Process for the preparation of preceramic metallopolysilanes and the polymers therefrom

Claim 1

A method of preparing a halogen-containing metallopolysilane, which method comprises treating a mixture containing 90 to 99.9 weight percent organohalogendisilanes and 0.1 to 10 weight percent reactive metal compound, where the reactive metal compound contains a metal M selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, with 0.001 to 10 weight percent of a rearrangement catalyst at a temperature of 100° to 340° C. while distilling by-produced volatile materials until there is produced a halogen-containing metallopolysilane composed of [R 2 Si], [RSi], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 2

A method of preparing a halogen-containing metallopolysilane, which method comprises treating a mixture containing 90 to 99.9 weight percent organohalogendisilanes and 0.1 to 10 weight percent reactive metal compound, where the reactive metal compound contains a metal M selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, with 0.001 to 10 weight percent of a rearrangement catalyst at a temperature of 100° to 340° C. while distilling by-produced volatile materials until there is produced a halogen-containing metallopolysilane composed of [R 2 Si], [RSi], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 26

A method of preparing a halogen-containing metallopolysilane, which method comprises treating a mixture of organohalogendisilanes containing 0 to 60 weight percent of a monoorganosilane of formula R'SiX 3 and 1 to 20 weight percent reactive metal compound, where R' is an alkyl radical containing five or more carbon atoms or a phenyl radical, X is chlorine or bromine, and the reactive metal compound contains a metal M selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, with 0.001 to 10 weight percent of a rearrangement catalyst at a temperature of 100° to 340° C. while distilling by-produced volatile materials until there is produced a halogen-containing metallopolysilane composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing five or more carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 27

A method of preparing a halogen-containing metallopolysilane, which method comprises treating a mixture of organohalogendisilanes containing 0 to 60 weight percent of a monoorganosilane of formula R'SiX 3 and 1 to 20 weight percent reactive metal compound, where R' is an alkyl radical containing five or more carbon atoms or a phenyl radical, X is chlorine or bromine, and the reactive metal compound contains a metal M selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, with 0.001 to 10 weight percent of a rearrangement catalyst at a temperature of 100° to 340° C. while distilling by-produced volatile materials until there is produced a halogen-containing metallopolysilane composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing five or more carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 58

A method of preparing a R" radical-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with a Grignard reagent having the general formula R"MgX' or an organolithium compound 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 suitable solvent, and thereafter recovering the R" radical-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 59

A method of preparing a R" radical-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with a Grignard reagent having the general formula R"MgX' or an organolithium compound 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 suitable solvent, and thereafter recovering the R" radical-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 62

A method of preparing a R"'O-- or RO-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with a reagent selected from the group consisting of (i) carbinols having the general formula R"'OH, (ii) alcoholates having the general formula R"'OQ, and (iii) alkyl orthoformates having the general formula (RO) 3 CH wherein R"' is an alkyl radical containing 1 to 4 carbon atoms or a phenyl radical, R is an alkyl radical containing 1 to 4 carbon atoms, and Q is sodium, potassium, or lithium, at a temperature of 0° to 110° C., in a suitable solvent, and thereafter recovering the R"'O-- or RO-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 63

A method of preparing a R"'O-- or RO-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with a reagent selected from the group consisting of (i) carbinols having the general formula R"'OH, (ii) alcoholates having the general formula R"'OQ, and (iii) alkyl orthoformates having the general formula (RO) 3 CH wherein R"' is an alkyl radical containing 1 to 4 carbon atoms or a phenyl radical, R is an alkyl radical containing 1 to 4 carbon atoms, and Q is sodium, potassium, or lithium, at a temperature of 0° to 110° C., in a suitable solvent, and thereafter recovering the R"'O-- or RO-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.9 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 66

A method of preparing a R iv 2 N-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with an aminolysis reagent having the general formula NHR iv 2 wherein R iv is hydrogen, an alkyl radical containing 1 to 4 carbon atoms, a phenyl radical or a --SiR v 3 radical wherein R v 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 suitable solvent, and thereafter recovering the R iv 2 N-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.5 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.

Claim 67

A method of preparing a R iv 2 N-containing metallopolysilane, which method consists of reacting under anhydrous conditions, a halogen-containing metallopolysilane with an aminolysis reagent having the general formula NHR iv 2 wherein R iv is hydrogen, an alkyl radical containing 1 to 4 carbon atoms, a phenyl radical or a --SiR v 3 radical wherein R v 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 suitable solvent, and thereafter recovering the R iv 2 N-containing metallopolysilane; where the halogen-containing metallopolysilane is composed of [R 2 Si], [RSi], [R'Si], and [M] units where R is an alkyl radical containing 1 to 4 carbon atoms, R' is an alkyl radical containing at least 5 carbon atoms or a phenyl radical, and M is a metal selected from the group consisting of aluminum, boron, chromium, lanthanum, molybdenum, neodymium, niobium, samarium, tantalum, titanium, tungsten, vanadium, yttrium, and zirconium, where the halogen-containing metallopolysilane contains 0 to 59.5 mole percent of [R 2 Si] units, 40 to 99.9 mole percent of [RSi] units, 0 to 99.9 mole percent [R'Si] units, and 0.1 to 10 mole percent of [M] units, and where the other bonds on silicon are attached to other silicon atoms and halogen atoms.