Patent GB-446568-A (GB)
Title: Processes for improving the wetting properties of aqueous liquids used for treating textiles and other fibrous materials
IPC: C07C309/17
Filed: 1934-07-26
Abstract: Esters having the formula <FORM:0446568/IV/1> in which R is an aliphatic carbon chain, Me is hydrogen or a metal or a basic group, X is hydrogen or an alcohol or phenol residue and Y is an alcohol or phenol residue, are used in the treatment of textiles and other fibrous materials with aqueous liquids.  The esters may be prepared by treating the ester of an unsaturated aliphatic dicarboxylic acid with an alkali bisulphite or by esterification of the sulphonated saturated acids.  Mixtures of esters and mixed esters derived from maleic acid and other acids with mono or polyhydric alcohols or alkylene oxides, e.g. propylene or butylene oxide may be used.  Mixed octylamyl and ethoxyethylamyl esters are mentioned. Sulphochlorsuccinic, sulphosebacic, sulphodimethylsuccinic, sulphomethylglutaric, sulphopimelic sulphopropylsuccinic, sulphooctyl glutaric acids are suitable starting materials for the esterification.  The products are stated to be wetting, detergent, dispersing and lubricating agents, and may be used in dye preparations, emulsions of fats, oils, shellac, gums and natural and synthetic resins, in finishing, saponaceous, waterproofing, coating, lubricating and mordanting compositions, in rosin, casein and starch compositions and in preparations for treating paper and pulp products.  Their use in mercerizing lyes and baths for degumming silk and impregnating wood is mentioned.  In examples: (1) esters derived from the following alcohols and maleic acid or anhydride are sulphonated by treatment with sodium bisulphite: amyl, capryl, octyl, tetrahydrofurfuryl, stearyl and oleyl alcohols, ethyleneglycolmonobutylether, glycerine, and ethylene glycol; (2) fumaric acid is esterified with 2-ethylhexanol and sulphonated with sodium bisulphite to give dioctylsulphosuccinate; (3) glutaconic acid is esterified with cyclohexanol and sulphonated with sodium bisulphite; (4) mesoconic acid dichloride is treated with sodium phenolate in toluene and the mesoconic acid diphenylester sulphonated with bisulphite to give sodium diphenylsulphopyrotartrate; (5) an ester product prepared from ethyleneoxide and maleic acid is sulphonated with bisulphite; (6) mixed esters derived from glycerine and maleic and acetic acid anhydrides are sulphonated with bisulphite; (7) a mixed ester derived from maleic anhydride, oleic acid, glycerine and amyl alcohol is sulphonated with bisulphite; the product, on drying, is a soft resin; (8) an acid ester obtained from amyl alcohol and phthalic anhydride or succinic, chlormalic or tartaric acid is esterified with glycerine and the product further esterified with maleic anhydride and finally sulphonated with bisulphite; (9) glycerine is esterified with phthalic anhydride or benzoic or benzoylbenzoic acid and the product further esterified in tetrahydronaphthalene with maleic anhydride; (10) a neutral ester obtained from castor oil and maleic anhydride is sulphonated with bisulphite; (11) an acid ester of maleic acid and castor oil is prepared and sulphonated with bisulphite; to increase its solubility it may be treated with caustic alkali or further sulphonated with sulphuric acid.  The following alcohols and phenols may be used in the preparation of the esters: methyl, ethyl and propyl alcohols, the amyl alcohol obtained by hydrolysis of the halogenated pentane fraction of natural gas, methylcyclohexanol, borneol, menthyl alcohol, furfuryl alcohol, cresols, xylenols and naphthols, polyglycerols, pentaerythrite and propylene and butyleneglycols.  The esters may be used in the form of their soluble salts.  The following bases are mentioned: alkali metals, ammonia, mono-, di-and tri-methyl and ethylamine, triethanolamine, pyridine, nicotine, cinchona alkaloids and basic dyes.  The fact that the salts of the esters with alkaloids give dispersions in aqueous media facilitates their use as mothproofing agents; the nicotine and pyridine salts are useful as insecticides.  The production of the following esters by direct esterification of the sulphodicarboxylic acids with the alcohols is described: dimethylsulphomaleate, dilaurylsulpho succinate, difenchylsulphosuccinate, diethoxyethyl sulphopyrotartrate, dibenzylsulphoadipate, the sulphosuberate of methylisobutylcarbinol and dibutylsulphosebacate.  