GB887394A - Polymerisable mixtures and the production of copolymers on the basis of unsaturated polyester resins - Google Patents

Abstract

A polymerizable mixture contains (a) an unsaturated polyester resin containing the radical of an a , b unsaturated polycarboxylic acid but no b , g unsaturated ether radical and (b) an unsaturated polyester resin containing b , g unsaturated ether radicals but no a , b unsaturated polycarboxylic acid radicals. The mixture may also contain (c) at least one copolymerizable monomer containing the group CH2=C=. Preferred weight proportions are 95-20 parts of (a), 5 to 80 parts of (b), and 0 to 80 parts of (c). The polyester resin (a) may be prepared by reacting (i) an a , b unsaturated polycarboxylic acid or the half-ester or anhydride thereof with (ii) a polyhydric alcohol and, optionally, (iii) a non-polymerizable polycarboxylic acid. Starting materials specified are:-(i) maleic, fumaric, itaconic, citraconic, mesaconic, aconitic, muconic, and dimerized methacrylic acids, anhydrides and half-esters and chlormaleic acid; (ii) mono, di, and tri-ethylene glycols, propane diols 1.2 and 1.3, butane diols 1.2, 1.3 and 1.4, 2.21-dimethylpropane-diol-1.3, glycerine, trimethylol propane, pentaerythritol, cyclohexane-diol-1.4, terephthalic alcohol, and ethoxylated dihydroxydiphenylalkanes; and (iii) succinic, glutaric, adipic, pimelic, sebacic, suberic, -methyl glutaric, oxa- and sulphone-dibutyric, phthalic, iso-, tere-, di or tetrahydro-, endomethylene-tetrahydro-, hexachlorendomethylene-tetrahydro-, and tetrachlor- -phthalic, phenylenediacetic and the cyclohexane dicarboxylic acids and anhydrides. The polyester resin (b) may be derived from various combinations of non-polymerizable poly- and/or hydroxy-carboxylic acids and polyhydric alcohols, optionally with some monocarboxylic acid and/or monohydric alcohol, at least one component having a b -d unsaturated ether radical therein. Extensive lists of acids and alcohols are given wherein the unsaturated ether radical may be derived from allyl, methallyl or crotyl alcohol; butene-1-ol-3, butene-2-diol-1,4; butene-1-diol-3,4; hexene-3-diol-2,5; or cyclohexene-2-diol-1,4. Numerous optional comonomers (c) are mentioned including mono- and di-vinyl mono- and poly-nuclear aromatic hydrocarbons; vinyl pyridine; N-vinyl carbazole; vinyl ketones; vinyl sulphones; vinyl and allyl esters of saturated and unsaturated mono- and polycarboxylic acids; N-vinyl lactams; vinyl and allyl ethers; and the esters, amides and nitriles of acrylic, methacrylic and chloracrylic acids. Styrene is used in specific examples. The mixture may also contain non-polymerizable solvents. Inhibitors which may be used to stabilize the mixtures are hydroquinone, resorcinol, pyrocatechol or 2,6-di-t-butyl-p-cresol. Catalysts specified for effecting the copolymerization are the usual azo compounds and peroxides and hydroperoxides and t-butyl perbenzoate or permaleate. Redox systems of a peroxide and a tertiary amine or mercaptan may be used. "Metal driers" which may be used are Fe, Co, Ni, Mn, Cr, Pb, Zn, Ce, Al or Ca naphthenates, resinates, octoates or linoleates.