Patent GB-835550-A (GB)
Title: Quaternary ammonium copolymers and methods of producing them
IPC: C08F20/34
Filed: 1956-03-13
Abstract: Flocculating and aggregating agents comprise copolymers of a quaternary ammonium ester or amide of acrylic or methacrylic acid, one or more derivatives of acrylic or methacrylic acid containing a carbonamido group N-substituted by a methylol or alkoxymethyl group and, optionally, another copolymerizable monomer (see Group IV (a)). Specifications 747,184 and 764,147 are referred to.ALSO:Textile materials, e.g. those made from cotton, cellulose acetate, cellulose acetobutyrate, polyamides, polyethylene terephthalate, acrylonitrile polymers and other vinyl polymers (listed) have applied thereto, in the form of a solution in a liquid vehicle, a copolymer of a quaternary ammonium ester or amide of acrylic or methacrylic acid, one or more derivatives of acrylic or methacrylic acid containing a carbonamido group N-substituted by a methylol or alkoxymethyl group and, optionally, another copolymerizable monomer (see Group IV (a)). Also present may be starches, glue and casein.  The copolymer may function as an anti-static agent when applied to textile materials of hydrophobic types or as a softening agent when applied to textile materials of cellulosic types.  After application the substrate is usually heated to a temperature of from 212 DEG  to 300 DEG  F. to dry the applied composition and insolubilize the copolymer. In Examples (6), (7) and (8), processes are described in which the tendency of textile materials made from nylon, polyethylene terephthalate and an acrylonitrile copolymer to develop static charges is reduced by the application thereto of aqueaus solutions of specified copolymers, followed by heating to 300 DEG  F. Specifications 747,184 and 764,417 are referred to.ALSO:Copolymers are made containing at least 30 mol. per cent of units represented by formula I below and at least 5 mol. per cent of units represented by the formulae II and/or III below <FORM:0835550/IV (a)/1> wherein R is hydrogen or methyl; Y is a -CONR- or -COO- group; A is a straight-chain or branched-chain alkylene group having 2 to 10 carbon atoms which may be substituted by one or more hydroxyl groups, at least two of the carbon atoms thereof being connected in a chain between the N atom and the Y group of the formula; R1 and R2, when not connected together, each represent a saturated or ethylenically unsaturated hydrocarbon group having 1 to 4 carbon atoms; R1 and R2, when connected together, collectively represent the morpholino residue: (C2H4)2O, the pyrrolidino residue -C4H8-, the piperidino residue -C5H10-, or an N-alkyl piperazino residue: (C2H4)2: NR0, where R0 is a C1-C18 alkyl group; R3 is benzyl or a saturated or ethylenically unsaturated hydrocarbon group of 1 to 4 carbon atoms; and X is a negative, salt-forming atom or radical; <FORM:0835550/IV (a)/2> wherein R is hydrogen or methyl, and R4 is a methylol or alkoxymethyl group. <FORM:0835550/IV (a)/3> wherein R, Y and A are as defined above, and R5 is a -NHCONHR4 group or a group <FORM:0835550/IV (a)/4> in which the radical R4 is as defined above. Also present in the copolymers may be up to 65 mol. per cent of one or more comonomers such as acrylonitrile and its methyl, ethyl and phenyl derivatives, styrene, isopropenyl toluene, dialkyl styrenes, the N-mono- and N-dimethyl, -ethyl, -propyl, -butyl and -phenyl acrylamides and methacrylamides, vinyl acetate, propionate, butyrate, isobutyrate and valerate, the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, decyl and dodecyl esters of acrylic, methacrylic, ethacrylic and phenylacrylic acids, N-vinyl pyrrolidone, ethylene, vinylidene fluoride and vinyl ethers, e.g. methyl, butyl, aminoisobutyl, formamidoethyl, N-methyl or N-dimethyl amidoethyl and ureidoethyl vinyl ethers and other ureidoalkyl ethers mentioned in Specification 747,184.  The copolymers may be prepared by the following methods: (a) by copolymerizing a quaternary ammonium monomer corresponding to formula I with at least one monomer corresponding to formula II and/or III with the aid of initiators such as hydrogen peroxide or a mixture of a persulphate and a hydrosulphite; (b) by copolymerizing a tertiary amino monomer with at least one monomer corresponding to formula II and/or III and quaternizing the resulting copolymer to provide units of formula I; (c) a modification of processes (a) and (b) wherein, instead of monomers corresponding to formula II and/or III, there are used monomers free from methylol or alkoxymethyl groups, which groups are introduced after formation of the copolymer by reaction with formaldehyde followed, optionally, by reaction with an alkanol to provide units of formula II and/or III; and (d) in the case of copolymers containing units of formulae I and III, by aminolysing a polymer of an ester of acrylic or methacrylic ester with a mixture of amines of the formulae <FORM:0835550/IV (a)/5> in which the symbols are as defined above, and quaternizing the resulting product, or alternatively by employing amines free from methylol or alkoxymethyl groups, which groups are introduced subsequently.  The copolymers, which are heat-curable, may be used as insecticides, bactericides and fungicides, as antistatic agents for the treatment of hydrophobic plastic materials, as sizes for textile materials, as additives to spinning solutions of cellulose acetate and polyacrylonitrile to improve the dyeing of products formed from such materials, as additives to paper pulp and as flocculating and aggregating agents.  Specification 764,147 also is referred to.ALSO:Agents in the purification of water comprise copolymers of a quaternary ammonium ester or amide of acrylic or methacrylic acid, one or more derivatives of acrylic or methacrylic acid containing a carbonamido group N-substituted by a methylol or alkoxymethyl group and, optionally, another copolymerisable monomer (see Group IV(a)). Specifications 747,184 and 764,147 are referred to.ALSO:As flocculating and aggregating agents in the concentration of ores there are used copolymers of a quaternary ammonium ester or amide of acrylic or methacrylic acid, one or more derivatives of acrylic or methacrylic acid containing a carbonamide group N-substituted by a methylol or alkoxymethyl group and, optionally, another copolymerizable monomer (see Group IV(a)). Specifications 747,184 and 764,147 are referred to.