Patent GB-806582-A (GB)
Title: Improvements in or relating to organosilicon polymers
IPC: C08F283/12
Filed: 1957-04-01
Abstract: Graft polymers are made by contacting an organosilicon polymer, which is substantially free from Si-bonded H atoms and from radicals having aliphatic unsaturation, with a non-silicic olefin in the presence of a free radical generator and in the presence of a finely-divided chemically inert inorganic solid, the particles of which have an average diameter of from 0.005 to 5 microns.  The free radical generator includes ionizing radiation such as b -, g - and X-rays, and accelerated electrons, neutrons, protons, deutrons and a -particles, as well as compounds known to initiate free radical formation such as organic peroxides and azo compounds which are numerously exemplified.  Organosilicon polymers or copolymers used may be partially hydrolysed and condensed silanes, silazanes, silcarbanes, partially or completely condensed polysiloxanes and polysilanes, preferably containing at least one Si-bonded alkyl radical of less than 5 carbon atoms, the other radicals, if any, being saturated alkyl, cycloalkyl, aryl, halogenated alkyl or aryl, or organofunctional such as carboxyphenyl, g -hydroxypropyl or g -aminopropyl.  Olefins specified are: ethylene, butadiene, cyclohexene, styrene, vinyltoluene, divinylbenzene, indene, isoprene, and hexadecene; tetrafluoroethylene, vinyl chloride, allyl chloride, trifluorochloroethylene, hexafluorobutadiene, vinylidene chloride, dichloroethylene and chlorocyclohexene; crotonaldehyde, acrylic aldehyde and cinnamic aldehyde; allyl alcohol, cyclohexenol, 4-methylpentene-3-ol-1, cinnamic alcohol and penten-4-ol-2; acrylic, methacrylic, crotonic, vinylacetic, cinnamic, maleic, dimethylmaleic, lauroleic, oleic, linoleic and linolenic acids and maleic anhydride; diallyl and allylethyl ethers; methyl acrylate, methyl methacrylate, vinyl acetate and allyl acetate; crotonamide, acrylamide and cinnamamide; acrylonitrile, methacrylonitrile and cinnamonitrile; allylmercaptan; allylamine, allylethylamine and vinyldimethylamine; allyl and vinyl sulphides; methylvinyl ketone, allylacetone, and benzalacetophenone; allyl and cinnamyl isocyanates; and polymeric olefins having substantial C=C residual unsaturation, e.g. polybutadiene, natural gum rubber, polychloroprene, copolymers of butadiene and styrene, acrylonitrile, or polyhexafluorobutadiene. Inert inorganic solids specified are: amorphous solids, e.g. silica xerogels and aerogels, fume silica and silicaalumina gels; complex silicates, e.g. cyanite (Al2SiO5), beryl 3 (BeO.Al2O3.6SiO2) garnets, phlogopite (or magnesium mica), phenacite (2BeO.SiO2), olivine [(Mg.Fe)2SiO4], muscovite (K2O.3Al2O3.6SiO2.2H2O), topaz [(AlF)2SiO4] and zircon (ZrSiO4); and simple ionic crystals: fluorides, chlorides, bromides and iodides of Li, Na, K, Cs and Rb; oxides, selenides, sulphides and tellurides of K, Na and Li: and the halides of Ba, Cd, Sr, Mg and Zn.  When certain peroxides are used it is preferable to exclude oxygen from the system, e.g. by using an atmosphere of nitrogen.  The reaction may, if desired, be effected in an inert mutual solvent, e.g. aliphatic or aromatic hydrocarbons.  Chain transfer agents can also be incorporated, either as solvents per se or as additional reactants, e.g. carbon tetrachloride, bromoform, chloroform and mercaptans.  In typical examples: (1) a mixture of a liquid trimethylsiloxy end-blocked dimethylpolysiloxane, CF2=CFCl, benzoyl peroxide and magnesium oxide of particle size less than 5 microns was heated and agitated in a rocker bomb at 150 DEG  C. for 17 hours; (10) a dimethylpolysiloxane gum was compounded with indene or styrene and silica, magnesium oxide or potassium chloride of specified particle size; each mixture was then placed in a metal container and subjected at room temperature to irradiation from a Van de Graaff generator; each sample was then devolatilized at a pressure of less than 1 mm. Hg for 100 hours to give, as volatile material, unreacted olefin and strong elastomers.  Uses.-As lubricants, surface-active agents, hydraulic fluids and electrical insulation. Specifications 632,563, 671,773, 675,912 and 786,142 are referred to.