Patent GB-600408-A (GB)
Title: Improvements in or relating to the manufacture of synthetic resinous condensation products
IPC: C08F16/36
Filed: 1944-11-16
Abstract: Synthetic resinous condensation products are prepared by heating an a b -unsaturated ketone, not containing conjugated ethylenic unsaturation and not itself readily polymerized to form a resin, or a substance capable of giving rise to the ketone under the conditions of the reaction with an a b -unsaturated dicarboxylic acid, anhydride, ester or non-resinous halogen derivative thereof or a substance capable of giving rise to the acid or its equivalent under the conditions of the reaction. Suitable ketones mentioned are mesityl oxide, phorone, benzal acetone, dibenzalacetone, dibenzalcyclohexanone, o-chlorobenzalacetone, monochloromesityl oxide, benzalacetonylacetone and o-hydroxybenzalacetone.  A substance giving rise to a ketone under the condition of the reaction is diacetone alcohol which loses water to produce mesityl oxide. Suitable acids or equivalents are maleic acid or anhydride, fumaric acid, glutaconic acid, citraconic acid, ethyl maleate, or chlormaleic acid.  Malic acid by loss of water gives rise to maleic acid and citric acid on heating gives a mixture of aconitic, itaconic and citiaconic acids.  The heating is preferably carried out with stirring in an inert atmosphere under conditions which facilitate removal of water especially during the latter stages of the reaction. With high boiling reactants an open vessel, if desired with an air reflux condenser, may be used. With lower boiling reactants a closed vessel and excess pressure may be used.  The products may be esterified, the esterification being modified, if desired, by oil fatty acids or esters thereof. Suitable alcohols for the esterification are butyl, allyl, cetyl, ethylene glycol, glycerol or pentaerythritol.  The resinous adducts may be dissolved in fatty oil or fatty acid before esterification, or the fatty acid or oil may be present during adduct formation.  Sometimes adduct, fatty acid and polyhydric alcohol may all be reacted together, or the adduct may be reacted with a partial ester of a fatty oil acid containing free hydroxyl groups, further polyhydric alcohol being added if necessary to complete esterification.  Natural resins, fossil gums and synthetic resins may be present during esterification.  When the adduct contains a group capable of reacting with an aldehyde, e.g. an adduct formed from o-hydroxybenzalacetone, or an adduct containing an amino or sulphonamido group, the adduct may be reacted with an aldehyde, e.g. formaldehyde, whilst still allowing esterification of the carboxylic groups.  Similarly, residual carbonyl groups in the adduct may be reacted with phenols, amines, urea or sulphonamides or these substances may be present during formation of the adduct. Unsaturated polymerizable substances such as styrene, di-isobutylene, methyl methacrylate and vinyl acetate may be present during the adduct formation or may be copolymerized with the adduct particularly when the adduct retains some unsaturation, e.g. the adduct formed from maleic acid and phorone.  The unesterified adducts may also form salts by treatment with a metal salt, oxide or hydroxide.  Sodium and potassium salts or soluble and insoluble heavy metal salts may be precipitated from their solutions, e.g. they may be formed in situ on textiles.  The aqueous salt solutions in combination with aqueous emulsions of other film-forming materials may be used for water paints, adhesives, as binding compositions and for treatment of paper, textiles and other fibrous materials.  The products of the invention may also be used for making shaped articles or, dissolved in volatile solvents, as coating compositions, to which benzoyl peroxide may be added or polymerization catalyst.  Fatty oil or acid modified adducts give air-drying compositions to which cobalt, manganese or lead driers may be added.  Cellulose esters or ethers may be mixed with the compositions to yield lacquers.  The resinous adducts may also be dissolved in drying oils to yield varnishes which may be thinned with mineral spirits.  Many of the resinous adducts are soluble in acetone, xylol, mineral spirits, butyl acetate, butyl alcohol or methylated spirits.  Many examples are given illustrating the above matters.  In one of them, crotonaldehyde is added to the reaction mixture of phorone and maleic anhydride.  In another, an adduct prepared from diethyl maleate and benzalacetone is stated to be compatible with a butyl-esterified urea-formaldehyde resin. A glycerine esterified benzalacetone-maleic adduct is also compatible with a linseed oil-modified glyceryl phthalate resin. Specification 517,684 is referred to.