US4962175A
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US
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Alkylpoly (polysilyl) azane preceramic polymers
Assignee: Dow Silicones Corp
•
Filing: 1986-12-22
•
Granted: 1990-10-09
•
Expires: 2006-12-22
Abstract
Abstract Alkylpoly(polysilyl)azanes are prepared by the reaction of chlorine-containing polysilane preceramic polymers and various disilazanes. The alkylpoly(polysily)azanes may be converted to ceramic materials by pyrolysis at elevated temperatures.
Inventors
- 👤 Duane R. Bujalski
- 👤 Gary E. Legrow
- 👤 Thomas F. Lim
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 07:01
CPC Classifications
C; C04; C04B; C04B35/00; C04B35/515; C04B35/56; C04B35/565; C04B35/571; C08; C08G; C08G77/00; C08G77/60; C08G77/62
Claims Analysis
Total Claims: 59
Claim 1
Independent Claim
87 words
An alkylpoly(polysilyl)azane of the average formula (R.sub.2 Si)(RSi) (I) containing from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " wherein each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical.
Claim 2
Dependent Claim
87 words
An alkylpoly(polysilyl)azane of the average formula (R.sub.2 Si)(RSi) (I) containing from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " wherein each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical.
Claim 3
Dependent Claim
13 words
An alkylpoly(polysilyl)azane as claimed in claim 1 wherein R is a methyl radical.
Claim 4
Dependent Claim
13 words
An alkylpoly(polysilyl)azane as claimed in claim 1 wherein R" is a methyl radical.
Claim 5
Dependent Claim
14 words
An alkylpoly(polysilyl)azane as claimed in claim 1 wherein R and R" are methyl radicals.
Claim 6
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 1 wherein the alkylpoly(poylsilyl)azane contains less than 2 weight percent chlorine or bromine.
Claim 7
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 1 wherein the alkylpoly(poylsilyl)azane contains less than 0.5 weight percent chlorine or bromine.
Claim 8
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 4 wherein the alkylpoly(poylsilyl)azane contains less than 2 weight percent chlorine or bromine.
Claim 9
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 4 wherein the alkylpoly(poylsilyl)azane contains less than 0.5 weight percent chlorine or bromine.
Claim 10
Dependent Claim
170 words
An alkylpoly(polysilyl)azane of the average formula (R.sub.2 Si)(RSi)(R'Si) (II) where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms wherein each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 )z-- where each A is independently selected from a hydrogen atom or alkyl radicals 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, wherein there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi), and 1 to 99 mole percent (R'Si) units, and wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " wherein each R" is independently selected from a vinyl radical, alkyl radicals having 1 to 4 carbon atoms, or a phenyl radical.
Claim 11
Dependent Claim
170 words
An alkylpoly(polysilyl)azane of the average formula (R.sub.2 Si)(RSi)(R'Si) (II) where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms wherein each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 )z-- where each A is independently selected from a hydrogen atom or alkyl radicals 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, wherein there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi), and 1 to 99 mole percent (R'Si) units, and wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " wherein each R" is independently selected from a vinyl radical, alkyl radicals having 1 to 4 carbon atoms, or a phenyl radical.
Claim 12
Dependent Claim
37 words
An alkylpoly(polysilyl)azane as claimed in claim 9 which contains from 0 to 40 mole percent ((CH 3 ) 2 Si) units, 40 to 99 mole percent (CH 3 Si), and 1 to 30 mole percent (R'Si) units.
Claim 13
Dependent Claim
37 words
An alkylpoly(polysilyl)azane as claimed in claim 10 which contains from 0 to 10 mole percent ((CH 3 ) 2 Si) units, 80 to 99 mole percent (CH 3 Si), and 1 to 20 mole percent (R'Si) units.
Claim 14
Dependent Claim
13 words
An alkylpoly(polysilyl)azane as claimed in claim 10 wherein R" is a methyl radical.
Claim 15
Dependent Claim
13 words
An alkylpoly(polysilyl)azane as claimed in claim 10 wherein R' is an n-octyl radical.
Claim 16
Dependent Claim
13 words
An alkylpoly(polysilyl)azane as claimed in claim 10 wherein R' is a phenyl radical.
