Patent GB-544707-A (GB)
Title: Manufacture of synthetic resins
IPC: C08F26/06
Filed: 1940-07-18
Abstract: 544,707. Vinyl polymerization products ; aromatic acid imides ; dyeing cellulosic materials. DU PONT DE NEMOURS & CO., E. 1. July 18, 1940, No.11844. Convention date, July 18, 1939. [Classes 2 (iii) and 15 (ii)] N-vinyl imides of aromatic (including aromatic heterocyclic) dicarboxylic acids having the carboxyl groups attached to adjacent ring carbon atoms are polymerized by the action of heat and or catalysts, either alone or in the presence of polymerizable negatively substituted vinyl or vinylidene compounds. Specified acids from which the imides are derived are phthalic, 3-nitrophthalic, 4-bromophthalic, tetracblorophthalic, cinchomeronic, 2:3-naphthalene-dicarboxylic, 3:6 dihydroxyphthalic and quinolinic acids. Specified vinyl and vinylidene compounds are methyl and ethyl  acrylates ; methyl, ethyl, butyl, octyl, n-dodecyl phenol, cyclohoxyl, and p-cyclohexylphenyl methacrylates ; methacrylic acid, amide and anilide ; acrylo and methacrylo nitriles ; vinyl acetate, chloracetate, propionate and butyrate ; methyl vinyl ketone ; phenyl vinyl ketone styrene ; chloroprene ; unsymmetrical dichloroethylene. The polymerization may be effected with or without the addition of solvents or diluents, in aqueous suspension with stirring in the presence of a protective colloid to give a granular polymer, or in emulsion without stirring. In examples the polymers are prepared by heating N -vinyl phthalimide (1) in contact with air, (2) and (12) with benzoyl peroxide with or without styrene, (3). with benzoyl peroxide in solution in acetic acid, cyclohexanone, ethyl alcohol, formamide or benzene, (4) and (6) with benzoyl peroxide and-methyl starch in aqueous suspension with or without methyl acrylate, methyl methacrylate or #- methoxyethyl methacrylate, (5) and (8) with benzoyl peroxide and methacrylic acid or methyl vinyl ketone in solution in toluene, (7) in aqueous emulsion with methyl acrylate, sulphated oleyl acetate, hydrogen peroxide and urea, (9) in aqueous emulsion with methacrylonitrile, sulphated oleyl acetate and hydrogen peroxide, (10) in aqueous emulsion with unsymmetrical dichloroethylene, vinyl acetate, sulphated oleyl acetate, hydrogen peroxide and hydrochloric acid, and (11) under pressure with vinyl acetate, water, methylated starch and hydrogen peroxide, (12) with chloroprene, carbon tetrachloride and benzoyl peroxide. N-vinyl-phthalimide is prepared by pyrolysis of #-phthalimidoethyl acetate. #-phthalimidaethyl acetate is prepared by heating phthalic anhydride with ethanolamine and adding acetic anhydride containing a trace of sulphuric acid.  α-ethyl vinyl-phthalimide is prepared by the pyrolysis of 2-phthalimidobutyl acetate. - 2-phthalimidobutyl acetate is prepared from phthalic anhydride, 2-aminobutanol-1, and acetic anhydride. According to the Specification as open to inspection under Sect. 91, the polymers may be hydrolysed (a) in an acid medium to give a compound containing free amino groups, (b) by treating with sodium hydroxide and phenol to give a polyvinyl phthamic acid, or (c) by heating with ethanolamine to give a product containing both free amino and carboxyl groups. The hydrolysed products may be used as sizes or dispersing agents, or to modify the dyeing characteristics of cellulosic materials such as regenerated cellulose or cellulose acetate. N-vinylimides of aromatic dicarboxylic acids are prepared by (a) the pyrolysis of α-methyl phthalimide acid halides, e.g. phthalyl-α-alanyl chloride, (b) the phthalimide with acetylene. This subject-matter does not appear in the Specification as accepted.