Patent GB-891758-A (GB)
Title: Production of graft copolymers from olefinically unsaturated monomers and nitrosated copolymers
Inventor: CRAUBNER HANS
IPC: C08F291/12
Filed: 1961-01-05
Abstract: Graft polymers are obtained by nitrosating all or part of the amide nitrogen atoms of copolymers with other unsaturated monomers of olefinically unsaturated aliphatic, cycloaliphatic and/or heterocyclic acylamines which are monosubstituted on the amide nitrogen atoms by alkyl, alkenyl aralkyl, cycloalkyl, cycloalkenyl, alkylene and/or cycloalkylene groups, and then grafting the nitrosated copolymers with olefinically unsaturated monomers. Unsaturated acylamines specified are the N- monosubstituted amides of acrylic, methacrylic and crotonic acids, N-monosubstituted monoamides of maleic and fumaric acids and esters thereof, N,N1-substituted diamides of maleic, fumaric, itaconic and mesaconic acids, N,N1-alkylene or -cycloalkylene substituted bis-acrylic, -methacrylic and -crotonic amides, N-methyl cyclohexen-1-yl carboxylamide, N,N1-methylene-bis-cyclohexenyl carboxylamide, N,N1-hexamethylene-bis-maleic monoamide and esters thereof, N-allyl acetamide, propionamide and butyramide, N,N1-diallylhexahydroterephthalamide, mono- and diureides of unsaturated acids, e.g. acrylic, methacrylic, maleic and fumaric acids, such compounds being substituted at one or more ureide nitrogen atoms, and barbituric acid derivatives substituted at the 5-position on the ring by a C2-C6 alkenyl group.  Monomers specified for use either as comonomers with the unsaturated amides or as grafting monomers are acrylic and methacrylic acids and their nitriles, amides or ester with C1-C12 alkanols or cycloalkanols, styrene, methyl styrenes, ethylene, propylene, butene-1, butene-2, isobutylene, butadiene, isoprene, chlorobutadiene, vinyl acetate and propionate, vinyl and vinylidene chloride, vinyl ethers of C1-C12 alcohols, vinyl sulphonic acid, vinyl pyridine, pyrrolidone and carbazole and unsaturated polyesters.  The nitrosation of the amide copolymers is accomplished by means of agents such as dinitrogen trioxide, nitrosyl chloride, alkyl nitrites and nitrous acid.  The grafting of the unsaturated monomer on to the nitrosated copolymer may be effected in bulk, solution, emulsion or suspension, and may be accelerated by means of alkali metal carbonates and/or hydroxides, amines, e.g. triethanolamine, salts of iron, nickel, cobalt and manganese, peroxides or azodiisobutyronitrile.  The Examples describe grafting of: (1) acrylic acid on to a nitrosated styrene-N-benzyl maleic monoamide copolymer, (2) a mixture of vinyl acetate and methyl methacrylate on to a copolymer as in (1), (3) butyl acrylate on to a nitrosated methyl methacrylate-N-(2-ethylhexyl)-maleic monoamide copolymer, (4) a mixture of vinyl acetate and acrylonitrile on to a nitrosated acrylonitrile-N,N1-methylene dimethacrylamide copolymer, (5) a mixture of styrene, butyl acrylate and acrylonitrile on to a nitrosated styrene-N,N1-methylene dimethacrylamide copolymer, (6) methyl methacrylate on to a nitrosated acrylonitrile-butadiene-N-benzyl maleic monoamide copolymer, (7) acrylonitrile on to a nitrosated styrene-butadiene-N-stearyl maleic monoamide copolymer, (8) methyl methacrylate on to a nitrosated styrene-N-allyl propionamide copolymer, (9) acrylonitrile on to a nitrosated N-methyl methacrylamide-N-isopropyl acrylamide copolymer, (10) acrylonitrile on to a nitrosated vinylidene chloride-styrene-N-lauryl maleic monoamide copolymer, (11) acrylonitrile on to a nitrosated methyl methacrylate-N,N-dimethyl maleic acid monureide copolymer, (12) a mixture of vinylidene chloride and vinyl pyrrolidone on to a nitrosated copolymer of styrene, N-cyclohexyl maleic monoamide and a polyester derived from maleic and phthalic acids and propylene glycol, (13) acrylonitrile on to a nitrosated methyl methacrylate-N-iso-octyl maleic monoamide copolymer, (14) acrylic acid on to a nitrosated styrene-N,N1-methylene dimethacrylamide copolymer, and (15) acrylonitrile on to a nitrosated vinyl chloride-vinyl propionate-N-allyl maleic amide copolymer.  Specification 546,459 is referred to.