Patent GB-608023-A (GB)
Title: Improvements in or relating to the manufacture of resinous condensation products
Filed: 1946-03-27
Abstract: Synthetic resins are prepared by heating an aldehyde or ketone containing two conjugated ethylenic linkages, one of which is a b  to the carbonyl group or a substance capable of giving rise to such an aldehyde or ketone under the conditions of the reaction with an a b -unsaturated dicarboxylic acid, anhydride, ester or nonresinous halogen substituted derivative thereof or a substance capable of giving rise to such a body under the conditions of the reaction.  In some cases the reaction is explosively violent and it may be modified by an inert solvent, e.g. xylol.  Suitable aldehydes and ketones are furalacetone, crotonalacetone, octatrienal, cinnamalacetone and hexadienal.  Polyaldols giving rise to aldehyde and ketones of the kind in question by dehydration may also be employed.  Suitable acid bodies are maleic acid or anhydride, fumaric acid, acetylene dicarboxylic acid, glutaconin, citraconic or itaconic acid, ethyl maleate, dibutyl maleate, chloromaleic acid or bromofumaric acid. Malic acid or citric acid may also be employed.  Means may be provided for removal of water during the process.  An inert atmosphere may be used and loss of volatile reactants other than water may be prevented.  The products may be esterified with mono- or polyhydric alcohols, the esterification being modified if desired with fatty oil acids or esters thereof.  If desired the fatty oil or acid therefrom may be present during preparation of the adducts. Natural or synthetic resins, or fossil gums may be added at any stage of the process.  If the adduct contains a group capable of reaction with an aldehyde, e.g. a phenolic hydroxyl, urea or sulphonamido group, it may be reacted with an aldehyde. Esterification of the carboxyl groups is still possible.  Residual carbonyl groups in the adduct may be reacted with phenols, amines, urea or sulphonamides, or subjected to the aldol condensation with another aldehyde or ketone. If desired, phenols, amines, urea or sulphonamides may be present during the adduct formation.  The adducts may be copolymerized with substances such as styrene, di-isobutylene, methyl methacrylate or vinyl acetate or these substances may be present during adduct formation.  Metallic salts of the adducts may be formed, and insoluble heavy metal salts may be precipitated, e.g. on textiles from solutions of the alkali metal salts.  Aqueous solutions of the metal salts may also be used with aqueous emulsion of other film-forming ingredients in water-paints, butiminous dispersions, rubber latex, or as binding agents for linoleum or for treating fibrous materials.  The adducts may also be used for making shaped articles or in volatile solvents as coating compositions.  Drying of films formed from solutions of the adducts may be hastened by addition of benzoyl peroxide.  Drying of fatty acid or fatty acid ester modified products may be catalysed by driers such as cobalt, manganese and lead salts.  The products may also be incorporated in cellulose ester or ether lacquers.  Examples describe the preparation of resins as follows: (1) from furalacetone and maleic anhydride; (2) from crotonalacetone and maleic anhydride; (3) from furalacetone and maleic anhydride in presence of xylols; (4) from crotonalacetone and maleic anhydride in presence of xylol; (5) from cinnamalacetone and maleic anhydride in presence of xylol; (6) from hexadienal and maleic anhydride in xylol; (7) from octatienal and maleic anhydride in xylol; (8) from crude crotonalacetone, containing polycondensation products and maleic anhydride; (9) from maleic anhydride and a mixture prepared by reacting crotonaldehyde in the calcium hydroxide. The mixture contained octatrienal, the corresponding aldol product, some more highly condensed products and crotonaldehyde; (10) from maleic anhydride and a balsam obtained as residue in steam-distillation of product of alkaline condensation of crotonaldehyde; (11) from maleic anhydride and hard product of prolonged alkaline condensation of acetaldehyde; (12), (13) and (14) the product of examples (3), (7) and (10) were esterified with glycerol; (15), (16) the products of examples (3), (4) were esterified with a linseed oil monoglyceride; (17) the product of example (7) was heated with linseed fatty acids and glycerol; (18) cinnamalacetone was reacted with citric acid; (19) cinnamalacetone was reacted with dibutyl maleate; (20) crotonalacetone was reacted with itaconic acid; (21) cinnamalacetone was reacted with acetylene dicarboxylic acid; (22) crotonalacetone and bromofumaric acid were reacted; (23) acetaldol was heated with calcium hydroxide and the product with maleic anhydride; (24) as in (23) using citric acid in place of maleic anhydride; (25) crotonalacetone and maleic anhydride were condensed in presence of phenol; (26) linseed oil, cinnamalacetone and maleic anhydride were reacted.  The product could be esterified with glycerol; (27) cinnamalacetone and maleic anhydride were condensed in presence of styrene.  Specifications 600,408 and 600,618 are referred to.