Patent GB-648959-A (GB)
Title: Improvements in or relating to the preparation of esters of 2,3-epoxy propanol and to polymerisation products thereof
IPC: C07D303/16
Filed: 1946-08-19
Abstract: Esters of 2,3-epoxypropanol obtained by reacting an epihalohydrin with an alkali metal salt of an acid having the formula R-CH= CR1-COOH, wherein R is hydrogen or a monovalent organic radical and R1 is hydrogen, a halogen atom or a monovalent organic radical (see Group IV (b)), may be polymerized either alone or with other polymerizable compounds and particularly with vinyl and vinylidene compounds, e.g. with the methyl, ethyl and octyl esters of acrylic, methacrylic and alphachloroacrylic esters and the amides of these acids, e.g. acrylamide and methacrylamide; styrene, chlorostyrenes, vinyl acetate, methyl vinyl ketone, butadiene, isoprene, chloro (or fluoro-)-2-butadiene-1,3; 5-ethyl-2-vinyl-pyridine; 2-vinyl-pyridine; vinyl furane, methacrylonitrile, acrylonitrile methylene malonic esters, vinylidene chloride, vinyl fluoride and fumaric and maleic esters.  When hydrolysed or subjected to conditions leading to scission of the ethylene oxide ring the polymers and copolymers are susceptible of cross-linking and consequent insolubilization.  In examples: (1) 2,3-epoxypropyl methacrylate prepared from epichlorohydrin and sodium methacrylate (see Group IV (b)) is polymerized in the presence of benzoin by exposure under a nitrogen atmosphere to the light of a Westinghouse H-4 lamp; (2) the same ester is mixed with vinyl chloride and lauroyl peroxide and the mixture heated in a glass container under nitrogen, to yield a copolymer; (3) and (4) 2,3-epoxypropyl methacrylate is copolymerized with methyl-alpha chloroacrylate and acrylonitrile respectively, by heating under nitrogen, a solution of ammonium persulphate and sodium bisulphite being included in the polymerization mixture in (4).  A copolymer of the same ester with acrylonitrile may also be prepared by bulk polymerization in the presence of benzoyl peroxide.  The Specification as open to inspection under Sect. 91 refers to the polymerization and copolymerization of monoesters obtained by reacting any epoxy alcohol or an ester-forming derivative thereof with the unsaturated acid or an ester forming derivative thereof (see Group IV (b)).  This subject-matter does not appear in the Specification as accepted.ALSO:Esters of 2, 3-epoxy propanol are obtained by reacting an epihalohydrin with an alkali metal salt of an acid having the formula R-CH=CR1-COOH wherein R is hydrogen or a monovalent organic radical and R1 is hydrogen, a halogen atom or a monovalent organic radical.  The reaction is preferably effected under substantially neutral conditions.  Specified acids are acrylic, methacrylic, and alpha-chloroacrylic acids, crotonic, cinnamic and sorbic acids, alpha-phenyl acrylic acid, beta-benzyl acrylic, beta-benzoyl acrylic, beta-acetyl acrylic and beta-furyl acrylic acids, 4-ethyloctadien-2,4-oic acid, hexadieneoic acid; 5,9-dimethyl decatrien-2,4,8-oic acid; D 1,13-cyclohexadienyl-propenoic acid, and butenedioic acids such as maleic and fumaric acids.  Specified alkali metal salts are sodium, potassium and ammonium acrylates, methacrylates, fumarates and maleates.  The reaction temperature may be from 0 DEG  to 100 DEG  C., but temperatures below 30 DEG  C. are preferred.  The esters are usually isolated by fractional distillation which should be effected in the presence of a polymerization inhibitor such as copper chloride, copper acetate, copper resinate, copper propionate, p-phenylene diamine and hydroquinone.  A polymerization inhibitor is also preferably included in the initial reaction mixture.  Water or aliphatic or aromatic hydrocarbons may be employed as reaction media.  In an example, methacrylic acid is added to an aqueous solution of sodium hydroxide and the resulting solution of the sodium salt is cooled and the pH adjusted to 7.0.  Cuprous chloride is added and epichlorhydrin is then added dropwise and the mixture stirred at room temperature.  It is then extracted with ether and after removing the ether and adding a little cuprous chloride the extract is fractionated under vacuum to yield 2,3-epoxypropyl methacrylate.  The esters may be polymerized or copolymerized with other polymerizable compounds (see Group IV (a)). U.S.A. Specification 2,381,880 is referred to.  The Specification as open to inspection under Sect. 91 is not restricted to esters of 2,3-epoxypropanol obtained in the above manner but refers to the production of an ester by reacting an epoxy alcohol or an ester forming derivative thereof, under substantially neutral or alkaline conditions, with the unsaturated acid or an ester forming derivative thereof, the following epoxy alcohols being also specified: epoxy oleyl alcohol, epoxy octadecanol, epoxy dodecanol, 5-6-epoxyhexanol-2,3,4-epoxy-2,2,4-trimethyl pentanol-3, beta-hydroxy ethyl ethylene oxide, 3-hydroxy-1,2-oxidocyclohexane, alpha - hydroxymethyl alpha - phenylethylene oxide, and 3,4 - dihydroxybenzyl ethylene oxide. Other specified starting materials are acrylyl chloride, methyl acrylate, ethyl methacrylate, diethyl maleate and diethyl fumarate.  The anhydrides, acyl halides, esters, salts and amides of the acids are also specified as starting materials.  This subject-matter does not appear in the Specification as accepted.