

Preceramic polycarbosilane derivatives

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