Patent GB-972070-A (GB)
Title: Stable aqueous dispersions of cross-linking copolymers and process for the production thereof
IPC: C08F20/10
Filed: 1960-10-17
Abstract: The invention comprises unsaturated amines of formula <FORM:0972070/C1/1> in which Y represents the group -OH, -COOH, -COO Me, -SO3H, -SO3Me, <FORM:0972070/C1/2> , -CH = CH2, or -O-[-(CH2)n-O]z-H, where Me is a metal atom or the ammonium radical, R1 and R11 are saturated aliphatic or cycloaliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, aralkyl radicals or aryl radicals, n is 1 to 4 and z is 1 to 25, x is 1 to 20, R1 and X are hydrogen atoms or saturated aliphatic or cycloaliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, and R2 is a hydrogen atom, a saturated aliphatic, cycloaliphatic, aralkyl, or aryl radical, having 1 to 12 carbon atoms, or the group -(CH2)x-Y where x and Y are as above. The unsaturated amines are prepared by reacting together at 30 DEG  to 100 DEG C. an unsaturated carboxylic acid amide of formula <FORM:0972070/C1/3> where X and R1 are as above, with formaldehyde and an amine of formula <FORM:0972070/C1/4> where Y, x and R2 are as above.  Compounds specified in the examples are condensation products of methacrylamide, formaldehyde and n-butyltaurine; acrylamide, formaldehyde and n-propyltaurine; methacrylamide, formaldehyde and sarcosine; acrylamide, formaldehyde and diethanolamine; acrylamide, formaldehyde and N-methyltaurine; methacrylamide, formaldehyde and diethanolamine; and methacrylamide, formaldehyde and dialllyamine. Other amides which may be used as starting materials are N-methylmethacrylamide N-ethylmethacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-propylacrylamide and N-butyl acrylamide. Other amines which may be used as starting materials are N-methylaminoethane sulphonic acid, N-ethylaminoethane sulphonic acid, N-propylaminoethane sulphonic acid, N-butylaminoethane sulphonic acid, N-methylaminoacetic acid, 3-N-ethylpropane sulphonic acid, iminodipropionic acid, b -alaninitrile, iminodipropionic acid nitrile, N-methylethanolamine, N-methyl-N-dimethylpropylene-1 3-diamine, and a polyglycolether of N-ethylaminoethanol.ALSO:Co-polymers are prepared from (1) 0.5 to 25% by weight of an unsaturated amine of formula <FORM:0972070/C3/1> in which Y represents the group <FORM:0972070/C3/2> or -O-[-(CH2)n-O]z-H, where Me is a metal atom or ammonium radical, R1 and R11 are saturated aliphatic or cycloaliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, aralkyl radicals or aryl radicals, n is 1 to 4 and z is 1 to 25, x is 1 to 20, and R1 and X are hydrogen atoms or saturated aliphatic or cyclo-aliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, and R2 is a hydrogen atom, a saturated aliphatic, cycloaliphatic, aralkyl or aryl radical, having 1 to 12 carbon atoms, or the group -(CH2)x-Y where x and Y are as above, with (2) 75 to 99.5% by weight of further olefinically unsaturated mono-mers. Component (2) of the copolymer may be an a , b  olefinically unsaturated monocarboxylic acid or derivative thereof; an aromatic vinyl compound; an aliphatic vinyl compound; a conjugated diolefine containing 4 to 6 carbon atoms; a methylol compound of an acrylic or methacrylic acid amide of formula <FORM:0972070/C3/3> where R is a hydrogen atom or a methyl group, R1 is a hydrogen atom or an alkyl, aralkyl or aryl group and R2 is an alkyl or cycloalkyl group; or a compound of formula <FORM:0972070/C3/4> where R is hydrogen or a methyl group, R1 is hydrogen or an alkyl, aralkyl or aryl group, and R3 and R4 are alkyl, cycloalkyl or aralkyl groups or together form a heterocyclic radical. The co-polymerization is carried out in aqueous dispersion using an emulsifying agent, e.g. a soap, a salt of a long-chain carboxylic acid, an alkyl sulphuric acid, sulphonic aci or sulphated hydrocarbon