Patent GB-1048913-A (GB)
Title: Coating polymeric material
IPC: C08J7/046
Filed: 1964-01-28
Abstract: Polymeric materials containing a basic group are coated by applying thereto a solution or dispersion of a normally solid linear addition polymers of an ethylenically unsaturated monomer containing at least 0.1 mole per cent of carboxylic acid halide group-containing monomers, and which is free from basic or other groups which react with said acid halide groups, and heating the coated material to react at least 0.1 mole per cent of said carboxylic acid halide group-containing polymer with the polymeric material to form ester or amide linkages between the applied polymer and the polymeric material.  The basic group of the polymeric material may be hydroxyl, mercaptyl, primary or secondary amine, or annide.  The polymeric material may be cellulosic e.g. cellulose, regenerated cellulose, cellulose ethers, cellulose esters, or otherwise modified cellulose, or proteinaceous e.g. wool, hair, silk, leather, or synthetic e.g. polyamides, polyesters.  It may be in the form of paper pulp, fabricated paper (e.g. cardboard, wallboard, boxboard) or fibre, or a woven or non-woven fabric, film or sheet.  The acid halide containing polymer may be applied by conventional techniques to the polymeric substrate.  The addition polymers containing the acid-halide groups may either be addition polymers of ethylenically unsaturated monomers containing a carboxylic acid halide group or ethylenically unsaturated monomers co-polymerized with ethylenically unsaturated carboxylic acid halides.  The acid halide co-polymers may be obtained by the halogenation of the corresponding acid copolymers.  Using phosphorus pentahalide, or by a method as disclosed in Specification 1,048,914.  The acid halide groups in the polymeric coating component may be obtained by the polymerization of an a , b -ethylenically unsaturated acid, which is then halogenated.  The acid preferably contains 3 to 8 carbon atoms e.g. acrylic, methacrylic, itaconic, maleic, crotonic, fumaric, glubaconic or cinnamic acids.  If a polycarboxylic acid is used, one of the acid groups can be esterfied. The acid monomers may be homo- or co-polymerized.  In the latter instance, they may also be copolymerized with ethylenically unsaturated monomers to give rise to acid polymers which can be then be converted to the acid halide copolymer.  Such monomers may have the general formula <FORM:1048913/B1-B2/1> where A is H, a hydrocarbon group e.g. alkyl, aryl, a halogen, carboalkoxy such that the monomer is an acrylate or methacrylate, acryloxy such that the monomer is a vinyl ester, an ether group e.g. alkoxy, a nitrile or aldehyde group such that the monomer is an acrolein or substituted acrolein, and B is H, or CH3 or halogen.  Preferred polymers are copolymers of olefins, R - CH = CH2 where R = H, or C1 - 8 alkyl or aryl, with acid halides of the described carboxylic acids.  Suitable olefins include-ethyline, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene-1, 4-methylpentene-1 and styrene.  The acid halide copolymer need not necessarily comprise a two-component polymer, and an inert copolymerisable monomer may be employed in conjunction with the olefin and acid halide. Specified acid copolymers, which may be converted to acid-halide copolymers, are ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/itaconic acid, ethylene/methyl hydrogen mallate, ethylene/mallic acid, ethylene/acrylic acid/methyl methacrylate, ethylene/methacrylic acid/ethyl acrylate, ethylene/itaconic acid/methyl methacrylate, ethylene/methyl hydrogen mallate/ethyl acrylate, ethylene/methacrylic acid/vinyl acetate, ethylene/acrylic acid/vinyl formate, ethylene/propylene/acrylic acid, ethylene/styrene/acrylic acid, ethylene/methacrylic acid/acrylonitrile, ethylene/fumaric acid/vinyl mothyl ether, ethylene/vinyl chloride/acrylic acid, ethylene/vinylidene chloride/acrylic acid, ethylene/vinyl fluoride/methacrylic acid/ethylene/chlorotrifluoro-ethylene/methacrylic acid, polyethylene/acrylic acid graft copolymers, polyethylene/methacrylic acid graft copolymens, ethylene/butene-1 methacrylic acid graft, ethylene/vinyl acetate/methacrylic acid graft, polypropylene/acrylic acid graft, polypropylene/methacrylic acid graft, polybutene/acrylic acid graft, poly-3-methyl butene/acrylic acid graft and polyethylene/acrylic acid/ethyl acrylate graft co-polymers. Examples relate to the coating of wool fabric, black-flannel, cotton poplin, polyamide film "cellophane" (Registered Trade Mark) film, tire cords, nylon cloth, and leather (goat skin).ALSO:Polymeric fibres containing a basic group are coated by applying thereto a solution or dispersion of a normally solid linear addition polymer of an ethylenically unsaturated monomer containing at least 0.1 mole per cent of carboxylic acid halide group-containing monomers, and which is free from basic or other groups which react with said halide groups, and heating the coated fibres to react at least 0.1 mole per cent of said carboxylic acid halide group-containing polymer with the fibre to form ester or amide linkages between the applied polymer and fibre. The basic group of the polymeric material in fibre form may be hydroxyl, mercatyl, primary or secondary amine, or amide.  The polymeric material may be cellulosic e.g. cellulose, regenerated cellulose, cellulose ethers or esters, or proteinaceous e.g. wool, hair, silk, leather, or synthetic e.g. polyamide, polyester. Conventional coating techniques may be used to apply the acid halide containing polymer.  The latter may either be addition polymers of ethylenically unsaturated monomers containing a carboxylic acid halide group or ethylenically unsaturated monomers copolymerized with ethylenically unsaturated carboxylic acid halides.  The acid halide copolymers may be obtained by halogenation of the corresponding acid copolymers, using phosphorous pentahalide, or by the method disclosed in Specification 1,048,914.  The acid halide groups in the polymeric coating component may be obtained by the polymerization of an a , b -ethylenically unsaturated acid, which is then halogenated.  The acid preferably contains 3 to 8 carbon atoms, e.g. acrylic, methacrylic, itaconic, maleic, crotonic, fumaric, glutaconic, or cinnamic acid. If a polycarboxylic acid is used, one of the acid groups can be esterified.  The acid monomers may be homo- or co-polymerized.  They may be co-polymerized with ethylenically unsaturated monomers to give rise to acid polymers which may then be converted to the acid halide copolymer.  Such monomers may have the general formula <FORM:1048913/D1-D2/1> where A is hydrogen; hydrocarbon group e.g. alkyl, aryl; halogen; carbalkoxy, acyloxy, ether group, nitrile, or aldehyde and B is hydrogen, halogen, or methyl.  Preferred co-polymers are co-polymers of olefins R - CH = CH2 where R is hydrogen or C1-8 alkyl or aryl with acid halides of the described carboxylic acids.  Suitable olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methyl butene-1, 4-methylpentene-1, and styrene.  An inert copolymerizable monomer may be used in conjunction with the olefin and acid halide. Numerous acid co-polymers, which may be converted to acid-halide copolymers, are specified.