Patent GB-786142-A (GB)
Title: A process for the production of organosilicon compounds
IPC: C08F230/08
Filed: 1956-03-19
Abstract: Organosilicon compounds are modified by grafting olefinic compounds on to silicon-bonded alkyl radicals, and this is effected by heating a mixture of (1) an organosilicon compound free from silicon-bonded hydrogen and aliphatic unsaturation but having at least one silicon-bonded radial containing less than 5 carbon atoms; (2) a substituted olefinic compound containing at least one aromatic hydrocarbon or at least one atom other than carbon and hydrogen, any remaining valencies being satisfied by hydrogen or carbon atoms; and (3) a free radical generator which is an organic peroxide (other than an aromatic acyl peroxide as claimed in the parent Specification) or an azo compound in which both nitrogen atoms of the azo linkage are attached to tertiary carbon atoms and the remaining valencies of these carbon atoms are satisfied by nitrile, carboxyalkyl, cycloalkylene, alkyl or YOOC-radicals, in which Y is an alkyl radical, at a temperature above that at which free radical generator forms free radicals. Reactant (2) is preferably used in amount of from 0.1 to 10 per cent by weight of (1) and may be, for example, styrene, vinyltoluene, divinylbenzene, p-phenylstyrene, tetrafluoroethylene, vinyl chloride, allyl chloride, trifluorochloroethylene, hexafluorobutadiene, vinylidene chloride, dichloroethylene, chlorocyclohexene, crotonaldehyde, acrylic aldehyde, cinnamic aldehyde, allyl alcohol, cyclohexenol, 4 - methylpenten - 3 - ol - 1, cinnamic alcohol and penten - 4 - ol - 2; acrylic, methacrylic, crotonic, vinylacetic, cinnamic, maleic, dimethylmaleic, lauroleic, oleic, linoleic and linolenic acids; diallyl and allylethyl ethers; methyl acrylate, methylmethacrylate, vinyl and allyl acetates; crotonamide, acrylamide and cinnamamide; acrylo -, methacrylo - and cinnamo - nitriles; allyl mercaptan; allyl -, allyl - ethyl - and vinyldimethyl - amines; allyl and vinyl sulphides; methylvinylketone, allylacetone and benzalacetophenone; allyl and cinnamyl isocyanates; and polymeric olefins containing residual c = c unsaturation such as polymers of perfluorobutadiene, chloroprene and copolymers of butadiene and acrylonitrile or styrene (polytetrafluoroethylene, polytrifluorochloroethylene and polyvinylchloride are inoperable).  The organosilicon compound (1) may be a hydrolysable, non-hydrolysable or partially hydrolysed silane, a silazane, a silcarbane, a polysilane, a silanol or salt thereof, an organosilicon sulphide or a completely or partially condensed polysiloxane, and may have as silicon-bonded radicals free from aliphatic unsaturation in addition to the above defined alkyl radicals, higher alkyl, cycloalkyl, aryl and halogenated alkyl and aryl radicals; organo functional radicals, e.g. carboxy phenyl, gammahydroxypropyl, gamma-aminopropyl, pentachlorophenoxymethyl and other hydrocarbon radicals having aldehyde, ketone, nitrile, nitro, carboxyl, amide and hydrosulphide substituents; methylene, ethylene, propylene, phenylene, xenylene and cyclohexylene radicals.  Compounds (3) specified are methyl, tertiary butyl, trans-decalin, 1-methyl cyclopentyl, 2-cyclohexene-1-yl, cumene, tetralin, triphenylmethyl, benzyl and p-nitrophenyldiphenylmethyl hydroperoxides; 3-methyl-3-hydroperoxy - 1 - butyne, a  - hydroperoxy tetrahydrofuran and a -hydroperoxyethyl ethyl ether; peroxy - acetic, isovaleric, crotonic, trichloroacetic, lactic, benzoic and cinnamic acids; mono- and di-peroxyphthalic, p-methoxyperoxybenzoic, m - nitroperoxybenzoic and 2 : 4-dichloroperoxybenzoic acids; di - tertiarybutyl, diethyl, tertiarybutylmethyl and ditriphenylmethyl peroxides; ascaridole, 1 : 4-epydioxy - p - menthane, 1 : 4 : 2 : 3 - diepoxy-p-menthane, diacetylperoxide, dialkyl and diaryl peroxy dicarbonates of the formula ROOCOOCOOR (R = methyl, ethyl, phenyl or tolyl), ethyl peroxyacetate, tertiary butyl peroxybenzoate, di-tertiary butyl diperoxyphthalate, bis(1 - hydroxycyclohexyl) - peroxide, 1 - hydroxy - 11 - hydroperoxycyclohexyl peroxide, bis(hydroperoxycyclohexyl)peroxide, trimeric cyclohexanone peroxide, bis(hydroxyethyl)peroxide, bis(phenylhydroxymethyl) - peroxide, trimeric acetone peroxide, methylhydroxymethylperoxide and (Me3COO2C.Me2; and the azo compounds Me2(NC)CN = NC (CN)Me2, MeEt(NC)CN = NC(CN)Me.Et, Et2 (NC)CN = NC(CN)Et2 Pr2(NC)CN = NC(CN) Pr2, AmMe(NC)CN = NC(CN)MeAm, (HOOC CH2.CH2)Me(NC)CN = NC(CN)Me(CH2.CH2. COOH), (MeOOC)Me2CN = NCMe2(COOMe), (EtOOC)Me2CN = NCMe2(COOEt) and: <FORM:0786142/IV (a)/1> wherein Me, Et, Pr and Am are methyl, ethyl, propyl and amyl respectively.  The reaction may be effected at normal, sub or super atmospheric pressure, at temperatures from 50 DEG  to 150 DEG  C. and in the presence or absence of inert hydrocarbon solvents.  The products are useful as lubricants, surface-active agents, hydraulic fluids and electrical insulating materials.  In Examples, trifluorochloroethylene was reacted with a trimethyl-end-blocked dimethylpolysiloxane in the presence of different free radical generators.