Patent GB-962109-A (GB)
Title: New copolymers and coating compositions thereof
IPC: C08L61/20
Filed: 1960-07-29
Abstract: Linear addition copolymers comprise at least 50% by weight of methyl and/or ethyl acrylate and from 3 to 50% by weight of one or more isopropyl phenyl acrylates of the formula: <FORM:0962109/C3/1> where n is 1 or 2, preferably p-isopropyl phenyl acrylate.  Also present in the copolymers may be up to 47% by weight of one or more monoethylenic compounds such as C1-C18 alkyl methacrylates, C3-C18 alkyl acrylates, acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyl toluene, vinyl and vinylidene chlorides acrylic, methacrylic and itaconic acids, acrylamide and its N-methyl derivative, N-methylol and N-methoxymethyl methacrylamides, ureidoethyl, hydroxyethyl and dimethylaminoethyl acrylates and methacrylates, ureidoisobutyl vinyl ether and sulphide, aminoethyl vinyl ether and sulphide methoxymethyl vinyl sulphide, vinyl pyridines and methacryloxy acetamidoethyl-N, N1-ethylene urea. Copolymers containing carboxyl groups or may be neutralized with ammonia, and amine or an alkali metal hydroxide. The copolymers may be made by bulk, solution, suspension or, preferably, emulsion polymerization methods, with the aid of an initiator such as organic peroxides, hydroperoxides and peresters, redox catalysts, e.g. potassium persulphate and sodium metabisulphite, which may be activated by multivalent metal salts, and azo catalysts. In aqueous emulsion polymerization there may be used a non-ionic, anionic or cationic emulsifier. Also present during the reaction may be a chain transfer agent, e.g. mercaptoethanol. The copolymers, particularly in the form of aqueous emulsions are used in coating applications, for which purpose they may be used in conjunction with: (a) pigments, e.g. carbon black, iron oxides, chrome yellows, zinc ozide titanium dioxide, lithopone, finely divided aluminium, bronze, brass, chromium or gold, azo pigments, phthalocyanine pigments and insoluble vat dyestuffs, (b) thickening agents, e.g. tragacanth, cellulose ethers and polyvinyl alcohol, (c) alkalies, e.g. sodium carbonate or acetate, chalk, morpholine, N-methylmorpholine, triethylamine and ammonia, (d) thermosetting aminoplast condensates, e.g. urea-formaldehyde, N,N1-ethyleneurea-formaldehyde and aminotriazing-formaldehyde condensates, which may be used in etherified form, (e) polyisocyanates, e.g. hexamethylene, toluene and p-phenylene diisocyanates, (f) polyepoxides e.g. those of the formulae: <FORM:0962109/C3/2> where X is a number having an average value of 1 to 3, <FORM:0962109/C3/3> where Y is a number having an average value of 2 to 4, <FORM:0962109/C3/4> where m is 2, 3 or 4 and Z is a number having an average value of 1 to 5, <FORM:0962109/C3/5> in which C10H13 is the radical of exo-dihydro-dicyclopentadiene, the two O1 groups are oxygen atoms which together with two adjacent carbon atoms in the C10H13 radicals form oxirane rings and R is either a C2-C12 alkylene group or a polyoxyalkylene group, and polyether derivatives of a polyhydric alcohol containing epoxy groups, e.g. those of the formula: <FORM:0962109/C3/6> where #F is a phenylene group and n has an average value of 0 to 7, (g) other copolymers of the invention, and (e) diethyl phthalate and diethylene glycol. After application to a substrate the coating, when thermosetting, may be heated to elevated temperatures to render it infusible and solvent- and water-resistant. The examples describe the emulsion copolymerization of: (1) p-isopropylphenyl acrylate, ethyl acrylate, methyl methacrylate and itaconic acid; (2) m-isopropylphenyl acrylate, ethyl acrylate, methacrylamide and methylol methacrylamide; (3) o-isopropylphenyl acrylate, ethyl acrylate and methacrylamide; (6) diisopropylphenyl acrylate, ethyl acrylate and itaconic acid; (7) (a) isopropylphenyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and itaconic acid, and (b) isopropyl phenyl