ROSIN-FATTY ACID VINYLIC POLYMER COMPOSITIONS
(19)AUSTRALIAN PATENT OFFICE (54) Title ROSIN-FA 1 1 This invention relates to novel rosin-fatty acid vinylic polymer compositions and the process for preparing them. In particular, the invention relates to novel rosin-fatty acid vinylic polymer compositions that exhibit properties which make them useful as components of paper sizes, as components of coatings, and as support resins for producing polymer latices that can be employed in formulating water-based coatings and inks. More particularly, these rosin-fatty acid vinylic polymer compositions are mixtures that are produced by the addition polymerization reaction of vinylic monomers in the presence of saturated fatty acids, hydrogenated dimer acids, hydrogenated rosins, or mixtures thereof. A method for producing rosin-fatty acid vinylic polymer compositions which comprises reacting in a free-radical addition polymerization reaction:
(A) About 40% to about 80% by total weight of the reactants of a monomer mixture comprising:
(1) about 15.0% to about 45.0% by total weight of the monomer mixture of a member selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, and combinations thereof, (2) about 55.0% to about 85.0% by total weight of the monomer mixture of a member selected from the group consisting of non-carboxylic acid-containing vinylic monomers and combinations thereof, (3) a catalytic amount of polymerization initiator, and (4) up to about 4.0% by total weight of the monomer mixture of chain transfer agent, and (B) about 20% to about 60% by total weight of the reactants of a carboxylic acid mixture comprising:
(1) about 30.0% to about 100.0% by total weight of the carboxylic acid mixture of a member selected from the group consisting of saturated fatty acids, hydrogenated dimer acids, hydrogenated rosins, and combinations thereof; (2) up to about 70.0% by total weight of the carboxylic acid mixture of a member selected from the group consisting of rosins, unsaturated fatty acids, and combinations thereof; and (3) up to about 0.1 % by total weight of the carboxylic acid mixture of bleaching agent, The method of claim 1 which comprises reacting in a free-radical addition polymerization reaction:
(A) About 40% to about 80% by total weight of the reactants of a monomer mixture comprising:
(1) about 20.0% to about 35.0% by total weight of the mixture of a member selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, and combinations thereof, (2) about 65.0% to about 80.0% by total weight of the mixture of a member selected from the group consisting of non-carboxylic acid-containing vinylic monomers and combinations thereof, (3) a catalytic amount of polymerization initiator, and (4) about 0.5% to about 2.0% by total weight of the mixture of chain transfer agent, and (B) about 20% to about 60% by total weight of the reactants of a carboxylic acid mixture comprising:
(1) about 50.0% to about 100.0% by total weight of the carboxylic acid mixture of a member selected from the group consisting of saturated fatty acids, hydrogenated dimer acids, hydrogenated rosins, and combinations thereof; (2) up to about 50.0% by total weight of the carboxylic acid mixture of a member selected from the group consisting of rosins, unsaturated fatty acids, and combinations thereof; and (3) up to about 0.1% by total weight of the carboxylic acid mixture of bleaching agent, The method of claim 1 wherein the rosin-fatty acid vinylic polymer composition has a weight average molecular weight in the range of about 5,000 to about 11,000. The method of claim 1 wherein the rosin-fatty acid vinylic polymer composition has an acid number in the range of about 180 to about 250. The method of claim 1 wherein the non-carboxylic acid-containing vinylic monomer is a member selected from the group consisting of styrene, substituted styrenes, acrylic esters, methacrylic esters, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, vinyl esters, vinyl chloride, vinylidene chloride, vinylpyridines, N-vinylamides, vinyl ethers, and combinations thereof. The method of claim 5 wherein the non-carboxylic acid-containing vinylic monomer is a member selected from the group consisting of α-methylstyrene, m-methylstyrene,
p-methylstyrene, p-tert-butylstyrene, chlorostyrenes, 3-chloromethylstyrene, 4-chloromethylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, acetoxyethyl methacrylate, acrylamide, N-methylolacrylamide, N-butoxyethylacrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, diacetone acrylamide, methacrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl neodecanoate, vinyl stearate, N-vinylpyrrolidione, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, decyl vinyl ether, hydroxybutyl vinyl ether, and combinations thereof. The method of claim 1 wherein the polymerization initiator comprises from about 0.5% to about 5.0% by total weight of the monomer mixture and is a member selected from the group consisting of thermal initiators, redox initiators, and combinations thereof. The method of claim 1 wherein the chain transfer agent is a member selected from the group consisting of dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, octyl mercaptan, 2-mercaptoethanol, and combinations thereof. The method of claim 1 wherein the saturated fatty acid contains from 8 to 24 carbon atoms. The method of claim 9 wherein the saturated fatty acid is a member selected from the group consisting of lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, isostearic acid, and combinations thereof. The method of claim 1 wherein the hydrogenated rosin is partially hydrogenated. The method of claim 1 wherein the unsaturated fatty acid is a member selected from the group consisting of fatty acids containing from 12 to 24 carbon atoms and at least one carbon-carbon double bond, and combinations thereof. The method of claim 12 wherein the unsaturated fatty acid is a member selected from the group consisting of oleic acid, linoleic acid, linolenic acid, eleostearic acid, tall oil fatty acids, linseed oil fatty acids, tung oil fatty acids, safflower oil fatty acids, soybean oil fatty acids, and combinations thereof. The method of claim 1 wherein the rosin is a member selected from the group consisting of tall oil rosin, wood rosin, gum rosin, and combinations thereof The rosin-fatty acid vinylic polymer composition of claim 1. A latex comprising as a support resin an aqueous solution of the rosin-fatty acid vinylic polymer composition of claim 15. An ink comprising the latex of claim 16. The ink of claim 17 wherein the ink further comprises a pigment. A varnish comprising the rosin-fatty acid vinylic polymer composition of claim 15. A paint comprising the latex of claim 16. The paint of claim 20 wherein the paint further comprises a pigment.