Patent GB-420812-A (GB)
Title: Processes for the treatment of textile and other fibrous material
IPC: C09K23/00
Filed: 1933-05-01
Abstract: As assistants in cleansing, wetting, bleaching, dyeing, finishing or oiling textiles, leather and other fibrous materials, use is made of ethers derivable from (1) a mono- or poly-hydric saturated or unsaturated aliphatic alcohol containing eight or more carbon atoms, with or without additional substituents such as halogen atoms, and (2) an aliphatic hydroxyaldehyde, hydroxyketone, hydroxycarboxylic acid, hydroxyamine or hydroxymercaptan containing not more than six carbon atoms and not more than two hydroxy groups.  Use may be made also of conversion products of such ethers obtainable (a) by acylating or etherifying any free hydroxy groups present, or (b) by introducing a hydrophile group into the residue of component (2); specified hydrophile groups are sulphonic and sulphuric ester groups, nitrogenous derivatives of the carboxyl group, and ester groups of phosphorus acids.  Such groups may be introduced by conversion of the carbonyl, carboxyl, amino or mercapto group in the residue of component (2), or by conversion of a free hydroxy group, if present in that residue.  Thus the ethers may be sulphonated or condensed with taurine and its homologues, ethionic acid, isethionic acid and its homologues and their hydroxy derivatives, hydroxymethanesulphonic acid, hydroxypropanedisulphonic acids and their homologues, and phosphorus acids.  Neutralization may be effected, if necessary, with alkali or alkaline earth hydroxides, ammonia, primary, secondary or tertiary amines, ammonium bases or hydroxyamines. The following specific applications of the ethers are mentioned: (a) use as emulsifying agents for water-insoluble substances used in the treatment of fibrous materials, such as fatty acids, waxes, alcohols and hydrocarbons; (b) addition to the beater in paper manufacture; (c) use for maintaining in colloidal dispersion precipitates used in waterproofing; (d) addition to washing compositions containing salts, such as soda, waterglass, or trisodium phosphate, vegetable mucilaginous substances, or polysaccharides; (e) addition to sizes containing magnesium chloride or other alkaline earth salt; (f) use of ethers derived from hydroxyaldehydes for treating leather; (g) use of insoluble metal salts of ethers derived from hydroxycarboxylic acids for waterproofing; (h) use of the water-insoluble ethers for reducing the lustre of artificial silk or for improving the adhesion of driving belts or as adhesives for woven fabrics; the water-insoluble ethers may be used as solutions in oils or as emulsions.  In the examples, (1) sodium oleylate is condensed with bromotricarballylic acid trimethyl ester; the ester groups in the product are saponified, and the acid is neutralized; the product is useful for improving the foaming properties of soap; (2) chloracetaldehyde is condensed with sodium stearylate; the product is useful as a wetting agent for cotton fibres or as an addition to sizing and fulling baths; emulsions of the product are useful for imparting suppleness to leather; (3) sodium laurylate is condensed with chloracetone or other halogenketone or halogenaldehyde containing one or more halogen atoms but not more than six carbon atoms; the products have the same uses as that of example 2; (4) glycerol-a -monolauryl ether is treated with hydrogen chloride to form a chlorhydrin, which is treated with ammonia to yield a hydroxyamine useful as a wetting agent; (5) the amine obtained in example 4 is sulphonated; the product is useful as a wetting and cleansing agent; (6) glycerol-a -monolauryl ether (as disodium compound) is condensed with glycol chlorhydrin, and the ether obtained is treated to replace one or both of the hydroxy groups by chlorine; the product is treated with ammonia to yield an amine, which may then be sulphonated; the amine and its sulphonation product are useful as wetting, cleansing and finishing agents; (7) glycerol monolauryl ether is sulphonated, and the neutralized product is boiled with potassium hydrosulphide solution, whereby the sulpho group is replaced by the mercapto group; the mercaptan is then sulphonated to yield a wetting and foaming agent; (8) the monolauryl ether of glycerol monochlorhydrin is condensed with ethylene diamine; the product is useful as a wetting agent; (9) sodium oleylate is condensed with chloracetic acid, and the acid obtained is converted into its amide by way of the chloride; the amide is useful as an emulsifying agent; (10) the acid chloride obtained in example 9 is condensed with diethylethylenediamine to yield a wetting agent; (11) lauryloxyacetyl chloride is condensed with sodium isethionate; the product is useful as a cleansing agent for cotton, wool and leather; (12) sodium chlorethanesulphonate is heated with sodium oleyloxyacetate; the product is useful as a cleansing agent for cotton, wool and leather; (13) oleyloxyacetyl chloride is treated with sodium