Patent GB-660377-A (GB)
Title: Process for the production of polymers of unsaturated ethers and compositions containing such polymers
Filed: 1949-01-07
Abstract: Polymers and copolymers of unsaturated ethers of formula ROR1, where R is an epoxy alkyl radical containing at least 3 carbon atoms and R1 is an alkenyl group, are made by heating the ethers alone or with another copolymerizable monomer, e.g. styrene and vinyl acetate, preferably in bulk, in the presence of actinic light and/or oxygen and/or organic peroxides. The polymers or copolymers alone or in admixture may be made infusible by (1) further polymerization through the epoxy linkage using a Friedel-Craft catalyst, e.g. metal halides and boron trifluoride complexes, alkali oxides, hydroxides or organic bases; (2) esterification of the epoxy group with dibasic acids or anhydrides, e.g. maleic acid or anhydride, phthalic acid or anhydride, citraconic acid or glutaconic acid.  The rendering of the polymers infusible may be carried out in bulk, solution or dispersion, in batches or in a continuous manner and under atmospheric, superatmospheric or reduced pressure or on a surface, e.g. as a coating for fabrics, and if desired the coating may be stripped from the coated surface.  The polyethers may be mixed prior to rendering infusible with synthetic rubbers or resins, drying and semi-drying oils, proteins, cellulose derivatives, natural resins, e.g. gilsonite, rosin, colophony, shellac, copal gum, pitch or asphalt, plasticizers, dyes, pigments or fillers.  The unsaturated ethers may be vinyl-2,3-, allyl-2,3-, ethallyl-2,3-, t-butenyl-, 1,1-dimethyl-2-octenyl-glycidyl ether, crotyl-2,3-epoxybutyl ether, 2-allyloxy-1,3-epoxypropane, or 1-vinyloxy-2-methyl-2,3-epoxypropane. Specified peroxide catalysts are di-t-butyl-, di-t-amyl-, t-butyl-t-amyl-peroxide, t-butyl hydroperoxide, benzoyl and acetyl peroxide, 2,2-bis-(t-butyl-peroxy) propane, t-amyl hydroperoxide, methyl n-propyl butane peroxide and dicyclohexyl peroxide.  The Specification includes an extensive list of synthetic resins and rubbers suitable for admixing with the polyether, specified classes are phenol-formaldehyde, urea-formaldehyde, alkylds, unsaturated polyesters of saturated polycarboxylic acids, e.g. vinyl, allyl and methallyl esters of oxalic, malonic, &c., unsaturated polyesters of polybasic inorganic acids, e.g. vinyl, allyl, methallyl, cyclohexenyl esters of silicon &c., unsaturated carboxylic acid polyesters of unsaturated polyhydric alcohols, e.g. acrylic polyesters of glycol, unsaturated polyethers of polyhydric alcohols, e.g. vinyl, allyl and methallyl polyethers of glycol, ethers having two or more unsaturated aliphatic radicals, e.g. divinyl, diallyl, dimethallyl ethers, saturated and unsaturated esters of acrylic and methacrylic acids, e.g. vinyl, allyl and methallyl esters, vinyl and vinylidene halides, and the compounds styrene, alpha-methyl styrene, ethylene, allyl alcohol, allyl halides, polyvinyl acetals, after-chlorinated polyvinyl chloride, and polymers and copolymers of conjugated dienes, e.g. butadiene, pentadienes, and hexadienes.  The polymeric epoxy ethers, alone or in conjunction with basic lead carbonate or strontium salts of organic acids, may be used for stabilizing halogen-containing polymers, e.g. polyvinyl chloride, polyvinylidene bromide, polyfluorochloroethylene, copolymers of vinyl chloride and vinylidene chloride, vinyl chloride and vinyl acetate, vinylidene bromide and vinyl acetate, ethylene and vinyl chloro-acetate, and further halogenated vinyl halide polymers. The polyether may also function as a plasticizer for polymeric materials alone or in conjunction with plasticizers such as dibutyl phthalate, dibutyl phosphate, tricresyl phosphate, dioctyl phthalate or methoxyethyl acetyl ricinoleate.  The Specification as open to inspection under Sect. 91 describes the simultaneous polymerization of the epoxy and alkenyl linkages and also includes compounds having alkynyl groups. This subject-matter does not appear in the Specification as accepted.ALSO:Volatile halogen containing organic compounds are stabilized by addition thereto of small amounts of polymers or copolymers of polyallyl glycidyl ethers and similar compounds of general formula ROR1, where R is an epoxy radical containing at least 3 C atoms and R is an alkenyl group, the polymers being prepared by carbopolymerization as contrasted with epoxypolymerization (see Group IV (a)).  Suitable polymers are poly-(allyl glycidyl ether) allyl glycidyl ether-styrene copolymer, poly-(vinyl glycidyl ether) vinyl glycidyl ether-vinyl acetate copolymer; poly-(crotyl 2,3-epoxybutyl ether); poly - (2 - allyloxy - 1,3 - epoxypropane); poly - (1 - vinyloxy - 2 - methyl - 2,3 - epoxypropane); poly - (tertiary - butenyl glycidyl ether); poly-(1,1-dimethyl-2-octenyl glycidyl ether).  Halogen-containing organic compounds specified are 2 - chlor - 2 - butene, trichloropropene, trichloropropane, 1,3-dibromopropane, 2-bromo-2-butene, allyl chloride, methallyl chloride, isocrotyl chloride.  In example (14) tables are given of stabilisation tests of allyl chloride, methallyl chloride, and isocrotyl chloride (a) when stored alone in glass bottles; (b) when stored with strips of drum metal; (c) when stored with poly-(allyl glycidyl ether); (d) when stored with allyl glycidyl ether-styrene copolymer.