Patent GB-620692-A (GB)
Title: Improvements in and relating to polymerizable polysiloxane compounds and copolymers thereof
IPC: C08G77/20
Filed: 1946-06-04
Abstract: A polymerizable polysiloxane is prepared by hydrolising a mixture of an alkenyl halogenosilane and an alkyl or aryl halogenosilane in proportions to produce a polysiloxane having a hydrocarbon Si ratio of 1.2 to 2, a minor proportion of the hydrocarbon radicals being alkenyl.  The products alone or with solvents, pigments or driers can be employed as coating compositions as fillers or binders for coil structures or for casting or moulding.  In the examples: (1) and (2) dimethyldichlorosilane and diallyl dichlorosilane were hydrolysed and polymerized to resins; (3) diethyldichlorosilane and diallyl dichlorosilane were hydrolysed and condensed in aqueous ether. Removal of solvent yielded an oil which heated with benzoyl peroxide yielded a resin; (4) diphenyldichlorosilane and diallyldichlorosilane were hydrolysed in aqueous ether, the solvent removed and the oily product polymerized to a resin by heating; (5) dimethyldichlorosilane and vinylmethyldichlorosilane were hydrolysed and condensed, and the oily product was polymerized with benzoyl peroxide; (6) dimethyldichlorosilane and vinyltrichlorosilane were cohydrolysed in aqueous ether.  The liquid polysiloxane obtained polymerized on heating to a clear resin; (7) dimethyldichlorosilane, methyltrichlorosilane and vinyltrichlorosilane were cohydrolysed and the product polymerized with benzoyl peroxide; (8) dimethyldichlorosilane and allyltrichlorosilane were cohydrolysed and the liquid product polymerized by heat; (9) dimethyldichlorosilane, diphenyldichlorosilane, phenyltrichlorosilane and vinyltrichlorosilane were hydrolysed together and the liquid product polymerized to a hard thermoplastic resin; (10) a mixture of dimethyldichlorosilane, methyl trichlorosilane and allyltrichlorosilane was used; (11) the starting materials were dimethyldichlorosilane, methyltrichlorosilane and allyltrichlorosilane; (12) a mixture of dimethyldichlorosilane and diallyldichlorosilane was hydrolysed.  The resulting oil was neutralised, and converted with phenyl phosphoryl chloride to a gum which was compounded with titanium dioxide and a peroxide to yield an elastomer as described in Specification 592,018. Specifications 542,655, 544,143, 548,911, 548,912 and 551,649 also are referred to. The Specification as open to inspection undef Sect. 91 describes the copolymerization or the polymers of the invention with substances containing a CH2=C< grouping, e.g. diallyl phthalate, styrene, vinyl chloride and acrylates or methacrylates. It also refers to copolymers of methyl vinyl siloxane with methacrylates, styrene, chlorostyrene, acrylonitrile, diethylmaleate or vinyl carbazole.  In examples: (17) dimethyldichlorosilane, and allytrichloro-silane were hydrolysed and condensed in presence of diallyl phthalate and the mixture polymerized with benzoyl peroxide; (18) dimethyl dichlorosilane, methyl trichlorosilane and allyltrichlorosilane were hydrolysed in ethereal solution.  The solvent was removed, diallyl phthalate and benzoyl peroxide added and the mixture polymerized to a resin either alone or on a glass tape; (19) a polysiloxane from dimethyldichlorosilane and allyltrichlorosilane was copolymerized with dichlorostyrene; styrene; diallylamine, methylmethacrylate; butyl methacrylate; acrylonitrile; and vinyl pyridine. Tert-butylperbenzoate was the catalyst.  The Specification also includes the preparation of silicones by hydrolysis of: (1) diallyldichlorosilane, the product cured in thin films on glass tape; (2) vinyltrichlorosilane; (3) a mixture of diallyldichlorosilane, dimethyldichlorosilane and allyltrichlorosilane; (4) a mixture of dimethyldichlorosilane, allyltrichlorosilane and methyltrichlorosilane and (5) allyldimethylchlorosilane to yield sym-diallyl tetramethyl disiloxane which was polymerized by heating with tert-butylperbenzoate.  This subject-matter does not appear in the Specification as accepted.ALSO:Alkenyl substituted silicon halides are prepared by reacting an alkenyl halide, e.g. alkyl or vinyl chloride, in the presence of heated silicon and a copper catalyst.  Alternatively, an ethyl silicon halide, e.g. ethyltrichlorosilane or ethylmethyldichlorosilane, may be chlorinated in the ethyl radical with, for example, sulphuryl chloride and the chloroethyl groups are then subjected to dehydrochlorination, e.g. by heating with quinoline or other suitable tertiary amine. Specifications 542,655, 544,143, 548,911, 548,912 and 551,649 are referred to.  The Specification as open to inspection under Sect. 91, describes sym. diallyl tetramethyl disoloxane prepared by the hydrolysis of allyldimethylchlorosilane.  This subject-matter does not appear in the Specification as accepted.