Patent GB-1005374-A (GB)
Title: Unsaturated dicarboxylic acid monoesters, polymers thereof, and methods of preparation
IPC: C08F222/14
Filed: 1962-05-16
Abstract: Monoesters of maleic, fumaric, chloromaleic, itaconic, mesaconic or citraconic acid with a monohydroxyalcohol of formula <FORM:1005374/C3/1> where R represents a C2-C8 alkylene group and R DEG  and A a C2 or C3 alkylene group with the proviso that R, R DEG and A each contain at least two carbon atoms extending in a chain between adjoining hereto oxygen or nitrogen atoms and n is an integer (see Division C2) are copolymerized with ethylenically unsaturated comonomers particularly vinyl and acrylic monomers, or in the case of itaconic derived monomers homopolymerized. Catalysts such as peroxides, persulphates, and azo compounds and bulk, solution, emulsion or suspension polymerization techniques may be used. Specified comonomers are acrylonitrile, methacrylonitrile, acrylic and methacrylic acids, their esters, amides and salts, itaconic acid and esters, maleic anhydride or maleic and fumaric acids and their esters, vinyl ethers, esters, and sulphides, styrene and its homologues and analogues, especially the vinyl toluenes and allyl esters of monocarboxylic acids, and many are listed.  Their copolymers may also be prepared by reacting a copolymer of the anhydride with the above specified alcohol, for example by dissolving the polymer in an inert solvent and adding the alcohol at a temperature between 40 DEG  and 200 DEG  C. The products may be cross-linked by heat or reaction with aldehydes, polyepoxides, polyisocyanates or anhydrides of polycarboxylic acids and they may be used in thermosetting compositions such as glass fibre-reinforced polyesters, as coating, impregnating or moulding compositions. Examples describe the copolymerization of b -(N,N1-ethyleneureido)-ethyl acid maleate, fumarate and itaconate with methyl methacrylate, styrene, and methacrylic acid using a benzoyl peroxide catalyst and a n-butanol and toluene solvent; b -(N,N1-ethyleneureido)-ethyl acid maleate with methyl methacrylate styrene, and ethyl acrylate; and the copolymerization of methyl methacrylate, styrene, ethyl acrylate, maleic anhydride using benzoyl peroxide, followed by a reaction with N-(b -hydroxyethyl)-ethylene urea.ALSO:The invention comprises a maleic, fumaric, chloromaleic, itaconic, mesaconic or citraconic acid monoester of a monohydroxy alcohol of formula <FORM:1005374/C2/1> where R represents C2-C8-alkylene group and R0 and A each represent a C2 or C3 alkylene group with the proviso that R, R0 and A each contain at least two carbon atoms in a chain between adjoining hetero oxygen or nitrogen atoms and n is an integer, and their preparation by reacting an anhydride with the monohydroxy-alcohol. The reaction may be in an inert solvent at a temperature from 40 DEG  to 200 DEG  C. and the fumaric ester may be prepared by isomerizing maleic ester. Examples describe the preparation of b -(N,N1-ethyleneureido) ethyl acid maleate, fumarate, and itaconate, b -(N,N1-propyleneureido) propyl acid itaconate and b -(N,N1-ethyleneureido) ethoxyethyl acid itaconate. The monoesters are solids of high melting-point and are copolymerizable with ethylenically unsaturated comonomers using conventional catalysts and the itaconate may in addition be homopolymerized.