Patent GB-741094-A (GB)
Title: Improvements in and relating to organoethynyl hydrolyzable organosilanes
IPC: C07F7/18
Filed: 1953-03-12
Abstract: Polymeric organo-silicon compounds are obtained by polymerizing organo-silicon compounds of the general formula <FORM:0741094/IV(a)/1> wherein R and R1 may be the same or different and represent hydrocarbon radicals free from olefinic or acetylenic unsaturation, and X represents a halogen, an acyloxy radical derived from a saturated aliphatic carboxylic acid, or an alkoxy radical derived from a saturated aliphatic alcohol, e.g. in the presence of a polymerization catalyst such as benzoyl peroxide. Copolymers are formed by carrying out the above polymerization in the presence of styrene, butadiene, vinyl chloride or acetate, an acrylate, a methacrylate or acrylonitrile.  The polymers thus formed contain hydrolysable radicals and may be hydrolysed to form siloxane linkages.  Polymeric siloxanes containing radicals having triple bonds are obtained by hydrolysing organo-silicon compounds of the above general formula, and further polymerization may then be effected through the triple bond.  A polymeric siloxane containing the unit structure <FORM:0741094/IV(a)/2> is referred to, and this siloxane may be chain stopped by hydrolysing in the presence of a hexaorganodisiloxane.ALSO:The invention comprises organo-silicon compounds of the general formula <FORM:0741094/IV(a)/1> wherein R and R1 represent hydrocarbon radicals free from olefinic or acetylenic unsaturation, and X represents a halogen, an acyloxy radical derived from a saturated aliphatic carboxylic acid or an alkoxy radical derived from a saturated aliphatic alcohol, and a process for the preparation thereof by reacting the Grignard reagent R-C = C-MgBr with an organo-silicon compound of the formula R1SiX13 wherein R and R1 have the above significance and X1 represents a halogen and, if necessary, reacting the product with a saturated aliphatic carboxylic acid or anhydride or a saturated aliphatic alcohol.  R and R1 may be the same or different and may represent alkyl radicals such as the methyl, ethyl, propyl, isopropyl, butyl, hexyl and dodecyl radicals, cycloaliphatic radicals such as the cyclopentyl and cyclohexyl radicals, aryl radicals such as the phenyl, diphenyl and naphthyl radicals, alkaryl radicals such as the tolyl, xylyl and ethylphenyl radicals, and aralkyl radicals such as the benzyl, phenylethyl and phenylbutyl radicals.  X is preferably chlorine, bromine or fluorine, an acyloxy radical of the formula <FORM:0741094/IV(a)/2> wherein Z is a lower alkyl radical such as the methyl, ethyl, propyl, isopropyl and butyl radicals, or an alkoxy radical such as the methoxy, ethoxy, propoxy, isopropoxy and butoxy radicals.  The Grignard reaction is preferably carried out with an excess of the Grignard reagent, and a catalyst such as a small quantity of powdered cuprous chloride may be used.  The reaction to form the acyloxy derivatives of the above general formula is preferably carried out with an excess of the acid anhydride, and a catalyst such as a solution of triethanolamine in the acid anhydride may be used.  The reactions to form the alkoxy derivatives of the above general formula are advantageously carried out in the presence of a hydrogen halide acceptor, e.g. a tertiary amine such as pyridine.  In the examples, 1-pentynylmethyldichlorosilane, 1-hexynylmethyldichlorosilane, 1 - pentynylmethyldiacetoxysilane, 1 - hexynylmethyldiacetoxysilane and 1-pentynylmethyldiethoxysilane are prepared.  The following compounds are also obtainable: 1-pentynylphenyldichlorosilane, 1 - hexynylphenyldichlorosilane, 1-pentynylmethyldibromosilane, phenylethynylpropyldichlorosilane, (benzylethynyl) ethyldibromosilane and 1-hexynylbenzyldichlorosilane.  The organosilicon compounds of the above general formula may be treated as follows: (a) hydrogenated to form olefinic or paraffinic derivatives; hydrogen halides may be added across the triple bond to completely saturate or partially saturate the triple bond; (b) the triple bond may be halogenated whereby all or part of the unsatisfied bonds may be taken up with halogens; (c) silicon compounds containing silicon bonded hydrogen and silicon bonded halogen, e.g. silicochloroform and methyldichlorosilane, may be added across the triple bond; and (d) hydrogen sulphide, hydrogen cyanide, a mercaptan or an organic nitrile may be added across the triple bond.  Bis - (1 - hexynyl) - methylchlorosilane is obtained as the result of reacting methyltrichlorosilane and 1-hexynyl magnesium bromide.