Patent GB-834410-A (GB)
Title: Novel polymers of quaternary ammonium compounds and methods of producing them
IPC: C08F20/34
Filed: 1956-03-13
Abstract: Dispersions are made with the aid, as dispersing agents, of a polymer or copolymer of an unsaturated amide, ester or ether containing quaternary ammonium groups attached to the polymer chain (see Group IV (a)) and having attached to the quaternary ammonium nitrogen atom a radical of the formula -CH2(CONH)mR DEG  or of the formula <FORM:0834410/III/1> wherein m is an integer of 1 or 2, R DEG  is H, -CH2OH or CH2OR5 where R5 is a C1-C4 alkyl group, p is an integer of 1 or 2 when p is 2 but only 1 when p is 1, and Z is <FORM:0834410/III/2> or -CH2- when p is 1 but only -CH2- when p is 2. In an Example (14) a stable 20% dispersion of carbon black in water is produced with the aid of the polymer obtained by quarternizing poly - (beta - dimethylaminoethyl vinyl ether) with either chloroacetamide or chloroacetylurea.  Specifications 777,488 and 834,411 are referred to.ALSO:Improved properties, particularly antistatic properties, are conferred upon textile materials made from wool, cellulose, cellulose acetate, cellulose acetate-butyrate, polyvinyl alcohol, nylons, acrylamide and methacrylamide polymers, polyethylene terephthalate, polyacrylonitrile and vinyl chloride-acrylonitrile copolymers by applying thereto, e.g. from aqueous solution, a polymer or copolymer of an unsaturated ester, amide or ether containing quaternary ammonium groups attached to the polymer chain (see Group IV (a)) and having attached to the quaternary ammonium nitrogen atom a radical of the formula -CH2(CONH)mR0 or of the formula <FORM:0834410/IV(c)/1> wherein m is an integer of 1 or 2; R0 is H, -CH2OH or CH2OR5, where R5 is a C1-C4 alkyl group; p is an integer of 1 or 2, when p is 2, but only 1 when p is 1, and Z is <FORM:0834410/IV(c)/2> or -CH2- when p is 1 but only -CH2- when p is 2. After application to the textile the polymers in which R0 is hydrogen may be insolubilized by treatment with an aldehyde followed by heat treatment; those polymers in which R0 is a methylol or alkoxymethyl group may be insolubilized by heat-treatment alone.  In the application to textile materials the polymers may be combined with auxiliary agents such as heat-convertible urea- and melamineformaldehyde condensates.  In examples: (4) a nylon fabric is padded with an aqueous solution of a polymer obtained by quaternizing poly - (beta - dimethylaminoethyl vinyl ether) with N-methoxymethyl-alpha-chloroacetamide followed by air-drying and curing at 300 DEG  F., which treatment may also be applied to fabrics made from polyethylene terephthalate, polyacrylonitrile and cellulose acetate; and (6) as in (4) but employing the methoxymethyl derivative of a polymer obtained by quaternizing a copolymer of beta-dimethylaminoethyl methacrylate and ethyl acrylate with N-[3-alphachloroacetamido) - propyl] - hexahydro - pyrimidone-2.  The feel or handle of the fibres, their resistance to shrinkage on washing and their resistance to creasing are also improved. Specifications 777,488 and 834,111 are referred to.ALSO:Homopolymers and copolymers are made which contain units of the formula <FORM:0834410/IV (a)/1> wherein R is H or methyl; Y is O, -CONR-or -COO-; A is a straight or branched chain C2-C10 alkylene group 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 are either (1) separate saturated or unsaturated p  C1-C4 hydrocarbon groups or (2) a single group which is the morpholino residue: (C2H4)2O, the pyrrolidino residue: -C4H8-, the piperidino residue: -C5H10-, or an N-alkyl piperazino residue: (C2H4)2NR4 where R4 is a C1-C18 alkyl group; X is a halogen; R3 is a radical of the formula -CH2(CONH)mR DEG  or of the formula <FORM:0834410/IV (a)/2> wherein m is an integer of 1 or 2, R DEG  is H, -CH2OH or CH2OR5 where R5 is a C1-C4 alkyl group, p is an integer of 1 or 2, n is an integer of 1 or 2 when p is 2 but only 1 when p is 1, and Z is <FORM:0834410/IV (a)/3> or -CH2 when p is 1 but is only -CH2- when p is 2. In the case of copolymers there may be present in the polymer molecules up to 90 mole. per cent of units derived from ethylene, N-vinylpyrrolidone and specified vinyl aromatic hydrocarbons, alkyl esters of acrylic and substituted acrylic acids, acrylonitrile and substituted acrylonitriles, acrylamide and C- and N-substituted acrylamides, vinyl esters of organic acids, vinyl ethers, fluorinated vinyl and vinylidene compounds and other quaternary ammonium monomers.  