Hydridosiloxanes as precursors to ceramic products

Claim 1

A method of preparing a ceramic precursor which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a hydroxyl-containing compound of the formula R'--OH, wherein R' is hydrogen, C 1 -C 10 alkyl, or aryl of 1-2 rings, and may be substituted with hydroxyl, lower alkyl, lower alkoxy, halogen, silyl, amino groups, or combinations thereof, in an inert atmosphere in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by OR' moieties.

Claim 2

A method of preparing a ceramic precursor which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a hydroxyl-containing compound of the formula R'--OH, wherein R' is hydrogen, C 1 -C 10 alkyl, or aryl of 1-2 rings, and may be substituted with hydroxyl, lower alkyl, lower alkoxy, halogen, silyl, amino groups, or combinations thereof, in an inert atmosphere in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by OR' moieties.

Claim 12

A method of preparing a silicious ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a hydroxyl-containing compound of the formula R'--OH, wherein R' is hydrogen, C 1 -C 10 alkyl, or aryl of 1-2 rings, and may be substituted with hydroxyl, lower alkyl, lower alkoxy, halogen, silyl, or amino groups, or combinations thereof, in an inert atmosphere in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by OR' moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 13

A method of preparing a silicious ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a hydroxyl-containing compound of the formula R'--OH, wherein R' is hydrogen, C 1 -C 10 alkyl, or aryl of 1-2 rings, and may be substituted with hydroxyl, lower alkyl, lower alkoxy, halogen, silyl, or amino groups, or combinations thereof, in an inert atmosphere in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by OR' moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 20

A method of preparing a silicious ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si--H bonds per mer unit; (b) introducing carbon-containing moieties into said polymer by reaction with a compound containing an unsaturated carbon-carbon bond, in the presence of a catalyst effective to activate Si--H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by carbon-containing moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 21

A method of preparing a silicious ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si--H bonds per mer unit; (b) introducing carbon-containing moieties into said polymer by reaction with a compound containing an unsaturated carbon-carbon bond, in the presence of a catalyst effective to activate Si--H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced by carbon-containing moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 32

A method of preparing a silicious, nitrogen-containing ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) introducing nitrogen-containing moieties into said polymer by reaction with a compound HNR"2 wherein the R" are independently selected from hydrogen, lower alkyl, silyl, and aryl of 1-2 rings, in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced with nitrogen-containing moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 33

A method of preparing a silicious, nitrogen-containing ceramic material, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) introducing nitrogen-containing moieties into said polymer by reaction with a compound HNR"2 wherein the R" are independently selected from hydrogen, lower alkyl, silyl, and aryl of 1-2 rings, in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which hydrogen atoms in the hydridosiloxane polymer have been replaced with nitrogen-containing moieties; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 42

A method of making a silicious ceramic material containing the metal M, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a compound selected from the group consisting of ML a and M-OH, wherein M is a metal atom, L is an organic ligand associated therewith, and a represents the molar ratio L/M in said complex, in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which said activated Si-H bonds have been replaced by Si-M bonds; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 43

A method of making a silicious ceramic material containing the metal M, which comprises: (a) providing a hydridosiloxane polymer containing one or more Si-H bonds per mer unit; (b) reacting said hydridosiloxane polymer with a compound selected from the group consisting of ML a and M-OH, wherein M is a metal atom, L is an organic ligand associated therewith, and a represents the molar ratio L/M in said complex, in the presence of a catalyst effective to activate Si-H bonds, to give a ceramic precursor in which said activated Si-H bonds have been replaced by Si-M bonds; and (c) pyrolyzing said ceramic precursor at a temperature of at least about 500° C. to give said ceramic material.

Claim 53

A method of preparing a ceramic precursor which comprises: (a) reacting, in the presence of a catalyst effective to activate Si--H bonds, a hydridosiloxane monomer H m Si(OR 1 )4-m with an alcohol R 2 OH, wherein R 1 and R 2 are selected from the group consisting of: (i) hydrogen; (ii) hydroxyl; (iii) C 1 -C 10 alkyl, which is either unsubstituted or substituted with hydroxyl, lower alkyl, lower alkoxy, halogens, silyl or NR"2 groups, wherein R" is hydrogen or lower alkyl; (iv) C 1 -C 10 alkoxy, optionally substituted as in (iii); (v) aryl of 1-2 rings, optionally substituted as in (iii); (vi) NR" 2 ; (vii) silyl; and (viii) ML a , OML a , and NR"ML a , wherein M is a metal atom selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, boron, aluminum, phosphorus, transition metals, lanthanides and actinides and L is a ligand associated therewith which is selected from the group consisting of carbonyl, cyano, cyclopentadienyl, phenyl, halide, alkoxy and αC|Cα, where α is lower alkyl or phenyl, to give the substituted siloxane monomer Si(OR 1 ) 4-m (OR 2 ) m ; and (b) hydrolyzing the substituted siloxane monomer in the presence of a Lewis acid or base catalyst, to give a polysiloxane ceramic precursor.

