High yield silicon carbide pre-ceramic polymers

Abstract

Pre-polymers which are alkoxylated or phenoxylated methylpolysilanes are useful for the preparation of fine grained silicon carbide ceramic materials and silicon carbide-containing ceramics. The pre-polymers exhibit ease of handling and their use to obtain silicon carbide ceramic materials results in high yields.

That which is claimed is: .[.1. A method of preparing a polysilane having the average formula 
     
       (B) thereafter recovering the polysilane (I)..]. 2. A method of preparing a polysilane as claimed in claim .[.1.]. .Iadd.14 .Iaddend.wherein there is present at least a stoichiometric quantity of a carbinol based on the 
     
     
        amount of halogen in the polysilane (II). 3. A method of preparing a polysilane as claimed in claim .[.1.]. .Iadd.14 .Iaddend.wherein there is present at least a stoichiometric quantity of an alcoholate based on the 
     
     
        amount of halogen in the polysilane (II). 4. A method of preparing a polysilane as claimed in claim .[.1.]. .Iadd.14 .Iaddend.wherein there is present at least a stoichiometric quantity of an alkyl orthoformate based on the amount of halogen in the polysilane (II). .[.5. A composition of matter consisting essentially of a polysilane having the average unit formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane..]. .[.6. A method of preparing silicon carbide ceramic materials which consists of heating a polysilane having the average unit formula     {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd.  units wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the   
     
     
        polysilane..]. 7. Silicon carbide ceramic material prepared by the method 
     
     
        as claimed in claim .[.6.]. .Iadd.16.Iaddend.. 8. A method of preparing a silicon carbide-containing ceramic article which consists of (A) forming an article of the desired shape from a polysilane having the average formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane; and     (B) heating the article formed in (A) in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the polysilane is converted to a silicon carbide-containing   
     
     
        ceramic article. 9. The silicon carbide-containing ceramic article 
     
     
        prepared by the method of claim .[.8.]..Iadd.17.Iaddend.. 10. A method of preparing a filled silicon carbide-containing ceramic article which consists of (A) mixing a polysilane with at least one conventional ceramic filler which polysilane has the average formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane,     (B) forming an article of the desired shape from the mixture of polysilane and fillers and,   (C) heating the article formed in (B) in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the polysilane is converted to a silicon carbide-containing   
     
     
        ceramic. 11. An article prepared by the method of claim .[.10.]. 
     
     
        .Iadd.17.Iaddend.. 12. A method of preparing an article coated with ceramic which consists of (A) mixing a polysilane with at least one conventional ceramic filler which polysilane has the average unit formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical and either 0 to 35 percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane;     (B) coating a substrate with the mixture of polysilane and fillers and,   (C) heating the coated substrate in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the coating is converted to a silicon carbide ceramic, whereby a   
     
     
        silicon carbide-containing ceramic coated article is obtained. 13. An article prepared by the method of claim .[.12.]. .Iadd.19.Iaddend.. .Iadd. 14. A method of preparing a solid polysilane having the average formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}                         (I)     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane which method consists of   (A) reacting under anhydrous conditions a polysilane having the average unit formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}                         (II)     in which there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein the remaining bonds on the silicon atoms are attached to either another silicon atom, a chlorine atom or a bromine atom such that the polysilane contains from 10-43 weight percent, based on the weight of the polysilane, of hydrolyzable chlorine or 21-62 weight percent based on the weight of the polysilane of hydrolyzable bromine, with a reagent selected from the group consisting of   (i) carbinols having the general formula ROH   (ii) alcoholates having the general formula ROM and   (iii) alkyl orthoformates having the general formula (R'O) 3  CH wherein R is the same as above, R' is an alkyl group of 1-4 carbon atoms, and M is sodium, potassium or lithium, at a temperature of from 0° to 110° C. for a period of from 1.5 to 65 hours, in a suitable solvent, and     (B) thereafter recovering the polysilane (I). .Iaddend..Iadd. 15. A composition of matter consisting essentially of a solid polysilane having the average unit formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane. .Iaddend..Iadd. 16. A method of preparing silicon carbide ceramic materials which consists of heating a solid polysilane having the average unit formula     {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}      in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane. .Iaddend. .Iadd. 17. A method of preparing a silicon carbide-containing ceramic article which consists of     (A) forming an article of the desired shape from a solid polysilane having the average formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane; and     (B) heating the article formed in (A) in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the polysilane is converted to a silicon carbide-containing ceramic article. .Iaddend..Iadd. 18. A method of preparing a filled silicon carbide-containing ceramic article which consists of   (A) mixing a solid polysilane with at least one conventional ceramic filler which polysilane has the average formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent of RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 25 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane,     (B) forming an article of the desired shape from the mixture of polysilane and fillers and,   (C) heating the article formed in (B) in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the polysilane is converted to a silicon carbide-containing ceramic. .Iaddend..Iadd. 19. A method of preparing an article coated with ceramic which consists of   (A) mixing a solid polysilane with at least one conventional ceramic filler which polysilane has the average unit formula   {(CH.sub.3).sub.2 Si}{CH.sub.3 Si}     in which polysilane there is from 0 to 60 mole percent (CH 3 ) 2  Si═ units and 40 to 100 mole percent CH 3  Si.tbd. units, wherein there is also bonded to the silicon atoms other silicon atoms and radicals having the formula     RO--     wherein R is an alkyl radical of 1 to 4 carbon atoms or phenyl wherein essentially all the remaining bonds on silicon are attached to chlorine or bromine atoms such that the polysilane contains from 24 to 61 weight percent or RO-- when R is an alkyl radical, 26 to 66 weight percent of RO-- when R is a phenyl radical, and either 0 to 35 weight percent chlorine or 0-35 weight percent bromine, all based on the weight of the polysilane,     (B) coating a substrate with the mixture of polysilane and fillers and,   (C) heating the coated substrate in an inert atmosphere or in a vacuum to an elevated temperature in the range of 1200° C. to 1600° C. until the coating is converted to a silicon carbide ceramic, whereby a silicon carbide-containing ceramic coated article is obtained. .Iaddend.