vegetable oil; a salt of an amine; or the reaction product of ethylene oxide with a long-chain alcohol, fatty acid or fatty acid amide. Polymerization catalysts are per salts, hydrogen peroxide or organic peroxide. Preferably polymerization modifiers e.g. mercaptans and polysulphides, are present. Dyes and pigments may be added to the dispersions, together with thickening agents. In examples copolymers are formed from butyl acrylate, styrene and a compound of formula <FORM:0972070/C3/5> from butyl acrylate, acrylonitrile and a compound of formula <FORM:0972070/C3/6> from butyl acrylate, styrene and a compound of formula <FORM:0972070/C3/7> from styrene, butyl acrylate, ethyl acrylate and a compound of formula <FORM:0972070/C3/8> from styrene, acrylonitrile and a compound of formula <FORM:0972070/C3/9> from butadiene, styrene and a compound of formula <FORM:0972070/C3/10> and from butadiene, acrylonitrile and a compound of formula <FORM:0972070/C3/110> To dispersions of these copolymers are added pigments and thickeners to obtain printing pastes which are used to print cotton, viscose rayon, nylon and acetate rayon. Specifications 539,963 and 545,618 are referred to.ALSO:Compositions for printing textiles, comprise aqueous dispersions of a copolymer of (1) 0.5 to 25% by weight of an unsaturated amine of formula <FORM:0972070/D1-D2/1> in which Y represents the group -OH, -COOH, -COOMe, -SO3H, -SO3Me, <FORM:0972070/D1-D2/2> , -CH = CH2, or -0-[-(CH2)n-0]z-H, where Me is a metal atom or ammonium radical, R1 and R11 are saturated aliphatic or cycloaliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, aralkyl radicals, or aryl radicals, n is 1 to 4 and z is 1 to 25, x is 1 to 20, and R1 and X are hydrogen atoms or saturated aliphatic or cycloaliphatic hydrocarbon radicals containing 1 to 7 carbon atoms, and R2 is a hydrogen atom, a saturated aliphatic, cycloaliphatic, aralkyl, or aryl radical, having 1 to 12 carbon atoms, or the group -(CH2)x - Y where x and Y are as above, with (2) 75 to 99.5% by weight of further olefinically unsaturated monomers, emulsifying agents and figments. Component (2) of the copolymer may be an a , b  olefinically unsaturated monocarbocylic acid or derivative thereof, an aromatic vinyl compound; an aliphatic vinyl compound; a conjugated diolefine containing 4 to 6 carbon atoms; a methylol compound of an acrilic or methacrylic acid amide of formula <FORM:0972070/D1-D2/3> where R is a hydrogen atom or a methyl group, R1 is a hydrogen atom or a alkyl, aralkyl or aryl group and R2 is an alkyl or cycloalkyl group; or a compound of formula <FORM:0972070/D1-D2/4> where R is hydrogen or a methyl group, R1 is hydrogen or an alkyl, aralkyl or aryl group, and R3 and R4 are alkyl, cycloalkyl or aralkyl groups or together form a heterocyclic radical.  The emulsifying agent may be a soap, a salt of a long-chain carboxylic acid, an alkyl sulphuric acid, sulphonic acid or sulphated hydrocarbon vegetable oil; a salt of an amine; or the reaction product of ethylene oxide with a long-chain alcohol, fatty acid or fatty acid amide.  In examples compositions comprise copolymers formed from butyl acrylate, styrene and a compound of formula <FORM:0972070/D1-D2/5> from butyl acrylate, acrylonitrile and a compound of formula <FORM:0972070/D1-D2/6> from butyl acrylate, styrene and a compound of formula <FORM:0972070/D1-D2/7> from styrene, butyl acrylate, ethyl acrylate and a compound of formula <FORM:0972070/D1-D2/8> from styrene, acrylonitrile and a compound <FORM:0972070/D1-D2/9> from butadiene, styrene and a compound of formula <FORM:0972070/D1-D2/100> and from butadiene, acrylonitrile and a compound of formula <FORM:0972070/D1-D2/111> To dispersions of these copolymers are added pigments and thickeners to obtain printing pastes which are used to print cotton, viscose rayon nylon and acetate rayon.