hydroxypropanedisulphonate; the product is useful as a cleansing and foaming agent; (14) sodium oleylate is heated with dichloracetone to yield a chlorinated ether-ketone, which is heated with sodium sulphite solution to replace chlorine by the sulpho group; the product is useful as a wetting agent; (15) oleyloxyacetaldehyde and glycerol oleyl ether are added to a fat-liquoring composition for leather containing yolk of egg and turkey red oil; (16) oleyloxyacetaldehyde, resin and turpentine are mixed together to form a paste to be applied to leather belts to reduce slipping; (17) a solution of sodium stearyloxyacetate is treated with aluminium sulphate solution, and the product is mixed with sodium stearate and stearylglycol acetate; a composition useful for waterproofing fabrics, leather and paper is obtained; (18) the dyeing effect of a bath comprising a substantive dye, e.g. Sulphon orange, sodium sulphate and acetic acid is improved by addition of a mixture of pyridine, dioxane, and the product of example 5; (19) cotton is impregnated with an aqueous mixture of an azo dye component, e.g. naphthol AS, turkey red oil, caustic soda, glue, and the product of example 5; coupling with a diazo component is then effected in the usual way; (20) sodium cetylate is condensed with chloracetaldehyde, and the ether-aldehyde obtained is converted into a sulphonic acid by treatment with sodium bisulphite; the product is useful as an addition to fat-liquoring compositions for leather. Reference is made to the use of ethers of the kind described derivable from octadecanediol, or from alcohols obtained by reduction of fatty acids and their esters or by oxidizing paraffins, or from wax alcohols or wool fat alcohols.  The Specification as open to inspection under Sect. 91 describes the manufacture, for the purposes stated above, of ethers derivable from components as under (1) above and polyhydroxy compounds such as glycol, propyleneglycol, glycerol and erythritol, or their acetyl, butyryl or other acyl derivatives, or ethers still containing a free hydroxy group such as glycol monoethyl ether, triglycolether, diglycerol ether, glycol glycerol ether, and diglycol monobutyl ether.  Reference is made also to the manufacture and use of ethers derivable from components as under (1) above and anhydrides or lactones of hydroxycarboxylic acids, or hydroxycarboxylic acids containing an ether group.  The Specification refers also to the introduction of polar groups into ethers derivable from components as under (1) above and polyhydroxy compounds, hydroxycarbonyl compounds, and hydroxycarboxylic acids, and mentions as polar groups the sulphuric ester, sulpho, amino and mercapto groups and groups derived from alkyl-, aralkyl-, aryl- and alkoxy-amines, aminocarboxylic acids, aminooxycarboxylicacids and their amides, aminoaldehydes, taurine and its homologues, ethionic acid and its homologues and their hydroxy derivatives, oxymethanesulphonic acid, oxypropanesulphonic acids and their homologues, oxypropanedisulphonic acids and their homologues, diamines and polyamines (including alkylated and acylated amines), ammonium bases, phosphorus acids, "phosphorous acid esters of alkoxyamines," and alkoxytetramines.  The following additional applications of any of the ethers described above are mentioned: (a) use as smoothing agents for artificial silk, cotton, wool and paper; (b) use in washing, carbonizing, fulling and dyeing wool; (c) use as emulsifying agents in conjunction with other emulsifying agents such as turkey red oil, gelatin, butylnaphthalenesulphonic acid, pyridine, dioxane, morpholine and butylamine; (d) use in preparing emulsions of tetrahydronaphthalene, methylcyclohexanol, butyl alcohol and other cleansing agents, and in dispersing dyes; (e) use as additions to coagulating baths for artificial silk; (f) use for sizing and finishing fibres; (g) use in association with ordinary soaps.  The following examples are given: (21) sodium laurylate is condensed with glycol chlorhydrin; (22) sodium stearylate is condensed with dichlorhydrin; (23) the sodium compound of wool fat alcohol is condensed with "dichlorethylene ether"; (24) oleyl alcohol is treated with ethylene oxide; (25) oleyl alcohol is treated with epichlorhydrin, preferably with addition of sulphuric acid as a catalyst; (26) the disodium compound of glycerol-a -monolauryl ether is condensed with glycol chlorhydrin; (27) the sodium compound of wool fat alcohol is condensed with glycol chlorhydrin; the ether-alcohol obtained is converted into its sodium compound and condensed with ethyl chloracetate; the ester group may then be saponified; (28) the sodium compound of glycol monolauryl ether is treated with ethyl chloracetate, and the ester group in the product is saponified; (29) sodium malonic ester is heated with "a -lauryl-b -chloroglycerol ether," and the product is saponified; (30) diethyleneglycol is treated with hydrogen chloride, and the chlorhydrin obtained is condensed with sodium laurylate; the