Patent GB-1117763-A (GB)
Title: Hydroxylated graft copolymer compositions
IPC: C03C25/27
Filed: 1965-06-18
Abstract: A blend comprises (A) a graft polymer comprising a diene rubber substrate and a hydroxylic superstrate polymer in a proportion of 15 to 200 parts by weight of superstrate per 100 parts of substrate, said substrate being a rubbery polymer of 40 to 100% by weight of butadiene and/or isoprene and 60 to 0% of one or more vinylidene, vinyl or vinylene monomers and said superstrate being a polymer of (a) from 1 to 100% of an ethylenically unsaturated alcohol, (b) from 0 to 50% of an ethylenically unsaturated nitrile and (c) from 0 to 95% of one or more other monomers, and one of the following: (B1) an interpolymer of a monovinyl or monovinylidene aromatic compound and an ethylenically unsaturated nitrile, said interpolymer having a specific viscosity of 0.04 to 0.15 as measured at 25 DEG  C. as a solution of 1% by weight of the interpolymer in dimethyl formamide or from 0.05 to 0.1 as measured at 25 DEG  C. as a solution of 0.1% of the interpolymer in dimethyl formamide; or (B2) (i) an interpolymer of (a) from 20 to 45 mol per cent of an acid monomer selected from a ,b -ethylenically unsaturated polybasic acids, the anhydrides of such acids and mixtures thereof and (b) 80 to 55 mol per cent of at least one vinyl, vinylene or vinylidene comonomer, said interpolymer having a Parr-Bar softening point of less than 225 DEG  C. and an intrinsic viscosity of less than 0.5 as determined in pyridine at 30 DEG  C., and (ii) an epoxy compound containing a plurality of epoxy groups in proportion so as to provide an average of from 0.2 to 1.2 epoxy groups per carboxyl group of component (i); or (B3) (i) an interpolymer of (a) from 2 to 30% by weight of at least one acid of formula CH2=CRCO2H where R is hydrogen, halogen or an alkyl group of 1-4 carbon atoms, (b) from 2 to 40% of acrylonitrile, methacrylonitrile or a mixture thereof and (c) at least one vinyl, vinylene or vinylidene comonomer, and (ii) an epoxy compound containing a plurality of epoxy groups in proportion so as to provide an average of at least 0.4 epoxy group per carboxyl group of said component (i).  In the examples, aqueous graft polymer latices are prepared using the following diene rubber substrates: polybutadiene, a copolymer of butadiene with styrene, and/or vinyl benzyl alchol or 2-phenylallyl alcohol, a butadiene-acrylonitrile copolymer or an isoprene-styrene copolymer.  The hydroxylic graft monomer is 2-phenylallyl alcohol, vinylbenzyl alcohol, 2-hydroxymethyl butadiene, ethyl betahydroxyethyl fumarate, betahydroxyethyl acrylate or bis(betahydroxyethyl)fumarate and the other graft monomers employed in some cases are selected from styrene, acrylonitrile, vinyl chloride, methyl methacrylate, ethyl acrylate, butene-1 and butadiene.  The graft polymer latices are blended with B1-a styrene-acrylonitrile copolymer emulsion and a styrenated phenol antioxidant, or (B2) (i) a copolymer of maleic anhydride with styrene or methyl methacrylate or with both styrene and ethyl acrylate, acrylonitrile, butadiene or 2-ethylhexyl acrylate and (B2) (ii) the diglycidyl ether of bisphenol A, or with (B3) (i) a copolymer of acrylic acid with acrylonitrile, or methacrylonitrile, and styrene, methyl methacrylate, vinyl acetate or vinyl chloride, or of methacrylic acid, acrylonitrile and vinyl chloride, or of chloroacrylic acid, acrylonitrile and vinyl acetate and (B3) (ii) the aforementioned diglycidyl ether.  The blends containing the (B2) and (B3) ingredients are dissolved in methyl ethyl ketone and used in the preparation of laminates (see Division B5). The preparation in solution of the (B2) (i) and (B3) (i) interpolymers employed is described in Examples V and VIII.ALSO:A coating composition comprising an organic medium containing a blend of A) a graft copolymer with a diene rubber substrate and a hydroxylic superstrate with B2i) an interpolymer of an alpha, beta-ethylenically unsaturated polybasic acid or an anhydride thereof with a vinylidene monomer and B2ii) a polyepoxy compound, or with B3i) an interpolymer of an acid monomer CH2=CR CO2H wherein R is hydrogen, halogen or a C1 to C4-alkyl group with acrylonitrile or methacrylonitrile and B3ii) a polyepoxy compound, is applied by e.g. spraying, brushing, rolling or dipping, to metal surfaces such as primed or unprimed steel, aluminium, chromium, nickel, copper and brass, paper, cardboard, plywood, leather, textiles, glass, porcelain or plastics e.g. polyesters, or methacrylate or styrene polymers. The coatings, which may also contain pigments, are cured.