Patent GB-777488-A (GB)
Title: New polymerizable quaternary ammonium compounds and their manufacture and use
IPC: C07D303/36
Filed: 1954-10-29
Abstract: Polymers and copolymers are prepared from a vinyl ether which contains at least one quaternary ammonium group which is not bound to a hetero-atom through a methylene bridge and in which the vinyl ether group is the sole ethylenically unsaturated group (see Group IV (b)). Polymerization of the quaternary compounds can be carried out in bulk, solution or emulsion.  For polymerization of the vinyl ethers alone aluminium chloride, boron fluoride or stannic chloride are suitable catalysts.  For copolymerization peracetic acid, acetyl peroxide, benzoyl peroxide, benzoylacetyl peroxide, lauryl peroxide, cumenehydroperoxide, tertiary butyl hydroperoxide, para menthane hydroperoxide, hydrogen peroxide, percarbonates, persulphate and perborates are suitable.  Heat and/or actinic rays with or without such catalysts can also be used.  The speed of polymerization and molecular weight of the product may be influenced by adding regulators such as mercaptans or terpenes.  As activators of the polymerization sulphur dioxide, sodium bisulphite, sodium sulphite, ammonium bisulphite, sodium hydrosulphite, sodium thiosulphate, triethanolamine and diethyl-ethanolamine are specified.  The action of the catalyst can be accelerated by adding a heavy metal compound capable of existing in more than one valency condition or a complex cyanide of iron, cobalt, molybdenum, mercury, zinc, copper or silver. A large number of suitable non-ionic and cation-active emulsifying agents (which may have wetting properties) is specified for use in emulsion polymerization.  Protective colloids such as polyvinyl alcohols, partially hydrolysed polyvinyl esters, starch, dextrin, cellulose ethers, polyethylene oxides and water-soluble polymers with free hydroxy, amino or carboxamide groups may also be present. Solvents for solution polymerization specified are methylene chloride or dichloro-ethane.  In forming copolymers there may be used as the other monomer, vinyl acetate, formate, butyrate or benzoate, vinyl alkyl ketones, vinyl chloride or fluoride, styrene, esters of acrylic acid with phenols, ethyl, butyl or dodecylacrylate, acrylonitrile, acrylamide and its N-substituted derivatives, corresponding methacrylic and a -chloracrylic acid derivatives, isobutylene, butadiene, 2-chlor-butadiene and vinylpyridine.  To the products may be added dibutyl or dioctyl phthalate, sebacic acid esters, organic or inorganic pigments or filling materials.  Textile material may be impregnated with a solution or emulsion of the monomers and polymerization then carried out.  The products may be used in mouldings, films, fibres, adhesives, lacquers and in the treatment of textiles.  In examples: (3) styrene and n-butyl acrylate are polymerized in an aqueous emulsion with a product obtained by quaternating b -diethylaminoethyl vinyl ether with chloracetamide, with trioxyethyllauryl-ammonium acetate as emulsifying agent and potassium persulphate as catalyst; (4) and (5) the quaternary compound used in Example (3) is replaced by one of formula: <FORM:0777488/IV(a)/1> The product is useful for producing a matt effect on polyamide fabric; (10) the quaternary compound from (b -di-n-butylamino) ethyl vinyl ether and dimethyl sulphate is polymerized in aqueous solution with a borofluoride dihydrate catalyst to give a water-soluble resin which can be bleached by oxidizing agents. The quaternary compound from (b -morpholinoethyl) vinyl ether and dimethyl sulphate can be similarly polymerized; (11) isobutyl acrylate, acrylonitrile and a compound of the formula: <FORM:0777488/IV(a)/2> are copolymerized in aqueous medium to give a product which is absorbed on wool, which dries to a rubber-like film, and which may be mixed with paraffin emulsions and aluminium salts to form water-fast dressings; (12) acrylonitrile and an aqueous solution of the quaternary compound used in Example (11) are emulsified with [b  - lauroylamido) - ethyl] - diethylmethyl ammonium sulphate. Polymerization is effected by heating half the emulsion with the addition of potassium persulphate and adding the other half, with more potassium persulphate dropwise, finally heating in the presence of further potassium persulphate; (13) acrylamide and the quaternary compound used in Example (11) are copolymerized in aqueous solution with a potassium persulphate catalyst; (14) methyl methacrylate and the quaternary compound from dimethyl sulphate and (b -morpholinoethyl) vinyl ether are copolymerized in ethylene chloride with a benzoyl peroxide catalyst.  