Patent GB-810222-A (GB)
Title: Hardenable synthetic resinous compositions
IPC: C09D167/06
Filed: 1956-06-28
Abstract: Hardenable compositions comprise monomeric polymerizable ethylene derivatives and unsaturated polyesters containing radicals of a ,b -ethylenically unsaturated carboxylic acids and radicals of b ,a -ethylenically unsaturated ethers or benzyl ethers, optionally together with catalysts and inhibitors.  The polyesters may be derived from hydroxy and carboxy ethers, e.g. glycerol-a -allyl ether, trimethylolethane - monomethallyl ether, trimethylol - propane monoallyl, diallyl, monomethallyl, - methallyl, monocrotyl, monobenzyl, dibenzyl and methylvinylcarbinyl ethers, pentaerythritol monoallyl, diallyl and tricrotyl ethers, ethylene glycol monoallyl ether, 2,2,6,6-tetramethylolcyclohexanol-triallyl ether, 1,4-butenediol mono-and dihydroxyethyl ethers, glycidallyl ether, allyloxyacetic acid, b -allyloxypropionic acid and allyloxysuccinic acid; a ,b -unsaturated acids, e.g. maleic, fumaric, itaconic, acrylic, methacrylic and cinnamic acids; polyhydric alcohols, e.g. ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butenediol, glycerol, trimethylol propane, b ,b -bis-(hydroxycyclohexyl) propane, pentaerythritol and sorbitol; polycarboxylic acids, e.g. succinic, adipic, phthalic, tetrachlorophthalic and mellitic acids and the adducts of maleic anhydride and cyclopentadiene; and hydroxy acids, e.g. lactic, ricinoleic and citric acids.  They may be modified with butanol, allyl alcohol, tetrahydrofurfuryl alcohol, benzoic acid, tertiary butyl benzoic acid, oleic acid, linseed oil fatty acids, and the fatty acids obtained by the oxidation of paraffin.  The polyesters may be prepared in an inert atmosphere, e.g. nitrogen or carbon dioxide, in the presence of an inhibitor, e.g. hydroquinone and tertiary butyl pyrocatechol, adding a monohydric alcohol or excess of a polyhydric alcohol to prevent premature gelation.  The polyesters may be partially prepolymerized, e.g. by treatment with oxygen or a catalyst, or mixed with other unsaturated polyester resins. Specified ethylene derivatives are styrene, vinyl toluene, divinyl adipate and diallylphthalate.  The catalyst may be a peroxide, e.g. benzoyl peroxide, 1-hydroxy-11 -hydroperoxy-dicyclohexyl peroxide or 1,2,3,4 -tetrahydronaphthalene - 1 - hydroperoxide, optionally together with tertiary amines, e.g. dimethyl aniline or amine modified polyesters of the type disclosed in Specification 757,989, and driers, e.g. cobalt naphthenate or octoate.  The products may be used as moulding and casting composition, or mixed with solvents, e.g. acetone and ethyl acetate, and pigments, e.g. chromium oxide, as lacquers.  The preparation of the following polyesters are described in the examples: (1) from maleic and phthalic anhydrides, ethylene glycol and trimethylolpropane-monoallyl ether; (3) maleic and phthalic anhydrides, 1,3-butanediol and glycerol-a -allyl ether; (4) as (1) in that ethylene glycol; (7) maleic and phthalic anhydrides, adipic acid, ethylene glycol and trimethylolpropanemonoallyl ether; (8) maleic and phthalic anhydrides, 1,3-butane diol and trimethylol-propane-monoallyl ether and another is the adipic in place of phthalic; (9) maleic and phthalic anhydrides, ethylene glycol, trimethylol-propane-monocrotyl ether and trimethylol-propane-monomethyl vinyl carbinyl ether; (10) maleic and phthalic anhydrides, glycerol and trimethylol propane monoallyl ether; (11) maleic and phthalic anhydrides, ethylene glycol, and trimethylol-propane mono-and di-benzyl ethers; (12) maleic anhydride, ethylene glycol and b ,b -bis-(hydroxy-cyclohexyl)-propane, later reacted with phthalic anhydride and trimethylol propane mono- and di-methallyl ethers; (13) maleic and phthalic anhydrides, ethylene glycol and trimethylolpropane diallyl ether; (14) maleic and phthalic anhydrides, ethylene glycol, trimethylol-propane and b -allyl-oxy-propionic acid.