Claim 17
Dependent Claim
24 words
An alkylpoly(polysilyl)azane as claimed in claim 10 which contains both (CH 3 (CH 2 ) 7 Si) and (C 6 H 5 Si) units.
Claim 18
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 10 wherein the alkylpoly(polysilyl)azane contains less than 2 weight percent chlorine or bromine.
Claim 19
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 10 wherein the alkylpoly(polysilyl)azane contains less than 0.5 weight percent chlorine or bromine.
Claim 20
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 15 wherein the alkylpoly(polysilyl)azane contains less than 2 weight percent chlorine or bromine.
Claim 21
Dependent Claim
19 words
An alkylpoly(polysilyl)azane as claimed in claim 15 wherein the alkylpoly(polysilyl)azane contains less than 0.5 weight percent chlorine or bromine.
Claim 22
Independent Claim
217 words
A method of preparing an alkylpoly(polysilyl)azane having the average formula (R.sub.2 Si)(RSi) (I) where there are from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " where each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, which method comprises (A) reacting under anhydrous conditions a (1) polysilane having the average formula (R.sub.2 Si)(RSi) (III) in which there are from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, wherein each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, and where the remaining bonds on silicon are attached to other silicon atoms and either chlorine atoms or bromine atoms with (2) a disilazane of general formula (R 3 "Si) 2 NH wherein each R" is independently selected from hydrogen, alkyl radicals containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical at a temperature of 50° to 300° C. and (B) thereafter recovering the alkylpoly(polysilyl)azane.
Claim 23
Independent Claim
217 words
A method of preparing an alkylpoly(polysilyl)azane having the average formula (R.sub.2 Si)(RSi) (I) where there are from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " where each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, which method comprises (A) reacting under anhydrous conditions a (1) polysilane having the average formula (R.sub.2 Si)(RSi) (III) in which there are from 0 to 60 mole percent (R 2 Si) units and 40 to 100 mole percent (RSi) units, wherein each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, and where the remaining bonds on silicon are attached to other silicon atoms and either chlorine atoms or bromine atoms with (2) a disilazane of general formula (R 3 "Si) 2 NH wherein each R" is independently selected from hydrogen, alkyl radicals containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical at a temperature of 50° to 300° C. and (B) thereafter recovering the alkylpoly(polysilyl)azane.
Claim 24
Dependent Claim
49 words
A method as claimed in claim 20 wherein the reaction in step A is carried out in the presence of 0.001 to 10 weight percent of a catalyst selected from the group consisting of ammonium halides, tertiary organic amines, quaternary ammonium halides, quaternary phosphonium halides, hexamethylphosphoramide, and silver cyanide.
Claim 25
Dependent Claim
69 words
A method as claimed in claim 21 wherein the reaction in step A is carried out in the presence of 0.1 to 2.0 weight percent of a catalyst selected from the group consisting of quaternary ammonium halides of general formula W 4 NX', quaternary phosphonium halides of the general formula W 4 PX', and hexamethylphosphoramide where W is an alkyl or aryl radical and X is a halogen atom.
Claim 26
Dependent Claim
59 words
A method as claimed in claim 22 wherein the catalyst is selected from the group consisting of quaternary ammonium halides of general formula W 4 NX' and quaternary phosphonium halides of the general formula W 4 PX' where W is an alkyl radical contain 1 to 6 carbon atoms or a phenyl radical and X' is chlorine or bromine.
Claim 27
Dependent Claim
16 words
A method as claimed in claim 23 wherein the catalyst is tetra-n-butylphosphonium bromide or tetra-n-butylphosphonium chloride.
Claim 28
Dependent Claim
35 words
A method as claimed in claim 20 wherein the disilazane is present in a stoichiometric excess relative to the chlorine or bromine content of polysilane III whereby the disilazane acts as both reactant and solvent.
Claim 29
Dependent Claim
35 words
A method as claimed in claim 23 wherein the disilazane is present in a stoichiometric excess relative to the chlorine or bromine content of polysilane III whereby the disilazane acts as both reactant and solvent.
Claim 30
Dependent Claim
24 words
A method as claimed in claim 20 wherein the alkylpoly(polysilyl)azane is further treated with ammonia whereby the halide content of the alkylpoly(polysilyl)azane is reduced.