The product may be mixed with urea or melamine formaldehyde resins to form stoving lacquers.ALSO:The invention comprises polymerizable vinyl ethers which contain at least one quaternary ammonium group which is not bound to a hetero-atom through a methylene bridge and in which the vinyl ether group is the sole ethylenically unsaturated group.  (The term "vinyl ether" is used to mean exclusively ethers of vinyl alcohol which contain the unsubstituted radical -O-CH=CH2).  Such compounds are obtained by reacting an appropriate vinyl ether containing at least one tertiary amino group which is not bound to a hetero-atom through a methylene bridge with the appropriate quaternating agent.  The ethers may contain in the molecule a radical rendering them capable of undergoing hardening to a condensation resin, e.g. the reaction product of a basic vinyl ether with the formaldehyde condensation product of an aminotriazine or a urea.  As suitable tertiary amino compounds are mentioned vinyl ethers containing dimethylamino, diethylamino, di - (hydroxyethyl) - amino, di - (hydroxypro - pyl) - amino, diisopropylamino, methylethylamino, di - (cyanoethyl) - amino, morpholino, piperidino and pyridyl groups, linked to the ether oxygen by various alkylene chains or by alkylene chains interrupted by nitrogen or oxygen atoms or p-phenylene groups.  As quaternating agents, in addition to alkylating and aralkylating agents are specified compounds with a further reactive grouping such as an epoxy group, halogen atoms, acetal groups and hydrogen attached to hetero-atoms and hydroxyl, amide and N-methylol-amide groups. Alkylene oxides, epichlorhydrin and chloracetamide are referred to. In examples: (1) b -diethylaminoethyl-vinyl ether is reacted with chloracetamide to give a water-soluble quaternary compound of the formula <FORM:0777488/IV(b)/1> (2) b -diethylaminoethyl vinyl ether and epichlorhydrin are reacted to give a quaternary compound of the formula <FORM:0777488/IV(b)/2> Further quaternary compounds are obtained by reacting (6) chloracetamide and (b -morpholinoethyl)-vinyl ether (from the reaction of acetylene and b -morpholino-ethanol in the presence of a basic catalyst); (7) dimethyl sulphate or methyl p-toluene sulphonate and (b -morpholinoethyl)-vinyl ether; (8) and (9) dimethyl sulphate and (b - di - n - butylaminoethyl) vinyl ether. The formation of polymers and their use in treating textiles is described (see Groups IV (a) and IV (c)).ALSO:Textiles are impregnated and coated with polymers and copolymers of polymerizable vinyl ethers which contain at least one quaternary ammonium group which is not bound to a hetero-atom through a methylene bridge and in which the vinyl ether group is the sole ethylenically unsaturated group.  (The term "vinyl ether" is used to mean exclusively ethers of vinyl alcohol which contain the unsubstituted radical - O - CH = CH2).  The resins may be used to render the textiles water-repellent, to animalize cellulose-containing textiles or in the after-treatment of dyeings and prints of water-soluble directdyeing dyestuffs. The latter treatment may be combined with an after-treatment with a copper salt. The polymers may also be used for producing a matt effect on polyamide fibres.  For the latter purpose polymers obtained by joint emulsion polymerization of a vinyl ether of the formula <FORM:0777488/IV(b)/1> or <FORM:0777488/IV(b)/2> with styrene or n-butyl acrylate are suitable.  Textiles may also be impregnated with the monomers which are then subjected to polymerization.  The polymers may also be used as adjuvants to sizing agents for increasing their electrical conductivity.  The vinyl ethers may be copolymerized with other vinyl compounds, of which many are specified.  In examples there are prepared (3) a copolymer of n-butyl arylate with a quaternary compound of the second formula above, suitable for producing a matt effect on fibrous polyamide fabric; (10) a polymer of the quaternary compound from dimethyl sulphate and (b  - di - n - butylamino) vinyl ether, suitable as an adjuvant for sizing agents; (11) a copolymer of isobutyl acrylate and the quaternary compound used in (10), suitable for mixing with paraffin emulsion and aluminous salts to produce a water-fast dressing; (13) a copolymer of acrylamide and the quaternary compound used in (10), suitable for preparing sizing agents to reduce the electrostatic charge of fibres.  The preparation of the monomers and polymers is described (see Groups IV(a) and IV(b)).