Patent GB-989746-A (GB)
Title: Hydroxy-and carboxylic ester- containing copolymerizable monomers and process for preparing same
IPC: C08F22/20
Filed: 1962-05-10
Abstract: In one aspect, the invention comprises compounds of formula <FORM:0989746/C2/1> wherein <FORM:0989746/C2/2> is part of an aliphatic chain of from 10 to 24 carbon atoms, R1 is an aliphatic, cycloaliphatic or aromatic group having up to 18 carbon atoms, and R2 and R3 are independently hydrogen, halogen or C1-4 alkyl.  The aliphatic chain may contain other groups such as epoxy, hydroxyl, carboxy, carboxylic ester, carbamoyl, carbamoyloxy, amino, nitrile or halogen.  They are prepared by reacting a half-ester of formula R1OOCCR2= CR3-COOH with an epoxy compound containing the group <FORM:0989746/C2/3> in a C10-24 aliphatic chain, e.g. at 80-200 DEG C. with or without an oxirane-ring opening catalyst of which many are specified.  Preferred epoxy compounds are epoxidized glyceride oils. The half esters are prepared from hydroxy compounds, or in the case of fumaric esters by heat isomerizing the maleic esters with or without an isomerisation catalyst of which many are specified. Alternatively maleate products after reaction with the epoxy compound may be isomerized. The products may be used as plasticizers or to form copolymers with vinylidene monomers (see Division C3).  In another aspect fumaric acid half esters, obtained by isomerizing maleic acid half esters prepared by reacting maleic anhydride and a monohydroxy organic compound free from ethylenic unsaturation, are reacted with any vicinal epoxy compound, e.g. ethylene oxide, 1,2-propylene oxide, styrene oxide, epichlorohydrin, or, as in Example 29, the diglycidyl ether of Bisphenol A.  The products may be copolymerized with vinylidene monomers.ALSO:Vicinal acryloyloxy-hydroxy monomers containing groups of type <FORM:0989746/C3/1> are copolymerized with vinylidene monomers. The acryloyloxy-hydroxy monomers may have the general formula <FORM:0989746/C3/2> wherein <FORM:0989746/C3/3> is part of an aliphatic chain of from 10 to 24 carbon atoms, R1 is an aliphatic, cycloaliphatic or aromatic group of up to 18 carbon atoms, and R2 and R3 represent hydrogen, halogen or C1- 4 alkyl.  The aliphatic chain may contain other substituents such as epoxy, hydroxyl, carboxy, carboxylic ester, carbamoyl, carbamoyloxy, amino, nitrile or halogen; the preferred compounds (obtained from long-chain epoxy compounds and unsaturated half-esters, see Division C2) are derived from epoxidized glyceride oils. Another class of acryloyloxy-hydroxy monomer is obtained by reacting fumaric acid half-esters, which have been obtained by isomerizing maleic acid half-esters prepared by reacting maleic anhydride and a monohydroxy organic compound free from ethylenic unsaturation, with any vicinal epoxy compound, e.g. ethylene oxide, 1,2-propylene oxide, styrene oxide, epichlorohydrin or, as in Example 29, the diglycidyl ether of Bisphenol A.  Suitable vinylidene monomers include acrylic acid and esters, styrene, methylstyrene, vinyltoluene, allyl alcohol and esters, acrylonitrile, vinyl chloride, divinylbenzene, butadiene, maleic acid, crotonic acid, cinnamic acid, dipentene and myrcene. Polymerization may be effected in bulk, solution, suspension or emulsion using free radical catalysts, e.g. peroxides.  In examples, styrene is polymerized with vicinal acryloyloxy-hydroxy monomers derived from epoxidized soybean oil, esters of epoxidized stearic, soy and tall oil acids or epoxidized soya fatty alcohol and maleic or fumaric half-esters.