Patent GB-685614-A (GB)
Title: Quaternary ammonium salts and articles containing them
IPC: C07C63/20
Filed: 1949-03-23
Abstract: The invention comprises polyvalent metal salts of phenylene dicarboxylic acids and nuclear substitution products thereof, one acid radical of each dicarboxylic acid residue being neutralized by the basic radical of a microbicidal quaternary ammonium compound having a phenol coefficient (as determined by the Rideal-Walker test) greater than 100, and the other radical of each residue being neutralized with a polyvalent metal.  The basic radical is preferably of the type R1R2R3R4N-, where R1 is alkyl containing from 10-20 carbon atoms, R2 is aryl, aralkyl or alkyl, and R3 and R4 are alkyl radicals.  The compounds are prepared by mixing in aqueous solution stoichiometric quantities of the quaternary ammonium halide and a water-soluble salt, e.g. an alkali metal salt, of a dicarboxylic acid, or by adding a soluble salt of a polyvalent metal to an aqueous solution of an acid salt of the dicarboxylic acid and the quaternary ammonium compound.  Metal salts specified are the aluminium, mercuric, iron, and cadmium salts.  Dicarboxylic acids mentioned include phthalic, terephthalic, monochlorophthalic, tetrachlorophthalic, meta-nitrophthalic, para-nitrophthalic and meta-nitroterephthalic acids.  Quaternary ammonium compounds include cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, cetyl benzyl dimethyl ammonium chloride, lauryl benzyl dimethyl ammonium bromide, p - tertiary - octylphenoxyethoxyethyl dimethyl benzyl ammonium bromide and p - tertiary - octyl - m - methylphenoxyethoxyethyl dimethyl benzyl ammonium bromide.  In examples: (1) equimolecular amounts of p - tertiary - octylphenoxyethoxyethyl dimethyl benzyl ammonium chloride and di-sodium phthalate are mixed in aqueous solution and the mercury salt precipitated by the addition of mercuric chloride; (2) equimolecular amounts of cetyl pyridinium bromide and di-sodium phthalate are mixed, and the mercuric salt precipitated as in example (1); (3) as in example (1) but using dodecyl trimethyl ammonium bromide; (4) the mercury salt of example (1) is fused with an equal part of benzyl benzoate and an emulsion prepared by adding oleic acid and pouring into 1 per cent aqueous ammonium caseinate to form an antiseptic composition for fabrics; (5) dodecyl trimethyl ammonium bromide, phthalic anhydride and aluminium bromide are refluxed in ethyl alcohol and the product mixed with aqueous mercuric chloride; (6) p-tertiary-octylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, phthalic anhydride and aluminium bromide are refluxed and added to mercuric chloride as in example (5).ALSO:Antiseptic rubber compositions are prepared by incorporating in a rubber mix polyvalent metal salts of phenylene dicarboxylic acids and nuclear substitution products thereof in which one acid radical of each dicarboxylic acid residue is neutralised by the basic radical of a microbicidal quaternary ammonium compound of the type R1R2R3R4.N- where R1 is an alkyl radical of 10-20 carbon atoms, R2 is an aryl, arakyl or alkyl radical and R3 and R4 are alkyl radicals. Metals mentioned include aluminium, mercury, iron and cadmium. Dicarboxylic acids mentioned include phthalic, terephthalic, monochlorophthalic, tetrachlorophthalic, metanitro-phthalic, p  para-nitro-phthalic and metanitroterephthalic acids.  Quaternary ammonium compounds include cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, cetyl benzyl dimethyl ammonium chloride, lauryl benzyl dimethyl ammonium bromide, p-tertiary octyl phenoxy ethoxy dimethyl benzyl ammonium bromide and p-tertiary octyl-m-methylphenoxy-ethoxy-ethyl-dimethyl benzyl ammonium bromide. The compounds may be added to rubber latex or may be incorporated in a finely divided state in the rubber mix during the mastication of the rubber.  The preparation of the salts is described in Group IV (b).