| 摘要 |
Polymers having hydrogen atoms attached to tertiary carbon atoms in the polymer chain are hydroperoxidized by contacting aqueous suspensions of the polymers with a gas containing molecular oxygen at a temperature between 20 DEG and 200 DEG C. in the presence of a cationic surface active agent and a water-soluble persulphate. Specified polymers are polymers of olefins, styrene and substituted styrenes, vinyl ethers and ketones, vinyl and allyl esters, vinyl pyridine, vinyl naphthalene, acrylic esters, amide and nitrile and vinyl chloride, and copolymers thereof with methacrylic esters, acid, amide and nitrile, isobutylene, vinylidene chloride, methyl isopropenyl ketone, maleic anhydride and ethyl fumarate. Specified surface active agents are alkyl trimethyl, alkyl dimethyl ethyl, alkyl triethyl, alkyl benzyl dimethyl and dialkyl dimethyl ammonium chlorides and bromides in which the alkyl groups contain 8 to 24 carbon atoms, oleoyl diethyl methylenediamine salts, dehydroabietylamine acetate and disproportionated rosin amine acetate. The gas may be air, oxygen or a mixture of oxygen with nitrogen or helium. Graft copolymers may be prepared by reacting the hydroperoxidized polymers with ethylenically unsaturated compounds, e.g. olefins, diolefins, vinyl aromatic and heterocyclic compounds, vinyl and vinylidene halides, unsaturated esters, alcohols, ethers, acids, nitriles and amides, and allyl amine, in the presence of a redox reducing agent, e.g. ferrous, vanadyl, cobalt, nickel, copper, mercury, chromium and manganese salts, sodium formaldehyde sulphoxylate, amines and sodium hyposulphite. The products are useful as coating, colloidal and surface active compositions, oil additives, plasticizers, film and fibre formers and elastomers. Examples using potassium persulphate as initiator describe the hydroperoxidizing of (1, 2 and 4) polypropylene and (9) a polypropylene fibre woven fabric in the presence of hexadecyl and octadecyl trimethyl ammonium chlorides; (3 and 5) polypropylene and (6) an ethylene/propylene copolymer rubber in the presence of dihexadecyl and dioctadecyl dimethyl ammonium chlorides; (7) polypropylene in the presenceof disproportionated rosin amine acetate; and (8) polypropylene in the presence of dioctyl, didecyl, didodecyl, ditetradecyl, dihexadecyl and dioctadecyl dimethyl ammonium chlorides. Graft copolymers are prepared from the product of Examples (3) with dimethylaminoethyl methacrylate in the presence of vanadyl sulphate dihydrate and ethylenediamine tetraacetic acid, (4) with methyl methacrylate in the presence of vanadyl sulphate, and (9) with methyl methacrylate in the presence of ferrous sulphate. |