Claim 31
Dependent Claim
30 words
A method as claimed in claim 23 wherein the alkylpoly(polysilyl)azane is further treated with ammonia whereby the halide content of the alkylpoly(polysilyl)azane is reduced to less than 0.5 weight percent.
Claim 32
Dependent Claim
13 words
A method as claimed in claim 20 wherein R is a methyl radical.
Claim 33
Dependent Claim
13 words
A method as claimed in claim 20 wherein R is a methyl radical.
Claim 34
Dependent Claim
14 words
A method as claimed in claim 20 wherein R and R" are methyl radicals.
Claim 35
Dependent Claim
13 words
A method as claimed in claim 23 wherein R is a methyl radical.
Claim 36
Dependent Claim
13 words
A method as claimed in claim 23 wherein R" is a methyl radical.
Claim 37
Dependent Claim
14 words
A method as claimed in claim 23 wherein R and R" are methyl radicals.
Claim 38
Dependent Claim
14 words
A method as claimed in claim 28 wherein R and R" are methyl radicals.
Claim 39
Independent Claim
386 words
A method of preparing an alkylpoly(polysilyl)azane having the average formula (R.sub.2 Si)(RSi)(R'Si) (III) where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, wherein each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 ) z -- where each A is independently selected from a hydrogen atom or 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, wherein there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi) units, and 1 to 99 mole percent (R'Si) units, and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " where each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, which method comprises (A) reacting under anhydrous conditions a (1) polysilane having the average formula (R.sub.2 Si)(RSi)(R'Si) (IV) in which each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 ) z -- where each A is independently selected from a hydrogen atom or alkyl radicals 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 there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi) units, and 1 to 99 mole percent (R'Si) units, wherein the remaining bonds on silicon are attached to other silicon atoms and either chlorine atoms or bromine atoms with (2) a disilazane of general formula (R 3 "Si) 2 NH where each R" is independently selected from hydrogen, alkyl, alkyl radicals containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical at a temperature of 50° to 300° C. and (B) thereafter recovering the alkylpoly)polysilyl)azane.
Claim 40
Independent Claim
386 words
A method of preparing an alkylpoly(polysilyl)azane having the average formula (R.sub.2 Si)(RSi)(R'Si) (III) where each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, wherein each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 ) z -- where each A is independently selected from a hydrogen atom or 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, wherein there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi) units, and 1 to 99 mole percent (R'Si) units, and where there is also bonded to the silicon atoms other silicon atoms and radicals having the formula --NHSiR 3 " where each R" is independently selected from hydrogen, alkyl radicals having 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical, which method comprises (A) reacting under anhydrous conditions a (1) polysilane having the average formula (R.sub.2 Si)(RSi)(R'Si) (IV) in which each R is independently selected from alkyl radicals containing 1 to 4 carbon atoms, each R' is independently selected from the group consisting of alkyl radicals of at least six carbon atoms, phenyl radicals, and radicals of the formula A y X.sub.(3-y) Si(CH 2 ) z -- where each A is independently selected from a hydrogen atom or alkyl radicals 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 there are from 0 to 40 mole percent (R 2 Si) units, 1 to 99 mole percent (RSi) units, and 1 to 99 mole percent (R'Si) units, wherein the remaining bonds on silicon are attached to other silicon atoms and either chlorine atoms or bromine atoms with (2) a disilazane of general formula (R 3 "Si) 2 NH where each R" is independently selected from hydrogen, alkyl, alkyl radicals containing 1 to 4 carbon atoms, a vinyl radical, or a phenyl radical at a temperature of 50° to 300° C. and (B) thereafter recovering the alkylpoly)polysilyl)azane.
Claim 41
Dependent Claim
39 words
A method as claimed in claim 36 wherein the alkylpoly(polysilyl)azane contains from 0 to 40 mole percent ((CH 3 ) 2 Si) units, 40 to 99 mole percent (CH 3 Si), and 1 to 30 mole percent (R'Si) units.
Claim 42
Dependent Claim
39 words
A method as claimed in claim 37 wherein the alkylpoly(polysilyl)azane contains from 0 to 10 mole percent ((CH 3 ) 2 Si) units, 80 to 99 mole percent (CH 3 Si), and 1 to 20 mole percent (R'Si) units.
