Patent GB-697289-A (GB)
Title: Process for polymerising vinyl-type compounds and polymers produced thereby
IPC: C08F20/50
Filed: 1950-05-02
Abstract: Polymers consisting of, or comprising monomers having a terminal methylene group joined through an ethylenic linkage to a carbon atom which carbon atom is joined to an atom or group other than hydrogen and to a carbon atom of an organic radical and/or monomers having a terminal methylene group joined to an aliphatic carbon atom through an ethylenic linkage which is in conjugated relationship with another carbon-to-carbon ethylenic linkage are made by initiating polymerization by irradiating with light of a wavelength in the range of 1800 to 17,000 Angstrom units the monomers, in bulk or in a medium which is a non-solvent for the polymers and in the absence of photopolymerization catalysts or photosensitizers and removing the light and continuing the polymerization of the monomers in the dark below the temperature at which thermal polymerization of the monomers would take place. In a modification any other polymerizable olefinically unsaturated monomer or monomers may be added before irradiation, at any intermediate stage, or when the polymerization of the initial monomer is substantially complete.  Specified monomers are 2-chloroprene-1, 2-chlorobutadiene - 1,3, 2 - chlorobutene - 1, alpha - chlorostyrene, isoprene, butadiene, 2,3-dimethylbutadiene, methallyl chloride, methallyl acetate, ethallyl benzoate, alpha-chloroallyl caproate, 3-methallylcyclohexanone, alpha - chloro - 4 - ethyl styrene, alpha-chloroacrylonitrile, butyl 4-chloro-4 pentenoate, ethyl alpha-bromoacrylate, alpha-methyl-4-methoxy-styrene, alphamethoxystyrene, alpha - acetyl - alpha - cyanostyrene, alpha - ethenylstyrene, 2 - cyanoallyl acetate, 2 - ethenylbutene - 1, alpha - phenylstyrene, butyl alpha-chloroacrylate, 2-bromo-1-hepten-3-one, 4-methallylbenzonitrile, 4-chloro-4-pentenamide, 4-amyl-4-pentamide, 4-butyl-4-penten - 2 - one, 4 - iodo - 4 - pentenamide, 3 - fluoro - 3 - butenenitrile, 3 - chloro - 3 - butenenitrile, 5 - isopropyl - 5 - hexenenitrile, 3 - alphachlorovinyl - 1 - carbethoxycyclohexane, 4 - methallyl - 1 - acetoxybenzene, 4 - carbamyl - 2 - butyl - 1 - butene, alpha - methylvinylcyclo - pentane, beta - chloroallylbenzene, 4 - carboxy - 2 - chloro - 1 - pentene, 4 - methallyl - benzamide, 3 - alpha - methylvinylcyclohexanamide, 2 - methallyl - cyclohexanecarboxamide, 7 - ethallyl - 2 - naphthamide, 7 - ethallyl - 2 - naphthonitrile, 2 - alpha - ethylvinylcyclohexanenitrile, 4 - ethallyl - 2 - cyclopentane - nitrile, 3 - methallylcyclopentanone, 3 - ethallyl - 1 - acetylbenzene, 4 - methoxy - 4 - pentenamide, butyl 2 - methyl - 2 - propenoate, ethyl 3 - methyl - 3 - butenoate, isobutyl 4 - ethyl - 4 - pentenoate, amyl 4 - butenyl - 4 - pentenoate, methallyl acetate, ethallyl benzoate, dimethallyl phthalate, 3-methyl-3-buten-2-one, 3-ethyl - 3 - buten - 2 - one, 2 - methallylcyclohexanone, 4 - butyl - 4 - penten - 2 - one, 4 - isopropyl - 4 - penten - 3 - one, 5 - amyl - 5 - penten-2 - one, 5 - ethyl - 5 - penten - 4 - one, methacrylonitrile, methyl methacrylate, 4-ethyl-4-pentenoate, amyl 4-amyl-4-pentenoate, 4-butyl - 4 - pentenenitrile, 4 - chloro - 4 - pentenoate, 4 - isobutyl - 4 - pentenamide, 4 - amyl-4-pentenamide, 4-chloro-3-buten-2-one, 4-isopropyl-4-penten-3-one and mixtures.  The other polymerizable monomer may be styrene, dichlorostyrene vinyl naphthalene, vinyl phenol, methyl acrylate, propyl acrylate, vinylidene chloride, vinylidene bromide, vinyl chloride, vinyl bromide, vinyl fluoride, acrylonitrile, vinyl acetate, vinyl chloroacetate, vinyl benzoate, vinyl valerate, divinyl succinate, divinyl adipate, vinyl allyl phthalate, vinyl methallyl pimelate, diallyl phthalate, allyl acetate and diallyl succinate.  Various types of additives may be added to the reaction mixture before or during the polymerization reaction.  Additives mentioned are poly-saccharides, gum arabic, soluble starch, dextrine, lubricants, dyes, pigments and plasticizers, e.g. dioctyl phthalate and tricresylphosphate.  The medium in which the polymerization is effected may be cyclohexane, butane, hexane, benzene, or water, e.g. in aqueous emulsion or suspension. Emulsifying agents mentioned are sodium and potassium myristate, laurate, palmitate, oleate stearate, rosinate, hydroabietate, sodium lauryl sulphate, potassium stearyl sulphate, sodium lauryl sulphonate, potassium stearyl sulphonate, sodium cetyl sulphonate, sulphonated mineral oil as well as the ammonium salts of these acids, lauryl amine hydrochloride and stearyl amine hydrobromide. The polymers are said to be internally plasticized, and may be moulded, e.g. in furniture and toys, used as impregnants or laminating agents, or used as paints, enamels or lacquers. Specifications 622,374 and 636,320 are referred to.