Claim 54

A method of preparing a ceramic precursor which comprises: (a) reacting, in the presence of a catalyst effective to activate Si--H bonds, a hydridosiloxane monomer H m Si(OR 1 )4-m with an alcohol R 2 OH, wherein R 1 and R 2 are selected from the group consisting of: (i) hydrogen; (ii) hydroxyl; (iii) C 1 -C 10 alkyl, which is either unsubstituted or substituted with hydroxyl, lower alkyl, lower alkoxy, halogens, silyl or NR"2 groups, wherein R" is hydrogen or lower alkyl; (iv) C 1 -C 10 alkoxy, optionally substituted as in (iii); (v) aryl of 1-2 rings, optionally substituted as in (iii); (vi) NR" 2 ; (vii) silyl; and (viii) ML a , OML a , and NR"ML a , wherein M is a metal atom selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, boron, aluminum, phosphorus, transition metals, lanthanides and actinides and L is a ligand associated therewith which is selected from the group consisting of carbonyl, cyano, cyclopentadienyl, phenyl, halide, alkoxy and αC|Cα, where α is lower alkyl or phenyl, to give the substituted siloxane monomer Si(OR 1 ) 4-m (OR 2 ) m ; and (b) hydrolyzing the substituted siloxane monomer in the presence of a Lewis acid or base catalyst, to give a polysiloxane ceramic precursor.

Claim 55

A method of preparing a ceramic precursor which comprises: (a) reacting, in the presence of a catalyst effective to activate Si-H bonds, a hydridosiloxane monomer H m Si(OR 1 ) 4-m with an alcohol R 2 OH, wherein R 1 and R 2 are selected from the group consisting of: (i) hydrogen; (ii) hydroxyl; (iii) C 1 -C 10 alkyl, which is either unsubstituted or substituted with hydroxyl, lower alkyl, lower alkoxy, halogens, silyl or NR"2 groups, wherein R" is hydrogen or lower alkyl; (iv) C 1 -C 10 alkoxy, optionally substituted as in (iii); (v) aryl of 1-2 rings, optionally substituted as in (iii); (vi) NR" 2 ; (vii) silyl; and (viii) ML a , OML a , and NR"ML a , wherein M is a metal atom selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, boron, aluminum, phosphorus, transition metals, lanthanides and actinides and L is a ligand associated therewith which is selected from the group consisting of carbonyl, cyano, cyclopentadienyl, phenyl, halide, alkoxy and αC|Cα, where α is lower alkyl or phenyl, to give the substituted siloxane monomer Si(OR 1 ) 4-m (OR 2 ) m ; and (b) hydrolyzing the substituted siloxane monomer in the presence of a Lewis acid or base catalyst, to give a polysiloxane ceramic precursor.

Claim 56

A method of preparing a ceramic precursor which comprises: (a) reacting, in the presence of a catalyst effective to activate Si-H bonds, a hydridosiloxane monomer H m Si(OR 1 ) 4-m with an alcohol R 2 OH, wherein R 1 and R 2 are selected from the group consisting of: (i) hydrogen; (ii) hydroxyl; (iii) C 1 -C 10 alkyl, which is either unsubstituted or substituted with hydroxyl, lower alkyl, lower alkoxy, halogens, silyl or NR"2 groups, wherein R" is hydrogen or lower alkyl; (iv) C 1 -C 10 alkoxy, optionally substituted as in (iii); (v) aryl of 1-2 rings, optionally substituted as in (iii); (vi) NR" 2 ; (vii) silyl; and (viii) ML a , OML a , and NR"ML a , wherein M is a metal atom selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, boron, aluminum, phosphorus, transition metals, lanthanides and actinides and L is a ligand associated therewith which is selected from the group consisting of carbonyl, cyano, cyclopentadienyl, phenyl, halide, alkoxy and αC|Cα, where α is lower alkyl or phenyl, to give the substituted siloxane monomer Si(OR 1 ) 4-m (OR 2 ) m ; and (b) hydrolyzing the substituted siloxane monomer in the presence of a Lewis acid or base catalyst, to give a polysiloxane ceramic precursor.

Claim 57

A method of preparing a ceramic precursor which comprises: (a) providing a hydridosiloxane starting material containing one or more Si-H bonds; and (b) reacting said hydridosiloxane starting material with a coupling agent H--Z--H, wherein Z contains one or more elements selected from the group consisting of oxygen, nitrogen, sulfur and phosphorus, to give a ceramic precursor containing --Z-- bridges.

Claim 58

A method of preparing a ceramic precursor which comprises: (a) providing a hydridosiloxane starting material containing one or more Si-H bonds; and (b) reacting said hydridosiloxane starting material with a coupling agent H--Z--H, wherein Z contains one or more elements selected from the group consisting of oxygen, nitrogen, sulfur and phosphorus, to give a ceramic precursor containing --Z-- bridges.