Patent GB-796543-A (GB)
Title: Quaternary ammonium derivatives of unsaturated esters and amides and polymers thereof
IPC: C08F20/62
Filed: 1954-10-27
Abstract: The invention comprises esters and amides of at least copolymerizable acids which contain at least one quaternary ammonium group bound to the nearest hetero-atom by a non-aromatic hydrocarbon bridge containing at least 2 carbon atoms in the alcohol or amine residue of the ester or amide molecule and bound to the quaternary nitrogen atom a radical containing an epoxy group or an N-methylol group, for example a glycidyl radical or an N-methylol carbamoyl-methyl radical; and comprises also the process for the manufacture of these esters and amides by reacting an ester or amide of a corresponding acid containing a tertiary amino group with a quaternating agent containing an epoxy or N-methylol group such as epichlorhydrin or N-methylol chloracetamide.  The Specification also describes the preparation in general of esters or amides of an at least copolymerizable acid containing in the alcohol or amine residue a quaternary ammonium grouping which is bound to the nearest hereto-atom by an hydrocarbon bridge containing at least 2 carbon atoms, by treating the corresponding tertiary amino compounds with agents capable of converting tertiary amino groups into quaternary amino groups.  Preferably the quaternating agents are ones which contain as additional reactive groups, epoxy groups, labile halogen atoms, acetal groups, or hydrogen atoms bound to hetero atoms. Preferably the quaternary compounds contain only aliphatic radicals, but they may also suitably contain heterocyclic radicals or an aromatic radical containing only one six-membered ring.  For example, chloroacetamide is used to quaternate N-(g -diethylamino - propyl) - methacrylamide, b  - diethylaminoethyl acrylate, N : N1 - (g  - dimethylaminopropyl) - fumaric acid diamide, N - (g  - dimethylaminopropyl) - crotonamide, bisdiethylaminoethyl fumarate and b -diethylaminoethyl - crotonate and N-(g -diethylaminopropyl) - methacrylamide is quarternated with dimethyl sulphate.  In examples: N - (b  - diethylaminoethyl) acrylamide is quaternated with epichlorhydrin and N-methylol chloracetamide; by similar methods N - (b  - dimethylaminoethyl) acrylamide, N-(g  - dimethylaminopropyl) acrylamide, N - (g -diethylaminopropyl) acrylamide and N-(g -morpholinopropyl)acrylamide may be quaternated.  Starting materials. Esters and amides containing tertiary amino groups corresponding to the quaternary compounds described above are made by known methods. For example, the esters or amides may be derived from crotonic, maleic, furyl-acrylic, a -chloro-acrylic, methacrylic and acrylic acids and an esterifiable compound such as triethanolamine, dimethylethanolamine hydroxyethylmorpholine or p-dimethylaminophenol or an amide-forming reactant such as N : N-diethyl-ethylenediamine, N : N - diethylpropylene diamine and polyalkylene polyamines and hetercyclic and aromatic diamines such as piperazine or p-dimethylamino aniline.  In examples the preparation of N - N1 - bis - (g  - dimethylaminopropyl) - fumaric acid diamide, N - g  - dimethylamino - propyl - crotonic acid amide, b  - diethylaminoethyl crotonate and bis - diethylaminoethyl fumarate is described.ALSO:The invention relates to certain polymers which may be employed for animalising cellulose textiles, for after-treating direct dyeings or prints, if desired in combination with a copper salt after-treatment, for dyeing or printing textiles with pigments and for producing matt effects on polyamide fibres.  The polymer is either a homopolymer of an ester or amide of an at least copolymerizable acid containing at least one quaternary ammonium group which is bound to the nearest hetero-atom by a nonaromatic hydrocarbon bridge containing at least 2 carbon atoms in the alcohol or amine residue of the ester or amide and, bound to the quaternary nitrogen atom, a radical containing an epoxy group or an N-methylol group; or a copolymer of an ester or an amide of an at least copolymerizable acid containing in the alcohol or amine residue at least one quaternary ammonium grouping bound to the nearest heteroatom by a hydrocarbon bridge containing at least 2 carbon atoms, with at least one other ethylenically unsaturated compound, acrylonitrile or its homologues, if used as the other polymerizable compounds, being present in amounts not exceeding 50 per cent of the total weight of the polymerizable compounds.  