Patent GB-714432-A (GB)
Title: Improvements in or relating to the manufacture of vinyl copolymers
IPC: C08F212/14
Filed: 1951-08-13
Abstract: Vinyl compounds, e.g. styrene, a -methyl styrene, a mixture thereof, vinyl acetate, butyrate and propionate, vinyl chloride, p  acrylic acid esters and acrylonitrile, are copolymerized with unbodied, non-conjugated, unsaturated drying or semidrying fatty acids, their esters or partial esters, with one or more polyhydric alcohols, or combined with polybasic acids as oil modified alkyd resins, by heating at 325 DEG  to 550 DEG F. in the presence of from 0.002 to 3.5 per cent. by weight of the vinyl compound, of a non-metallic reducing polymerization inhibitor and from traces up to 5 per cent. of a non-metallic oxidizing polymerization catalyst.  The fatty acids may be derived from linseed, soya bean, flax, chia, perilla, safflower, sunflower, menhaden, and sardine oils and may be modified with dibasic acids or anhydrides free from ethylenic unsaturation, e.g. malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, and phthalic acids, conjugated drying oil fatty acids (not more than 20 per cent.) and saturated fatty oil acids.  Excess acidity may be removed by esterification with polyhydric alcohols such as glycol, glycerine, pentaerythritol, di- and polypenta-erythritols, mannitol, sorbitol, and poly-allyl alcohols. Oil-modified alkyd resins with not more than one part of china wood oil to four parts of non-conjugated oil may also be used.  The oxidizing catalysts include oxygen, air, sulphur dioxide, hydrogen, di-t-butyl, and benzoyl peroxides, cumene hydroperoxide, anthraquinone, b -chloro-anthraquinone, benzo-, naphtha-, and anthraquinones and retene quinone and the reducing inhibitors may be alkyl mercaptans, e.g. n-amyl, hexyl to t-dodecyl mercaptans such as octyl, and t-hexadecyl mercaptans, hydroquinone, nonyl alcohol, benzidine, t-butyl-catechol, acetaldoxime, guiacol, p-phenylene diamine, resorcinol, phenyl naphthylamine and 2-4-diamino-azobenzene. The vinyl compound, which may be used in amounts of 10 to 100 per cent. of the fatty acids, may be added portionwise or continuously during the reaction.  The product may be purified by blowing or by steam distillation and when pigmented may be used as a coating composition.  Examples describe (1) and (2) the copolymerization of linseed oil or fatty acids with styrene using a sulphur-dioxide-benzidine or para-t-butyl-catechol catalyst combination and the preparation of an oil modified, glycerolphthalic anhydride alkyd resin using the styrenated oil; (4) a soyabean oil-pentaerythritol-phthalic anhydride alkyd resin reacted with styrene using cumene hydroperoxide, t-butyl catechol and t-dodecyl mercaptan; and (5) an alkyd resin derived from pentaerythritol and phthalic anhydride modified with soya, safflower, dehydrated castor, linseed, or fish oil, or 10 per cent. tung and 90 per cent. soya oil reacted with styrene with the following catalyst combinations, cumene hydroperoxide and para t-butyl catechol with t-dodecyl, n-amyl, or octyl mercaptan; di-t-butyl peroxide with para-t-butyl-catechol and t-dodecyl mercaptan; and anthraquinone with para-t-butyl catechol, t-dodecyl mercaptan or hydroquinone.