Patent GB-436075-A (GB)
Title: Improvements in and relating to processes for cleansing, wetting, bleaching, dyeing,finishing or oiling textile and other fibrous materials, including leather
Filed: 1934-01-29
Abstract: As assistants in processes for cleansing, wetting, bleaching, dyeing, finishing or oiling textile and other fibrous materials, including leather, use is made of compounds with a straight chain of at least six carbon atoms containing (a) a terminal carboxylic group esterified or amidated with an alcohol or amine containing a group derived from an oxygenated acid of sulphur, or (b) a terminal sulphonic group, or (c) a terminal persulphonic group, the straight chain carrying also a side chain which contains at least two carbon atoms and is free from acidic salt-forming groups; the side chain is linked to the main chain either directly or through an atom of oxygen or nitrogen, and the carbon atom in the main chain to which the side chain is attached must not be in the a - or b -position.  The side chain may be built up (1) by introducing an alkyl group into the straight chain; (2) by esterifying with a mono- or poly-hydric alcohol a carboxylic group linked to the main chain, or by converting the carboxylic group into a substituted amide group; the carboxylic group may be introduced into the straight-chain compound by way of the cyano group; (3) by reaction of a straight-chain compound containing halogen with a compound such as a malonic ester, a tricarballylic ester, or an acetoacetic ester, i.e. a compound in which a hydrogen atom linked to carbon can be substituted by an alkali metal; (4) by esterifying or etherifying a hydroxy group linked to the straight chain, e.g. by etherifying the hydroxy group or groups of hydroxy fatty acids, such as ricinoleic acid; (5) by substituting a carbonaceous group, e.g. by acylation, into an amino group linked to the straight chain ; (6) by reacting a straight-chain compound containing halogen with an amine, a diamine, or a hydroxy- or oxo-amine; the side chain may contain substituents such as hydroxy, oxo, or nitrogenous groups, or esterified or etherified hydroxy groups.  In examples of the preparation of typical compounds, (1) the dichlorinated acid of coconut oil is converted into a dibutyl ether by reaction with sodium butylate, and then amidated by condensation with taurine; the product is useful as a wetting-agent; (2) trichlorostearic acid is treated with the sodium compound of glycerol monoethyl ether, and the free hydroxy groups in the product are acetylated; this product is then condensed with isethionic acid; the final product is useful as a wetting-agent, as a dispersing agent in dyebaths or, in association with soap, for emulsifying mineral oils; (3) tetrachlorocetylsulphonic acid is converted into a propyloxy derivative, useful as a wetting-agent, by reaction with sodium propylate; (4) ricinoleic acid is treated with butyric acid chloride and the product is condensed with taurine; (5) hexachlorostearic acid is treated with sodium octylate and the product is condensed with taurine; (6) dichlorocetylsulphonic acid is heated with sodium hydroxide solution to yield dioxycetylsulphonic acid, which is treated with butyric acid chloride; (7) dichlorocetylsulphonic acid is heated with potassium cyanide solution, and the nitrile groups in the product are saponified; the carboxylic groups thus formed are then esterified with amyl alcohol; (8) ricinoleic acid is treated with phosphorus pentachloride, and the chloro-fatty acid obtained is condensed with sodium glycerate; the free hydroxy groups in the product may be acylated and (or) etherified, e.g. with butyric acid or butyl alcohol, and finally the carboxylic group is esterified or amidated with isethionic acid or taurine; the product obtained from taurine has dispersing properties; instead of butyl alcohol the alkylates of hydroxy fatty acids may be used, e.g. the disodium compound of lactic acid, the carboxylic group of the hydroxy acid radicle being then esterified, e.g. with amyl alcohol; similar products may be obtained by heating salts of hydroxy fatty acids, e.g. dihydroxystearic acid, with sodium or a sodium alkylate, condensing the compound with a halogen compound of a mono- or polyhydric alcohol or of an acylated or etherified mono- or poly-hydric alcohol, and finally reacting the carboxylic group with taurine or isethionic acid; (9) the potassium salt of ricinoleic acid is heated with sodium or sodium methylate and