Patent GB-1100395-A (GB)
Title: 2-hydroxyalkyl acrylate and methacrylate dicarboxylic acid partial esters and the oxyalkylated derivatives thereof
Inventor: BEARDEN CHARLES RAY
IPC: C08F299/02
Filed: 1965-05-20
Abstract: Dicarboxylic acid half-esters derived from 2-hydroxyalkyl-acrylates or methacrylates and a dicarboxylic acid anhydride, or their oxyalkylated derivatives (see Division C2) may be cured by reaction with an ethylenically unsaturated monomeric compound to form thermosetting resins, the term "alkyl" being defined as including "haloalkyl."  The half-ester or its oxyalkylated derivative may be reacted with a polyepoxide, polyisocyanate or polyamine before or during the reaction with the ethylenically unsaturated compound or the polyepoxide, polyisocyanate or polyamine may be reacted alone with the half-ester or its oxyalkylated derivative to form a curable resin, the reaction being preferably effected at 20-120 DEG  C. in the presence of a vinyl polymerization inhibitor.  When the oxyalkylated derivative of the half-ester is used an equimolar proportion of the dicarboxylic acid anhydride used in its preparation should also be present.  Specified ethylenically unsaturated compounds are styrene, vinyl toluene, ethyl vinyl benzene, isopropyl-, t-butyl- and sec-butyl styrene, a -methyl styrene, divinyl benzene, dichlorostyrene, diallyl phthalate, triallyl cyanurate, acrylic acid, vinyl acetate, methyl and ethyl acrylate and methacrylates, cyclohexyl acrylate and beta-hydroxyethyl acrylate. The curing is preferably carried out in bulk and in a mould at from 20 DEG  to 150 DEG  C., preferably in the absence of air, and a peroxy catalytic compound, e.g. benzoyl, lauryl or methyl ethyl ketone peroxide, may be present, with or without a naphthenate or amine accelerator.  The polyepoxides may be glycidyl polyethers of a polyhydric alcohol or phenol, epoxidized-fatty acids or -drying oil acids, epoxidized diolefins or epoxidized diunsaturated acid esters or -unsaturated polyesters.  The polyisocyanates may be 2,4- or 2,6-tolylene diisocyanate, the phenylene or naphthalene diisocyanates, 1,2,4-benzene triisocyanate, or hexamethylene-, trimethylene-, ethylene-, 1,4-cyclohexylene- or 1,3 - cyclopentylene - diisocyanates.  Suitable polyamines include melamine, hexamethylol-melamine and the hexabutyl ether of hexamethylol melamine.  The dicarboxylic acid anhydride from which the half-ester is derived-may be unsaturated or saturated, maleic anhydride being used in the examples given.  The thermosetting compositions may include other additives such as plasticizers, glass, metal filings, sand, and clay, and are useful in the production of pottings, castings or laminates (see Division B5).ALSO:The invention comprises a dicarboxylic acid half ester of a dicarboxylic acid anhydride and either a 2-hydroxy alkyl acrylate or a 2-hydroxy alkyl methacrylate and the oxyalkylated derivatives of said half ester, the term "alkyl" being defined as including "haloalkyl." Specified acid anhydrides are maleic anhydride, chloromaleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride and chlorendic anhydride and mixtures thereof.  The 2-hydroxy alkyl group preferably has from two to six carbon atoms.  The oxyalkylated derivatives are obtained by reacting an alkylene oxide, particularly a C2-C4 alkylene oxide, e.g. ethylene-, propylene-, or butylene-oxide, or an halogenated alkylene oxide, e.g. epichlorohydrin, with the half ester.  The half ester is preferably prepared by condensing 0.8 to 1.2 moles of the dicarboxylic acid anhydride per mole of the 2-hydroxyalkyl acrylate or methacrylate in the absence of a solvent at 20 DEG  to 150 DEG  C. Alternatively, it may be obtained by reacting acrylic acid or methacrylic acid with a lower alkylene oxide or halogenated alkylene oxide in the presence of the dicarboxylic acid anhydride.  A vinyl polymerization inhibitor may be present. The 2-hydroxyalkyl acrylate or methacrylate may contain small amounts of their oxyalkylated derivatives and the specified acrylates or methacrylates are 2-hydroxyethyl-, 2-hydroxypropyl-, and 2-hydroxybutyl acrylates and methacrylates.  In examples, half esters are prepared from maleic anhydride and 2-hydroxyethyl- and 2-hydroxypropyl acrylates respectively.  The products may be reacted with ethylenically unsaturated compounds and/or with polyfunctional reactants to give resins (see Division B5 and C3).