acrylate, N-methylolmethacrylamide and methyl acrylate; (9) p-isopropylphenyl acrylate, methyl acrylate and itaconic acid; and (10) isopropylphenyl acrylate, ethyl acrylate, methyl methacrylate and methacryloxyacetamidoethyl-N,N1-ethyleneurea. Specifications 518,057 and 579,698 are referred to.ALSO:Surfaces of paper, leather, textiles, ceramics, wood, metals, stone, cement, bricks, asbestos cement and cinder block are coated by applying thereto aqueous dispersions of copolymers comprising at least 50% by weight of methyl and/or ethyl acrylate and from 3-50% by weight of one or more isopropylphenyl acrylates of the formula:  <FORM:0962109/B1-B2/1> where n is 1 or 2.  Also present in the copolymers may be up to 47% by weight of one or more other monoethylenic compounds.  The aqueous dispersions may also contain thickeners, alkalies, pigments, thermosetting aminoplast condensates and polyepoxides. After application to a substrate the coating, when thermosetting, may be heated to elevated temperature to render it infusible and solvent-resistant.  In the examples: (1) leather with a base coat of a polyacrylic ester is coated with an aqueous dispersion containing dimethoxymethylpolymethylolmelamine and a copolymer of p-isoproplyphenyl acrylate, ethyl acrylate, methyl methacrylate and itaconic acid, dried and then smooth plated at 150-155  DEG F.; (3) chipboard, kraft paper and wall paper are coated with an aqueous dispersion containing a mixture of copolymers of (a) m-isopropylphenyl acrylate, ethyl acrylate, methacrylamide and methylol acrylamide and (b) o-isopropylphenyl acrylate, ethyl acrylate and methacrylamide, and then dried; (4) asbestos cement sheets are coated with an aqueous dispersion containing a copolymer of o-isopropylphenyl acrylate, ethyl acrylate and methacrylamide, a resin-forming methoxymethylpolymethylolmelamine condensate, diethyl phthalate and, optionally, a copolymer of m-isopropylphenyl acrylate, ethyl acrylate, methacrylamide and methylol methacrylamide, and then dried; (8) a pile fabric having a base fabric of cotton and a pile of viscose rayon and cellulose acetate is back-coated with an aqueous dispersion containing a copolymer of isopropylphenyl acrylate, ethyl acrylate and itaconic acid, and then dried and cured by heating at 300  DEG F.; (9) the process of (1) is repeated using a copolymer in which the ethyl acrylate is replaced by methyl acrylate and the melamine condensate is replaced by a polyepoxide; and (10) wood surfaces including those primed with alkyd resin paints, and masonry surfaces are coated with an aqueous dispersion containing a copolymer of isopropylphenyl acrylate, ethyl acrylate, methyl methacrylate and methacryloxyacetamidoethyl-N,N1-ethyleneurea, titanium dioxide, zinc oxide, the sodium salt of diisobutylene/maleic anhydride copolymer and an octylphenoxypolyethoxyethanol. Specifications 518,057 and 579,698 are referred to.ALSO:Textile materials are coloured by applying thereto pigmented aqueous dispersions of copolymers comprising at least 50% by weight of methyl and/or ethyl acrylate and from 3 to 50% by weight of one or more isopropylphenyl acrylates of the formula: <FORM:0962109/D1-D2/1> where n is 1 or 2.  In examples: (5) cotton percale is padded with an aqueous dispersion containing a copolymer of isopropylphenyl acrylate, ethyl acrylate and itaconic acid, copper phthalocyanine pigment, sodium alginate and an octylphenoxypolyoxyethanol, followed by drying at 300 DEG F.; (7) cotton fabric is coloured by a composition similar to that of (5) but in which the copolymer is made from isopropylphenyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and itacionic acid.  In an example (6) the fibres in a non-woven cotton textile fabric are bound together by spraying with an aqueous dispersion of a copolymer of diisopropylphenyl acrylate, ethyl acrylate and itaconic acid, followed by drying at 140 DEG C.  Specifications 518,057 and 579,698 are referred to.