Patent GB-644287-A (GB)
Title: Improvements in or relating to the production of crystalline unsaturated alkyd resins and copolymerizable compositions and amorphous resins therefrom
IPC: C08L67/06
Filed: 1945-10-29
Abstract: A crystalline unsaturated alkyd resin is formed by reacting fumaric acid with a glycol of general formula HO(CH2)xOH (where x=2 to 18) or a dialkyl derivative thereof in which both alkyl groups are attached to the same carbon atom until the product has an acid number below 100.  Glycols mentioned are ethylene, neopentyl, trimethylene, tetramethylene, pentamethylene and hexamethylene glycol, decanediol, 1.10; and octadecane diol 1.18, or mixtures thereof.  The reaction mixture may include up to 75 mol. per cent (based on total carboxylic groups) of a symmetrical saturated dicarboxylic acid, e.g. succinic, glutaric, pimerlic, azelaic, terephthalic or sebacic acid, up to 10 mol. per cent of an unsymmetrical dicarboxylic acid, e.g. phthalic or indo-methylene-tetrahydrophthalic, up to 20 mol. per cent of monocarboxylic acid having at least 12 carbon atoms, e.g. lauric or stearic acid, up to 10 mol. per cent of monohydroxy monocarboxylic acid, e.g. o -hydroxycaproic, o -hydroxypelargonic, or o -hydroxydecanoic acid, or up to 10 mol. per cent (based on the total hydroxyl groups) of a monohydric alcohol, e.g. n-butanol, amyl alcohol, cyclohexanol, n-hexanol, 2-methyl hexanol, n-octanol, decanol, dodecanol, tetradecanol, cetyl alcohol, octadecanol, reduced geraniol, benzyl alcohol, phenylethyl alcohol, furfuryl alcohols, tetrahydrofurfuryl alcohol, hydroabietyl alcohol or reduced fatty oil acids.  The total proportion of modifiers (other than symmetrical dicarboxylic acids) should not exceed 20 mol. per cent of total hydroxy groups and 20 mol. per cent of total carboxyl groups. Preferably the number of hydroxyl groups in the reaction mixture is equivalent to the number of carboxyl groups.  Polymerization catalysts and oxygen are preferably excluded, e.g. by distillation of the reactants in the reaction chamber in absence of air.  Inert gas may be introduced into the reaction vessel, e.g. by bubbling through the reactants.  Reaction temperature is preferably 150-200 DEG  C. or lower if reaction is azeotropic, in which case an esterification catalyst is employed.  Examples describe the preparation of unsaturated alkyds from (1) and (2) ethylene glycol and fumaric acid; (3), (4) and (5) ethylene glycol, fumaric and sebacic acid; (6) ethylene glycol, fumaric and stearic acid; (7) neopentyl glycol and fumaric acid; (8) ethylene glycol, fumaric acid and o -hydroxy-decanoic acid.  Crystallisation of the resin may be aided by addition of a small proportion of aromatic hydrocarbon.  The products may be polymerized by heat or light with the aid of organic peroxides or may be copolymerized with a substance having a CH2=C< group, no conjugated carbon-to-carbon double bonds and a boiling point of at least 60 DEG  C.  In examples, unsaturated alkyds are copolymerized with (9) to (13) styrene and lauric peroxide; (14) p-methyl styrene and lauric peroxide; (15), (16) diallyl phthalate and benzoyl peroxide; (17), (18) diallyl ammelide and benzoyl peroxide; (19) diallyl phthalate which had been partially polymerized by heating in xylene.  These examples include description of the preparation of laminated glass cloth with the compositions, the inclusion of fillers, e.g. wood flour or glass flock, in the compositions to yield moulding powders, the inclusion of p-tertiary butyl catechol in the compositions and the preparation of films from the compositions. The composition may also be used for caulking and sealing seams. Other compounds mentioned as suitable for copolymerizing with the unsaturated alkyd resins are vinyl acetate, acrylonitrile, methacrylonitrile, maleic nitrile, fumaric nitrile, esters of acrylic and methacrylic acids, acrylamide, methacrylamide, p-methyoxystyrene, p-ethoxystyrene, p - cyanostyrene, mono - halogeno - styrenes, iso - propenyl toluenes, dimethyl styrenes, isopropenyl benzene, vinyl naphthalene, vinyl mesitylene, vinyl diphenyls, vinyl carbazole, vinyl phenols, vinyl furane, dialkyl esters of maleic, fumaric or itaconic acid, and a very large number of compounds containing one or more allyl groups.  The Specification as open to inspection under Sect. 91 is not limited to the use of fumaric acid, but covers any symmetrical a ,b -unsaturated dicarboxylic acid with transconfiguration, e.g. trans 1,2-dimethyl ethylenedioic acid-1,2. It also mentions still more compounds which may be copolymerized with the unsaturated alkyd resin.  This subject-matter does not appear in the Specification as accepted.  Specification 600,917 is referred to.