Patent GB-506666-A (GB)
Abstract: 506,666. Polymerizable oils. DU PONT DE NEMOURS & CO., E. I. Dec. 1, 1937, No. 33269. Convention date, Dec. 1, 1936. [Class 2 (iii)] Polymerizable oils are manufactured by reacting methacrylic anhydride with a polyhydric alcohol which is partly esterified with a polycarboxylic acid and partly esterified with an aliphatic monocarboxylic acid containing at least twelve carbon atoms, e.g. an acid of a drying or semi-drying oil, or a natural resin acid, or a mixture of such acids, but still contains some unesterified hydroxyl groups, the reaction being carried out at a temperature not substantially above 110‹ C., e.g. at 80- 90‹ C., preferably in the presence of a non- reactive solvent, e.g. an ether or an aliphatic or aromatic hydrocarbon boiling between about 60 and 200‹ C., and preferably in the presence of an organic acid alkali metal salt. When the reaction is complete, but before the product becomes insoluble in toluene, the reaction mixture is cooled, filtered, treated with aqueous calcium hydroxide solution to remove acidic ingredients, and again filtered. The products form films when baked with driers' or with peroxides, if desired after the addition of pigments. They are therefore suitable as ingredients of coating compositions, alone or in admixture with natural or synthetic resins, vegetable or animal oils, fats, waxes, plasticizers, pigments, dyes or fillers. They are also useful for coating, impregnating or sizing cellulosic materials such as textiles or paper, or for coating surfaces such as wood, metals, brick, stone or concrete. The partial esters employed as starting materials may be prepared by esterifying, by reaction with a polycarboxylic acid or its anhydride, a part of the residual hydroxy groups of a polyhydric alcohol partially esterified with a saturated or unsaturated aliphatic monocarboxylic acid containing at least twelve carbon atoms or a natural resin acid e.g. by reacting the polycarboxylic acid, if desired together with additional polyhydric alcohol, with a fatty oil monoglyceride obtainable by heating two molecular proportions of glycerol with one of a fatty oil in the presence of an alcoholysis catalyst, or with the products obtainable by partial esterification of glycerol with fatty oil acids or their anhydrides or natural resin acids, e.g. lauric, oleic, ricinoleic, linolenic, myristic, eleostearic, stearic or abietic acid. In examples : (1) methacrylic anhydride is heated in the presence of toluene and fused sodium acetate with the partial phthalate of soya bean oil monoglyceride, obtainable by heating raw soya bean oil with two molecular proportions of glycerol in the presence of litharge and heating the product with phthalic anhydride and glycerol; the product may be polymerized by heating with benzoyl peroxide ; coating compositions comprise solutions of the product in toluene with the addition of cobalt linoleate or benzoyl peroxide, in the former case with or without titanium dioxide or zinc oxide ; the properties of these solutions are compared with those of corresponding solutions of soya bean oil-modified alkyd resins; (2) the partial phthalate of soya bean oil monoglyceride is replaced by the product obtainable similarly from chinawood oil; (3) the product obtainable similarly from alkali refined linseed oil is heated with methacrylic anhydride in the presence of dioxane and fused sodium acetate. In these examples, the sodium acetate may be replaced by potassium methacrylate, propionate or phthalate, sodium butyrate or succinate, or lithium acetate, whilst 'as alternative solvents may be employed di-n-propyl, di-n-butyl, diisobutyl, di-sec.-butyl or di-n-amyl ethers, propyl butyl ethers, dioxane, #: #<1>-dichlorodiethyl ether, heptanes, octanes, nonanes, decanes, cyclohexane, benzene, toluene, xylenes or mesitylene, or mixtures thereof. Additional starting materials specified are : succinic, adipic, sebacic, maleic, diglycollic, diphenic, quinolinic, tartaric, citric and terephthalic acids and anhydrides; pentaerythritol, mannitol, sorbitol, arabitol, xylitol, ethylene glycol, diethylene glycol, hexamethylÚne glycol and diglycerol.