Patent GB-959418-A (GB)
Title: Resinous compositions
IPC: C08L29/14
Filed: 1962-05-01
Abstract: Coating compositions comprise a polymer of 5 to 100 weight per cent of an a ,b -ethylenically unsaturated aldehyde and 95 to 0 weight per cent of at least one ethylenically unsaturated compound copolymerizable with said aldehyde, or a hemiacetal or acetal derivative of said polymer; a catalyst which is a mineral acid, organic acid, organo-substituted mineral acid and/or metal halide or a material yielding said catalyst on decomposition; and a polyglycidyl ether of a polyhydroxy compound. The compositions preferably comprise a polyol, e.g. an aliphatic polyhydric compound, polyester of allyl alcohol copolymer. The preferred aldehyde is acrolein. Many suitable comonomers are listed including monoolefins; diolefins; halogenated olefins; vinyl and isopropenyl esters; esters of allyl, methallyl and b -ethylallyl alcohols, 1-butene-4-ol, 2-methyl butene-4-ol, 1-pentene-4-ol and 2(2,2-dimethylpropyl)-1-butene-4-ol; esters of acrylic methacrylic, a -haloacrylic, a -cyanoacrylic, crotonic, tiglic, maleic, fumaric and glutaconic acids; nitriles; and acids such as acrylic, methacrylic, crotonic, 3-butenoic, angelic and tiglic acids. The polyglycidyl ethers may be reaction products of epihalohydrins with bisphenols, polyhydric phenols, aliphatic polyols and novolacs, many suitable components being listed. Specified catalysts are phosphoric, hydrochloric, sulphuric, p-toluenesulphonic, p-chlorotoluene sulphonic, chromomethyl phosphoric, perfluorosuccinic, trichloracetic and oxalic acids; and stannous, ferric, stannic and zinc chlorides; boron trifluoride; and complexes of such metal halides such as SnCl2. HCl.6H2O. Examples describe the copolymerization of acrolein with (I) ethyl acrylate and styrene, (II) methyl methacrylate, (III) ethyl acrylate and vinyl chloride, (IV) ethyl acrylate, (V) ethyl acrylate and acrylonitrile, (VI and XII) ethyl acrylate and acrylic acid, and (XI) ethyl acrylate and vinyl acetate in butanol in the presence of benzoyl peroxide; (VII) 2-ethylhexyl acrylate, ethyl acrylate and acrylic acid in butanol in the presence of t-butyl hydroperoxide; (VIII) ethyl acrylate and acrylic acid, and (IX) methyl methacrylate, ethyl acrylate and acrylic acid in isopropanol in the presence of benzoyl peroxide; (X) styrene, methyl methacrylate, 2-ethylhexyl acrylate and acrylic acid in glycol monoethyl ether, xylene and isopropanol in the presence of benzoyl peroxide; and (XIII) ethylhexyl acrylate in water in the presence of potassium persulphate and silver nitrate; and (XIV), the conversion of the copolymer of Example VII to acetal; and (XV) the preparation of a pigment paste from titanium dioxide, the copolymer of Example XII and toluene. Further examples describe coating compositions comprising (A to H) the pigment paste of Example XIII, the copolymer of Example XII, a solution of zinc chloride in ethanol, an epoxy resin, an epoxide oil and a polyester derived from adipic acid, phthalic anhydride, 1,3-butanediol and trimethylol ethane; (I to P) the copolymer of Example XIV, an epoxy resin, an allyl alcohol-styrene copolymer, and ethanol solutions of phosphoric acid and zinc chloride; and (Q to T) acrolein-styrene copolymers, allyl alcohol-styrene copolymers, epoxy resins and zinc chloride. The epoxy resins used in Examples A to T are glycidyl ethers of bis (4-hydroxyphenyl) 2,2-propane. The compositions may be used for coating phosphatised steel panels, and the coatings cured by heating. Specification 797,459 is referred to.ALSO:Substrates, e.g. phosphatized steel panels, may be coated, e.g by spraying, with compositions comprising a polymer of 5-100 weight per cent of an a ,b -ethylenically unsaturated aldehyde and 0-95 weight per cent of at least one ethylenically unsaturated compound copolymerizable with said aldehyde, or a hemiacetal or acetal derivative of said polymer; a catalyst which is a mineral acid, organic acid, organo-substituted mineral acid and/or metal halide or a material yielding said catalyst on decomposition; a polyglycidyl ether of a polyhydroxy compound and optionally a polyhydroxy compound or polymer, and the coatings cured by heating. Specified aldehyde polymers are polyacrolein and copolymers of acrolein with olefins, diolefins, halogenated olefins, esters of unsaturated alcohols, unsaturated acids and esters thereof.  The polyglycidyl ethers may be reaction products of epihalohydrins with bisphenols, polyhydric phenols, aliphatic polyols and novolacs.  Many suitable monomers and reactants are listed.  Specified polyhydroxy compounds and polymers are aliphatic polyols, hydroxyl-containing polyesters and allyl alcohol copolymers.  Specified catalysts are phosphoric, hydrochloric, sulphuric, p-toluene sulphonic, p-chlorotoluenesulphonic, chloromethyl phosphoric, perfluorosuccinic, trichloracetic and oxalic acids; and stannous, ferric, stannic and zinc chlorides; boron trifluoride; and complexes such as SnCl2.HCl.6H2O.  Examples describe the coating of phosphatized steel panels with compositions comprising (A to H) a pigment paste of titanium dioxide, a copolymer of acrolein, ethyl acrylate and acrylic acid, butanol and toluene; an ethanol solution of zinc chloride; the glycidyl ether of bis(4-hydroxyphenyl) 2,2-propane; an epoxide oil and a polyester derived from adipic acid, phthalic anhydride, 1,3-butanediol and trimethylolethane; (I to P) the butanol acetal of a copolymer of acrolein, 2-ethylhexyl acrylate, ethyl acrylate and acrylic acid; the glycidyl ether of bis(4-hydroxyphenyl) 2,2-propane; a copolymer of allyl alcohol and styrene and ethanol solutions of orthophosphoric acid and zinc chloride; and (Q to T) acrolein-styrene copolymers; allyl alcohol-styrene copolymers; the glycidyl ether of bis(4-hydroxyphenyl)-2,2-propane and zinc chloride.  Specification 797,459 is referred to.