Patent GB-702675-A (GB)
Title: Copolymers of fatty oil modified polyesters and vinyl monomers
IPC: C09D125/14
Filed: 1951-02-23
Abstract: Copolymers are made by heating together in an organic solvent, present in amount sufficient to prevent gelation of the reaction mixture, (1) a vinyl monomer having the formula CH2 = CHR wherein R is an aryl, heterocyclic, carboxy, carbalkoxy, ketonic, nitrile, or amido group, each of said groups having unsaturation in conjugation with the vinyl group, such as styrene, o-chlorostyrene, p-iodostyrene, fluorostyrene, dichlorostyrene, p-ethylstyrene, tert.-butylstyrene, ethoxystyrene, p-phenoxystyrene, p-dimethyl amino-styrene, vinyl biphenyl, vinyl naphthalene, o-vinyl benzoic acid, o-vinyl phenyl acetic acid, methyl, ethyl, propyl and phenyl vinyl ketones, 2-vinylpyridine, 2-vinylquinoline, vinyl pyrrole, vinyl carbazole, vinyl thiophene, acrylic acid, acrylonitrile, acrylamide, and methyl, butyl, octyl, lauryl, cyclohexyl, phenyl and benzyl acrylates, and (2) a fusible polyester of a polyhydric alcohol esterified with a fatty acid which is substantially free from conjugated double bonds, and with a Diels-Alder dibasic adduct of cyclopentadiene or dicyclopentadiene and an unsaturated dibasic acid or anhydride, such as maleic, fumaric, and acetylene dicarboxylic acids, said polyester having a calculated fatty oil content of at least 50 per cent., and a calculated average of 1 and not more than 3 diacyl residues of the adduct per polyester molecule.  In a modification of the process the adduct of cyclopentadiene or dicyclopentadiene with an unsaturated dibasic acid may be replaced by delta-1, 4-dihydrophthalic acid which is the adduct of butadiene with acetylene dicarboxylic acid.  A portion of the unsaturated adduct may be replaced by other dibasic acids such as succinic, adipic, sebacic, phthalic, chlorophthalic, and homophthalic acids, phthalic anhydride, dimerized linoleic acid, cis- or trans-delta-4-tetrahydrophthalic acid, and 3, 6-endomethylene hexahydrophthalic anhydride.  Polyhydric alcohols specified are diethylene glycol, triethylene glycol, propylene and dipropylene glycols, 2-ethylhexane diol, glycerol, trimethylol propane, sorbitol, pentaerythritol, and dipentaerythritol.  Fatty acids specified are those from perilla, linseed, walnut, safflower, poppyseed, soyabean, sunflower, corn, cottonseed, castor, coconut, menhaden and sardine oils, which may be employed in esterification either as the free acid, or as the oil, in which case an ester interchange reaction with the polyhydric alcohol is carried out. Fatty acids containing conjugated unsaturation, such as those from dehydrated castor oil or tung oil, may be employed in making the polyester in amount up to 20 per cent. of the total fatty acid content.  Suitable solvents are toluene, xylene, cumene, mineral spirits, benzine, naphtha, dipentene, amyl acetate, butyl propionate, dibutyl phthalate, cyclohexanol, ethylene glycol monoethyl ether, diethylene glycol diethyl ether, cyclohexanone, acetophenone, chlorobenzene, n-butyl ether, propionic acid, and a xylene/carbon tetrachloride mixture; solvents useful when using acrylonitrile as the vinyl monomer are dimethylformamide, acetonitrile, dimethyl methoxy-acetamide, N-formyl-morpholine, and N-formyl hexamethylene imine.  The copolymerization may be carried out with the aid of catalysts such as benzoyl peroxide, ditert.-butyl peroxide, p-chlorobenzoyl peroxide, bis (tert.-butyl peroxy) butane, dibenzal diperoxide, methylamyl ketone peroxide, cumene hydroperoxide, tert.-butyl hydroperoxide, tert.-butyl perbenzoate, diazoaminobenzene, tetraphenyl hydrazine, and azo-bis-isobutyronitrile.  The reaction may be carried out by heating the whole amount of the ingredients together, or certain of the ingredients may be added portionwise to the reaction mixture during copolymerization.  The copolymers may be used in preparing coating compositions, for which purpose the solution of copolymer in the reaction solvent with a pigment such as titanium dioxide may be employed.