The Specification as open to inspection under Sect. 91 comprises also the use of the esters in colour lakes, solvents for fats, printing and writing inks, automobile, metal, furniture and shoe creams, in carbonizing and fat liquoring and in emulsions of perfumes, cosmetics, shaving creams, shampoos, petroleum (kerosene and naphtha), rubber, asphaltic paints, varnishes, shellac, pigments, germicides and in fire extinguishing emulsions and emulsions of boring, wire-drawing and cutting (lathe) oils.  This subject-matter does not appear in the Specification as accepted.ALSO:Esters having the formula <FORM:0446568/III/1> in which R is an aliphatic carbon chain, Me is hydrogen or a metal or a basic group, X is hydrogen or an alcohol or phenol residue and Y is an alcohol or phenol residue, are used as emulsifying agents in the treatment of textiles and other fibrous materials. Mixtures of esters and mixed esters derived from maleic acid and other acids with mono- or polyhydric alcohols or alkylene oxides, e.g. propylene or butylene oxide may be used.  Mixed octylamyl and ethoxyethylamyl esters are mentioned.  Sulphochlorsuccinic, sulphosebasic, sulphodimethylsuccinic, sulphomethylglutaric, sulphopimelic, sulphopropylsuccinic and sulphooctyl glutaric acid are suitable starting materials for the esterification.  The products may be used in emulsions of fats, oils, shellac, gums and natural and synthetic resins and in rosin, casein and starch compositions.  In examples: (1) esters derived from the following alcohols and maleic acid or anhydride are sulphonated by treatment with sodium bisulphite amyl, capryl, octyl, tetrahydrofurfuryl, stearyl and oleyl alcohols, ethyleneglycolmonobutylether, glycerine, and ethylene glycol; (2) fumaric acid is esterified with 2-ethylhexanol and sulphonated with sodium bisulphite to give dioctylsulphosuccinate; (3) glutaconic acid is esterified with cyclohexanol and sulphonated with sodium bisulphite; (4) mesoconic acid dichloride is treated with sodium phenolate and the mesoconic acid diphenylester sulphonated with bisulphite to give sodium diphenylsulphopyrotartrate; (5) an ester product prepared from ethyleneoxide and maleic acid is sulphonated with bisulphite; (6) mixed esters derived from glycerine and maleic and acetic acid anhydrides are sulphonated with bisulphite; (7) a mixed ester derived from maleic anhydride, oleic acid, glycerine and amylalcohol is sulphonated with bisulphite; the product, on drying is a soft resin; (8) an acid ester obtained from amyl alcohol and phthalic anhydride or succinic, chlormalic or tartaric acid is esterified with glycerine and the product further esterified with maleic anhydride and finally sulphonated with bisulphite; (9) glycerine is esterified with phthalic anhydride or benzoic or benzoylbenzoic acid and the product further esterified with maleic anhydride; (10) a neutral ester obtained from castor oil and maleic anhydride is sulphonated with bisulphite; (11) an acid ester of maleic acid and castor oil is sulphonated with bisulphite; to increase its solubility it may be treated with caustic alkali or further sulphonated with sulphuric acid.  The following alcohols and phenols may be used in the preparation of the esters: methyl, ethyl and propyl alcohols, the amyl alcohol obtained by hydrolysis of the halogenated pentane fraction of natural gas, methylcyclohexanol, borneol, menthyl p  alcohol, furfuryl alcohol, cresols, xylenols and naphthols, polyglycerols, pentaerythrite and propylene and butyleneglycols. The esters may be used in the form of their soluble salts.  The following bases are mentioned: alkali metals, ammonia, monodi- and tri-methyl and ethylamine, triethanolamine, pyridine, nicotine, cinchona alkaloids and basic dyes.  The production of the following esters by direct esterification of the sulphodicarboxylic acids with the alcohols is described: dimethylsulphomaleate, dilaurylsulphosuccinate, difenchylsulphosuccinate, diethoxyethyl sulphopyrotartrate, dibenzylsulphoadipate, the sulphosuberate of methylisobutylcarbinol and dibutylsulphosebacate.  The Specification as open to inspection under Sect. 91 comprises also the use of the esters in colour lakes, solvents for fats, printing and writing inks, automobile metal, furniture and shoe creams, in carbonizing and fat liquoring and in emulsions of perfumes, cosmetics, shaving creams, shampoos, petroleum (kerosene and naphtha), rubber, asphatic paints, varnishes, shellac pigments, germicides and in fire extinguishing emulsions and emulsions of boring, wire-drawing and cutting (lathe) oils. This subject-matter does not appear in the Specification as accepted.