Patent GB-944322-A (GB)
Title: Ethylenically polymerizable long-chain compound and method of preparing same
IPC: C08L27/06
Filed: 1960-03-09
Abstract: The invention comprises an ethylenically unsaturated hydrocarbon, carboxylic acid or derivative thereof with at least one aliphatic chain of from 10 to 24 carbon atoms, with at least one pair of adjacent carbon atoms substituted thus: <FORM:0944322/C2/1> where p is an integer from 0 to 2, and X is hydrogen halogen, cyano, -CH2-COO alkyl (C1-4), phenyl, benzyl, or alkyl (C1-4).  The carboxylate derivatives are esters, amides, salts, alcohols, ethers, amines, mercaptans isocyanates, nitriles, halides or quaternary ammonium salts. Compounds described are animal or vegetable oils e.g. soy bean, corn, cotton seed, hemp seed, safflower, peanut, linseed, rice bran, olive, cod, herring, tall, or menhaden oil wherein at least one fatty acid chain in each glyceride molecule has a pair of adjacent carbon atoms substituted as above; a compound derived from a vegetable oil fatty acid ester and monohydric alcohol substituted in at least one C10 to C24 chain as above and in which p is O; the mono- or diglyceride of the fatty acid with the substituted C10 to C24 chain; a monohydric alcohol with the alkyl radical, C10 to C24 substituted as above; or esters of general formula: <FORM:0944322/C2/2> wherein Z represents phenyl, benzyl, 0-, m-, and p-tolyl, rescorcinyl, furfuryl, cyclohexyl, inosityl, glyceryl, pentaerithrityl, orabityl, sorbityl, alkylene (C2-C12) and alkyl (C12-C24), m is 1-6, n is 0 to 5, R is alkyl C1-C24, and Z and R provide at least one ethylenically unsaturated aliphatic chain of C10 to C24 atoms.  The compounds are prepared by reacting an epoxy compound e.g. a fatty acid glyceride epoxidised in at least one glyceride acyl group, and an aliphatic carboxylic acid H2C=CX-(CH2)n-COOH, amide or alcohol, wherein n is 0, 1 or 2 and X is hydrogen, halogen, cyano, -CH2-COO alkyl (C1-C4), phenyl, benzyl, or alkyl (C1-C4) in the presence of a polymerization inhibitor.  Oxygen or oxygen containing gas may be continually passed through the reaction mixture and examples of the acid are, acrylic, methacrylic, vinyl acetic, vinyl acrylic and alkyl acetic acids and methyl acid itaconate. Examples describe the reaction of epoxidised soybean oil with acrylic or methacrylic acids; epoxidised soybean fatty acid 2-ethyl hexyl esters with methacrylic acid; epoxidised soybean oil and monomethyl itaconate; epoxidised tall oil fatty acid isooctyl esters and methacrylic acid; epoxidised soybean oil fatty acid monoglyceride and methacrylic acid epoxidised soybean oil fatty alcohol and methacrylic acid, a -chloroacrylic a -phenyl acrylic, a -benzyl acrylic, and a -cyanoacrylic acids.  The products may be polymerized or copolymerized with cross-linking.ALSO:Polymers and copolymers of ethylenically unsaturated hydrocarbons and carboxylic acids or derivatives thereof with at least one aliphatic chain of from 10 to 24 carbon atoms and with at least one pair of adjacent carbon atoms substituted thus: <FORM:0944322/C3/1> where p is an integer from 0 to 2 and X is hydrogen, halogen, cyano, -CH2.COO (alkyl C,1-4,), phenyl, benzyl, or alkyl (C, 1-4), (see Division C2) are prepared using peroxide catalysts. Copolymers with methyl and ethyl methacrylates, ethyl and stearyl acrylate, acrylic and methacrylic acids, styrene and methyl styrene, alkyl alcohol, vinyl acetate and stearate, acrylonitrile, butadiene, maleic, crotonic and cinnamic acids, dipentene, myrcene are mentioned and the products are viscous liquids to rubbery and hard resins.  Examples describe the reaction of epoxidised soybean oil with acrylic or methacrylic acid and the homo polymerization of the product and the copolymerization of the soybean oil-acrylic acid and the soybean oil-methacrylic acid products with styrene and the copolymerization of the soybean oil-methacrylic acid product with methyl methacrylate; of epoxidised soybean fatty acid 2-ethylhexyl ester and methacrylic acid and the homo- and copolymerization of the product with methyl and butyl methacrylates; of epoxidised soybean oil and monomethylitaconate and the homopolymerization of the product; of epoxidised tall oil fatty acid isooctyl esters and epoxidised soybean oil and the copolymerization of the product with methacrylic acid; of epoxidised soybean oil fatty acid monoglyceride and methacrylic acid and the homo- or copolymerization of the product with styrene; of epoxidised soybean oil fatty alcohol and methacrylic acid and the homopolymerization of the product. The products are useful as protective coatings, sizing and textile and paper additives, laminating and potting resins, stabilizer-plasticizers and adhesives.