LIQUID COPOLYMERS OF VINYL MONOMERS AND UNSATURATED ESTERS

摘要

1448829 Polyalkylene ether copolymers; polyurethanes GENERAL TIRE & RUBBER CO 18 Sept 1973 [24 Nov 1972] 52073/74 Divided out of 1448828 Headings C3P and C3R A copolymer having an average functionality of 2 to 6 and selected from a copolymer of a vinyl monomer selected from styrene, methacrylonitrile, acrylonitrile and a methyl or ethyl acrylate or methacrylate with a polyalkylene ether itaconate macro-monomer having an equivalent weight of 100 to 3000 per hydroxyl group, having one to three hydroxyl groups per molecule, and having one copolymerizable carbon-to-carbon double bond per molecule; and a copolymer of a vinyl monomer selected from vinyl chloride, vinylidene chloride and vinyl acetate with a polyalkylene ether maleate or fumarate macromonomer having an equivalent weight of 100 to 3000 per hydroxyl group, having one to three hydroxyl groups per molecule, and having one copolymerizable carbon-to-carbon double bond per molecule is prepared by (1) mixing the macromonomer and the vinyl monomer in a mole ratio of 1 : 5 to 1 : 50 simultaneously with a chain transfer agent and an initiator for radical polymerization, the initiator being selected from peroxides and aliphatic diazo compounds, and (2) activating the initiator to cause the polymerization of the vinyl monomer and macromonomer. The macromonomer may be prepared by the telomerization of one or more alkylene oxides of the general formula where R is hydrogen or an alkyl group of less than ten carbon atoms, and a is hydrogen or an alkyl group of less than ten carbon atoms or R1CH 2 - where R1 is an aryl, alkoxy or alkyl carboxy group of less than ten carbon atoms, in the presence of a catalyst and a telogen selected from maleic, fumaric and itaconic acids and their derivatives. In the examples macromonomers prepared by the telemerization of propylene oxide in the presence of Zn 3 (CO(CN) 6 ) 2 - dimethoxy ethane complex, maleic acid and itaconic acid are copolymerized with vinyl chloride, acrylonitrile, styrene and methyl methacrylate in the presence of azo-bis-isobutyronitrile, benzene, carbon tetrachloride, trichlorobromomethane and triethylamine. Polyurethane films and foams may be prepared from the macromonomers or the copolymers. In the examples 1,2,4-butanetriol, stannous octoate, triethylene diamine, 2,4- and 2,6-toluene diisocyanates, polypropylene ether triol, tetramethylbutane diamine, N-methyl morpholine, water, silicone surfactant and diglycidyl ether of bisphenol A are used.