The polymers may be prepared by the following methods: (a) by polymerizing a quaternary monomer corresponding to the above formula in bulk, solution or aqueous dispersion with the aid of catalysts such as hydrogen peroxide, benzoyl peroxide, butyl perbenzoate, persulphates or azodiisobutyronitrile; (b) by polymerizing a tertiary amino monomer and then quaternizing it, the monomer and quaternizing agent being chosen to provide an appropriate quaternary group; and (c) by aminolyzing a polymer of an acrylic or methacrylic ester with an appropriate amine and then quaternising the amino groups in the resulting polymer.  In the Examples: (1) polyN - [3 - (dimethylamino) propyl] acrylamide is quaternized with N - (2 - [alpha - chloroacetamido] ethyl) - N,N1 - ethyleneurea; (3) poly-(beta-dimethylaminoethyl vinyl ether) is quaternized with N-methoxymethyl-alpha-chloroacetamide; (5) a copolymer of dimethylaminoethyl methacrylate and ethyl acrylate is quaternized with N - [3 - (alpha - chloroacetamido) propyl]-hexahydropyrimidone-2 and the resulting product treated with a solution of formaldehyde in methanol to produce a methoxymethyl derivative; (7) a copolymer of vinyl pyrrolidone and 2-dimethylaminooctyl acrylate is quaternized with the methylol derivative of N-(beta-[alphachloroacetamido] ethyl)-N,N1-ethylene urea; (8) a copolymer is prepared by heating together in the presence of azodiisobutyronitrile a mixture of n-butylacrylate, the product obtained by quaternizing dimethylaminoethyl acrylate with N - (alpha - chloroacetyl) - N,N1-ethyleneurea and the product obtained by quaternizing the same acrylate ester with benzyl chloride; (9) the procedure of (3) is repeated but using chloracetamide as the quaternizing agent; (10) the procedure of (9) is repeated but using alpha-chloracetylurea as the quaternizing agent; (11) a copolymer of methyl acrylate and N-(3-dimethylaminopropyl)-acrylamide is quaternized with N-(betachloroethyl) - N,N1 - ethyleneurea; (13) poly-(N - [3 - dimethylaminopropyl] acrylamide) is quaternized with N - methoxymethyl - alphachloroacetamide.  The polymeric products in which R DEG  is hydrogen may be reacted with formaldehyde or other aldehyde, e.g. glyoxal, proteins, enzymes and polyacids, the reaction with formaldehyde producing a methylol derivative or, when the reaction is carried out in the presence of an alkanol, an alkoxymethyl derivative.  The products in which R DEG  is methylol or alkoxymethyl are insolubilized by heating, preferably in the presence of an acidic catalyst.  The polymers may be applied to substrates made from natural or synthetic fibres or leather and may be used as bactericides, fungicides, insecticides, flocculating agents and suspension stabilizers, they may also be used as additives to solutions of cellulose acetate, polyvinyl alcohol, polyvinyl pyrrolidone, nylon or acrylonitrile polymers, from which there may be produced films and fibres which may be further treated with an aldehyde and then heattreated to convert the polymer to insoluble form.  Specifications 777,488 and 834,411 are referred to.ALSO:As flocculants for suspended matter in water purification and the concentration of ores there are used polymers or copolymers of an unsaturated amide, ester or ether containing quaternary ammonium groups attached to the polymer chain (see Group IV(a)) and having attached to the quaternary ammonium nitrogen atom a radical of the formula: -CH2 (CON H)m R DEG  or of the formula: <FORM:0834410/I/1> Wherein m is an integer of 1 or 2 R DEG  is H, CH2OH or CH2OR5 where R5 is a C1-C4 alkyl group p is an integer of 1 or 2 n is an integer of 1 or 2 when p is 2 but only 1 when p is 1, and Z is - <FORM:0834410/I/2> - or -CH2- when p is 1 but is only -CH2- when p is 2 In an Example (12) aqueous 10% suspensions of clay are flocculated by the addition thereto of the polymers obtained by (a) quaternising poly-N-[3- (dimethylamino) propyl] acrylamide with N -(2-[alpha-chloroacetamido] ethyl)-N,N1 and the methoxymethyl derivative of such a polymer, (b) quaternising a copolymer of ethyl acrylate and beta-dimethylaminoethyl methacrylate with N-[3-(alpha-chloroacetamido) propyl]-hexapyrimidone-2 and (c) copolymerizing a mixture of butly acrylate with the products obtaining by quaternising beta-dimethylaminoethyl acrylate with N-(alpha-chloroacetyl)-N,N1-ethyleneurea and benzyl chloride; the filtration of the suspensions is thereby hastened as may be that of suspensions obtained by the acid leaching of pulverized gold ores. Specifications 777,488 and 834,411 are referred to.