Claim 43
Dependent Claim
49 words
A method as claimed in claim 37 wherein the reaction in step A is carried out in the presence of 0.001 to 10 weight percent of a catalyst selected from the group consisting of ammonium halides, tertiary organic amines, quaternary ammonium halides, quaternary phosphonium halides, hexamethylphosphoramide, and silver cyanide.
Claim 44
Dependent Claim
68 words
A method as claimed in claim 37 wherein the reaction in step A is carried out in the presence of 0.1 to 2.0 weight percent of a catalyst selected from the group consisting of quaternary ammonium halides of general formula W 4 NX', quaternary phosphonium halides of the general formula W 4 PX', and hexamethylphosphoramide where W is an alkyl or aryl radical and X' is a halogen.
Claim 45
Dependent Claim
59 words
A method as claimed in claim 40 wherein the catalyst is selected from the group consisting of quaternary ammonium halides of general formula W 4 NX' and quaternary phosphonium halides of the general formula W 4 PX' where W is an alkyl radical contain 1 to 6 carbon atoms or a phenyl radical and X' is chlorine or bromine.
Claim 46
Dependent Claim
16 words
A method as claimed in claim 41 wherein the catalyst is tetra-n-butylphosphonium bromide or tetra-n-butylphosphonium chloride.
Claim 47
Dependent Claim
35 words
A method as claimed in claim 37 wherein the disilazane is present in a stoichiometric excess relative to the chlorine or bromine content of polysilane IV whereby the disilazane acts as both reactant and solvent.
Claim 48
Dependent Claim
35 words
A method as claimed in claim 41 wherein the disilazane is present in a stoichiometric excess relative to the chlorine or bromine content of polysilane IV whereby the disilazane acts as both reactant and solvent.
Claim 49
Dependent Claim
24 words
A method as claimed in claim 37 wherein the alkylpoly(polysilyl)azane is further treated with ammonia whereby the halide content of the alkylpoly(polysilyl)azane is reduced.
Claim 50
Dependent Claim
30 words
A method as claimed in claim 41 wherein the alkylpoly(polysilyl)azane is further treated with ammonia whereby the halide content of the alkylpoly(polysilyl)azane is reduced to less than 0.5 weight percent.
Claim 51
Dependent Claim
30 words
A method as claimed in claim 44 wherein the alkylpoly(polysilyl)azane is further treated with ammonia whereby the halide content of the alkylpoly(polysilyl)azane is reduced to less than 0.5 weight percent.
Claim 52
Dependent Claim
20 words
A method as claimed in claim 37 wherein R and R" are methyl radicals and R' is an n-octyl radical.
Claim 53
Dependent Claim
19 words
A method as claimed in claim 41 wherein R" is a methyl radical and R' is an n-octyl radical.
Claim 54
Dependent Claim
19 words
A method as claimed in claim 37 wherein R" is a methyl radical and R' is a phenyl radical.
Claim 55
Dependent Claim
19 words
A method as claimed in claim 41 wherein R" is a methyl radical and R' is a phenyl radical.
Claim 56
Dependent Claim
27 words
A method as claimed in claim 37 wherein the polysilane IV contains both (CH 3 (CH 2 ) 7 Si) and (C 6 H 5 Si) units.
Claim 57
Dependent Claim
27 words
A method as claimed in claim 41 wherein the polysilane IV contains both (CH 3 (CH 2 ) 7 Si) and (C 6 H 5 Si) units.
Claim 58
Dependent Claim
27 words
A method as claimed in claim 43 wherein the polysilane IV contains both (CH 3 (CH 2 ) 7 Si) and (C 6 H 5 Si) units.
Claim 59
Dependent Claim
27 words
A method as claimed in claim 46 wherein the polysilane IV contains both (CH 3 (CH 2 ) 7 Si) and (C 6 H 5 Si) units.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-10-08 | 1994-04-09 | 1994-10-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-10-08 | 1998-04-09 | 1998-10-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-10-08 | 2002-04-09 | 2002-10-09 | $7700.00 | Window Closed / Lapsed |