Process for the preparation of polymetallo(disily)silazane polymers and the polymers therefrom

Claim 2

A process for preparing an R 3 'SiNH-containing metallosilazane polymer, which process consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a chlorine-containing disilane or a mixture of chlorine-containing disilanes of a general formula (Cl.sub.a R.sub.b Si).sub.2, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide at a temperature in the range of 25° C. to 300° C. while distilling byproduced volatile products, wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a+b) is equal to three; the metal atom of said halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 3

A process as defined in claim 1 where said R 3 'SiNH-containing metallosilazane polymer contains 0.05 to 10.0 weight percent of said metal atom.

Claim 4

A process as defined in claim 2 wherein said metal halide is selected from the group consisting of BBr 3 , TiCl 4 , and PCl 3 .

Claim 5

A process as defined in claim 3 wherein said metal halide is BBr 3 and said R 3 'SiNH-containing metallosilazane polymer contains 0.5 to 2.5 weight percent boron.

Claim 6

A process as defined in claim 3 wherein said metal halide is TiCl 4 and said R 3 'SiNH-containing metallosilazane polymer contains 1.0 to 5.0 weight percent titanium.

Claim 7

A process as defined in claim 3 wherein said metal halide is PCl 3 and said R 3 'SiNH-containing metallosilazane polymer contains 0.5 to 5.0 weight percent phosphorous.

Claim 8

A process as defined in claim 2 wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 9

A process as defined in claim 3 wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 )CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 10

A process as defined in claim 4 wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 11

A process as defined in claim 5 wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 12

A process as defined in claim 6 wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 13

A process as defined in claim 1 wherein the temperature is in the range of 125° C. to 300° C.

Claim 14

A process as defined in claim 2 wherein the temperature is in the range of 125° C. to 300° C.

Claim 15

A process as defined in claim 3 wherein the temperature is in the range of 125° C. to 300° C.

Claim 16

A process as defined in claim 7 wherein the temperature is in the range of 125° C. to 300° C.

Claim 17

A process as defined in claim 8 wherein the temperature is in the range of 125° C. to 300° C.

Claim 18

A process as defined in claim 9 wherein the temperature is in the range of 125° C. to 300° C.

Claim 19

A process as defined in claim 10 wherein the temperature is in the range of 125° C. to 300° C.

Claim 20

A process as defined in claim 11 wherein the temperature is in the range of 125° C. to 300° C.

Claim 21

A process for preparing an R 3 'SiNH-containing metallosilazane polymer, which process consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a chlorine-containing disilane or a mixture of chlorine-containing disilanes of the general formula (Cl.sub.a R.sub.b Si).sub.2, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide at a temperature in the range of 25° C. and the boiling point of said metal halide and thereafter removing byproduced volatile products by distillation at a temperature of less than 300° C., wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a +b) is equal to three; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 22

A process for preparing an R 3 'SiNH-containing metallosilazane polymer, which process consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a chlorine-containing disilane or a mixture of chlorine-containing disilanes of the general formula (Cl.sub.a R.sub.b Si).sub.2, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide at a temperature in the range of 25° C. and the boiling point of said metal halide and thereafter removing byproduced volatile products by distillation at a temperature of less than 300° C., wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a +b) is equal to three; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 23

A process as defined in claim 20 wherein said chlorine-containing disilane or mixture of chlorine-containing disilanes, said disilazane, and said metal halide are refluxed at a temperature in the range of 25° C. and the boiling point of said metal halide.

Claim 24

A process as defined in claim 20 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.05 to 10.0 weight percent of said metal atom and wherein said metal halide is selected from the group consisting of BBr 3 , TiCl 4 , and PCl 3 .

Claim 25

A process as defined in claim 21 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.05 to 10.0 weight percent of said metal atom and wherein said metal halide is selected from the group consisting of BBr 3 , TiCl 4 , and PCl 3 .

Claim 26

A process as defined in claim 22 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.5 to 5.0 weight percent of said metal atom; wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 2 Si] 2 NH.

Claim 27

A process as defined in claim 23 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.5 to 5.0 weight percent of said metal atom; wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixture, the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 2 Si] 2 NH.

Claim 28

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 1.

Claim 29

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 2.

Claim 30

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 3.

Claim 31

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 4.

Claim 32

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 5.

Claim 33

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 6.

Claim 34

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 7.

Claim 35

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 8.

Claim 36

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 9.

Claim 37

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 10.

Claim 38

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 11.

Claim 39

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 12.

Claim 40

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 13.

Claim 41

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 14.

Claim 42

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 15.

Claim 43

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 16.

Claim 44

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 17.

Claim 45

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 18.

Claim 46

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 19.

Claim 47

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 20.

Claim 48

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 24.

Claim 49

A composition of matter which is an R 3 'SiNH-containing metallosilazane polymer which is prepared by the process of claim 25.