In an example, a polyamide fabric is impregnated with an emulsion obtained by copolymerizing N : N - diethyl - N - acryloylaminoethyl - N - methylolcarbamoylmethyl ammonium chloride with styrene and n-butyl acrylate in aqueous emulsion in the presence of tri-(hydroxyethyl)-lauryl-ammonium acetate and a small quantity of iso-octanol, whereby a matt effect is obtained.ALSO:Copolymers in the form of solutions or stable finely-divided aqueous dispersions are prepared by copolymerization of at least one ester or amide of an at least copolymerizable acid, in which the alcohol or amine residue of the ester or amide molecule contains at least one quaternary ammonium grouping which is bound to the nearest hetero-atom by an hydrocarbon bridge containing at least 2 carbon atoms, and at least one other ethylenically unsaturated polymerizable compound, acrylonitrile or its homologues, if they are used as said other polymerizable compounds, being present at most in amounts not exceeding 50 per cent of the polymerizable compound.  The invention also comprises homopolymers of the above quaternary esters or amides containing bound to the quaternary nitrogen atom a radical containing an epoxy or an N-methylol group.  Suitably, the quaternary compound contains only aliphatic radicals, but it may also contain heterocyclic radicals or aromatic radicals containing only one six-membered ring. Preferably the quaternary compound contains, as an additional reactive grouping, an epoxy group, a labile halogen atom, an acetal group or a group containing hydrogen attached to a hetero atom such as an amide, hydroxyl or N-methylol group.  The quaternary compound is suitably an acrylic acid derivative such as an amide or ester containing at least one quaternary ammonium group.  The other polymerizable compound is suitably a vinyl compound such as a vinyl halide or ester, or styrene, or an acrylic, crotonic, fumaric or maleic acid derivative.  The polymerization may suitably be carried out in bulk, emulsion or solution with the optional addition of catalysts, activators and/or emulsifying agents, with or without the acid of heat or actinic rays.  In examples, the preparation of copolymers in emulsions or solutions is described in which the polymerizable quaternary ammonium compound is chosen from N:N - diethyl - N - (b  - acryloylaminoethyl) - N - (2:3 - epoxypropyl) - ammonium chloride; N:N - diethyl - N - (b  - acryloylaminoethyl) - N - (N1 - hydroxymethyl - carbamoylmethyl) - ammonium chloride; N:N-diethyl (or dimethyl) - N - (g  - acryloylaminopropyl) - N - carbamoylmethyl - ammonium chloride; N:N - diethyl - N - (g  - methacryloylaminopropyl) - N - carbamoylmethyl-ammonium chloride; N:N - diethyl - N - (b  - acryloxyethyl) - N - carbamoylmethyl ammonium chloride; N-methyl-N:N - diethyl - N - (g  - methacryloylaminopropyl)-ammonium methosulphate; N1:N11-fumaroyl-bis - [N - (g  - aminopropyl) - N:N - dimethyl-N - carbamoylmethyl - ammonium chloride]; N:N - dimethyl - N - (g  - crotonoylaminopropyl) - N - carbamoylmethyl ammonium chloride; fumaroyl - bis - [oxyethyl - (N:N - diethyl-N-carbamoylmethyl ammonium chloride)] and N:N - diethyl - N - (crotonyloxyethyl) - N - carbamoylmethyl - ammonium chloride, and the other polymerizable component or components are chosen from styrene, butyl acrylate, vinyl acetate, acrylamide, methyl methacrylate and acrylonitrile.  The products are useful for the treatment of textiles for water-proofing, diminishing electrostatic charges and producing matt effects.  They may also be used for animalizing cellulose fibres and as after-treating agents for improving the fastness of water-soluble sulphonic or carboxylic dyestuffs.  This after-treatment may be combined with after-treatment with a copper salt.