Claim 50

A process for preparing a ceramic material which consists of heating an R 3 'SiNH-containing metallosilazane in an inert atmosphere or in a vacuum to at least a temperature of 750° C. until the R 3 'SiNH-containing metallosilazane polymer is converted to ceramic material, which R 3 'SiNH-containing metallosilazane polymer is obtained by a process which consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a chlorine-containing, disilane or a mixture of chlorine-containing disilanes, wherein the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms, of said disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide at a temperature in the range of 25° C. to 300° C. while distilling byproduced volatile products, wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a+b) is equal to three; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 51

A process for preparing a ceramic material which consists of heating an R 3 'SiNH-containing metallosilazane in an inert atmosphere or in a vacuum to at least a temperature of 750° C. until the R 3 'SiNH-containing metallosilazane polymer is converted to ceramic material, which R 3 'SiNH-containing metallosilazane polymer is obtained by a process which consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a chlorine-containing, disilane or a mixture of chlorine-containing disilanes, wherein the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms, of said disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide at a temperature in the range of 25° C. to 300° C. while distilling byproduced volatile products, wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a+b) is equal to three; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 52

A process as defined in claim 48 wherein said R 3 'SiNH-containing metallosilazane contains 0.05 to 10.0 weight percent of said metal atom and wherein said metal halide is selected from the group consisting of BBr 3 , TiCl 4 , and PCl 3 .

Claim 53

A process as defined in claim 49 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.5 to 5.0 weight percent of said metal atom; wherein a mixture of chlorine-containing disilanes is used; wherein the mixture contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 54

A process as defined in claim 50 wherein the temperature is in the range of 125° C. and 300° C.

Claim 55

A ceramic material is prepared by the process of claim 48.

Claim 56

A ceramic material as prepared by the process of claim 49.

Claim 57

A ceramic material as prepared by the process of claim 50.

Claim 58

A ceramic material as prepared by the process of claim 51.

Claim 59

A process for preparing an R 3 'SiNH-containing metallosilazane polymer, which process consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide with (i) a mixture of a chlorine-containing disilane having the general formula (Cl.sub.a R.sub.b Si).sub.2 and a chlorine-containing monosilane having the general formula R.sub.n 'SiCl.sub.4-n, (ii) a mixture of chlorine-containing disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2 mixed with a chlorine-containing monosilane having the general formula R.sub.n 'SiCl.sub.4-n, or (iii) a mixture of chlorine-containing disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2 mixed with a mixture of chlorine-containing monosilanes having the general formula R.sub.n 'SiCl.sub.4-n at a temperature in the range of 25° C. to 300° C. while distilling byproduced volatile products, wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a+b) is equal to three; n has a value of 1 or 2; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 60

A process for preparing an R 3 'SiNH-containing metallosilazane polymer, which process consists of contacting and reacting in an inert, essentially anhydrous atmosphere, a disilazane having the general formula (R.sub.3 'Si).sub.2 NH, and a metal halide with (i) a mixture of a chlorine-containing disilane having the general formula (Cl.sub.a R.sub.b Si).sub.2 and a chlorine-containing monosilane having the general formula R.sub.n 'SiCl.sub.4-n, (ii) a mixture of chlorine-containing disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2 mixed with a chlorine-containing monosilane having the general formula R.sub.n 'SiCl.sub.4-n, or (iii) a mixture of chlorine-containing disilanes having the general formula (Cl.sub.a R.sub.b Si).sub.2 mixed with a mixture of chlorine-containing monosilanes having the general formula R.sub.n 'SiCl.sub.4-n at a temperature in the range of 25° C. to 300° C. while distilling byproduced volatile products, wherein R is a vinyl radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; R' is a vinyl radical, a hydrogen radical, an alkyl radical containing 1-3 carbon atoms, or a phenyl radical; a has a value of 0.5-3; b has a value of 0-2.5; the sum of (a+b) is equal to three; n has a value of 1 or 2; the metal atom of said metal halide is selected from the group consisting of boron, phosphorous, and titanium; said metal halide is a liquid at the reaction temperature; and the boiling point of said metal halide is less than 300° C.

Claim 61

A process as defined in claim 56 wherein said R 3 'SiNH-containing metallosilazane polymer contains 0.05 to 10.0 weight percent of said metal atom and wherein said metal halide is selected from the group consisting of BBr 3 , TiCl 4 , and PCl 3 .

Claim 62

A process as defined in claim 57 wherein said R 3 'NH-containing metallosilazane polymer contains 0.5 to 5.0 weight percent of said metal atom; wherein the mixtures (ii) or (iii) are used; wherein the chlorine-containing disilanes contain [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; wherein, in the mixtures (ii) or (iii), the number of diorgano-substituted silicon atoms does not exceed the number of monoorgano-substituted silicon atoms; and wherein the disilazane is [(CH 3 ) 3 Si] 2 NH.

Claim 63

A process as defined in claim 58 wherein the temperature is in the range of 125° C. and 300° C. and the chlorine-containing monosilane or mixture of chlorine-containing monosilanes contains phenyl radicals.

Claim 64

A process as defined in claim 59 wherein the chlorine-containing monosilanes or mixture of chloro-containing monosilanes further contains vinyl radicals.

Claim 65

A composition of matter as prepared by the process of claim 56.

Claim 66

A composition of matter as prepared by the process of claim 58.

Claim 69

A process as defined in claim 63 wherein a mixture of disilanes is used; wherein the mixture of disilanes contains [Cl 2 (CH 3 )Si] 2 , [Cl(CH 3 ) 2 Si] 2 , and Cl(CH 3 ) 2 SiSi(CH 3 )Cl 2 ; and wherein said metal halide is present in such amounts so that the resulting metallosilazane polymer contains 0.5 to 5.0 weight percent of said metal atom.

Claim 70

A process as defined in claim 64 wherein said ceramic article is a fiber.

Claim 71

A ceramic article as prepared by the process of claim 63.

Claim 72

A ceramic article as prepared by the process of claim 64.

Claim 73

A ceramic article as prepared by the process of claim 65.