then with monochlorhydrin; the free hydroxy groups in the product are acetylated by means of acetic anhydride, and the carboxylic group is then reacted with isethionic acid; a dihydroxystearic acid derivative in which one hydroxy group is etherified with butyl alcohol and the other with glycerol is similarly obtainable; (10) dichlorostearic acid is heated with sodium butylate to yield the sodium salt of dibutyloxystearic acid; the latter is heated with glycol monochlorhydrin and the ester obtained is sulphonated; (11) the dibutyric ester of dioxycetylsulphonic acid, prepared as in example 6, is converted into a persulphonic compound by treatment with sodium peroxide; the product is useful as a bleaching and detergent agent; other esters (or ethers) may be used instead of the dibutyric ester; (12) dichlorocetylsulphonate of sodium is heated with dibutylamine, whereby chlorine is replaced by the dibutylamino group; (13) dichlorocetylsulphonate of sodium is heated with the sodium compound of diethyl malonate.  Di- and tetra-chlorocetylsulphonic acid are obtainable by chlorinating cetylsulphonic acid in carbon tetrachloride.  Cetylsulphonic acid is obtainable by heating cetyl chloride or the sodium salt of cetylsulphuric acid ester with sodium bisulphite.  Hexachlorostearic acid is obtainable by chlorinating oleic acid in carbon tetrachloride.  The Specification as open to inspection under Sect. 91 refers generally to the manufacture of wetting, cleaning, bleaching, foaming and dispersing agents by introducing a side chain into (a) compounds containing a straight chain of at least six carbon atoms and a terminal carboxylic, hydroxymethyl, aminomethyl, sulphomethyl, aldehyde or sulphuric ester group, or functional derivatives of these, and (b) naphthenic compounds containing any of the groups specified under (a); the side chains may be combined directly or through an atom of oxygen or nitrogen, and the compounds may contain one or more double or triple bonds. Specified functional derivatives include (1) the partial esters of appropriate compounds as specified above with polycarboxylic acids, sulphocarboxylic acids, or polysulphonic acids, such as oxalic, adipic, phthalic, sulphoacetic, sulphosalicylic, sulphophthalic or naphthalene-disulphonic acid; (2) ethers and esters of appropriate compounds as specified above with alcohols or phenols, or sulphonation products of these ethers and esters; (3) the bisulphite compounds of the aldehydes; (4) the sulphonation products of the amines, or the condensation products of the amines with chlorhydrin or hydroxychloropropionic acid; (5) the xanthogenates of the alcohols; (6) persulphonic compounds derived from the sulphonic acids.  The following additional methods of introducing a side chain are referred to: (1) an aryl or aralkyl group is introduced into the main chain; (2) a carboxylic group linked to the main chain is amidated or esterified with an aminoalcohol; the side chain may contain a free carboxylic group.  The Specification inincludes the following examples: (1) ricinoleic acid is treated with butyric acid chloride and the product is converted into its sodium salt; (2) tetrahydroxystearic acid is esterified with valeric acid and then neutralized; (3) oleic acid which has absorbed six atoms of chlorine per molecule is heated under pressure with caustic soda until three chlorine atoms have been replaced by hydroxyl, and the product is successively etherified with sodium butylate and esterified with butyric acid; (4) the hexachlorinated acid of coconut oil is treated with sodium methylate; (5) the tribrominated acid of palm oil is treated with the sodium compound of the dibutyl ether of glycerol until all the bromine atoms are replaced; (6) the dibrominated acid of castor oil is treated with sodium methylate and then acylated with butyric acid; (7) hexachlorostearylsulphonic acid is reacted with sodium amylate; (8) dichlorostearic acid is reacted with the sodium compound of carvacrol; the product may then be condensed with ethanolamine; (9) "hexachloroleic acid" is treated with the sodium compound of octanol-2 and the product is condensed with 2-amino-2<1>-sulphodiethyl ether or with an aminocarboxylic acid; (10) ricinoleic acid is treated to replace the hydroxy group by chlorine, and then condensed with sodium butylate; the product is esterified with butyl alcohol and then reduced with sodium and ethanol; the final product is mainly the monobutyl ether of the dihydric alcohol derivable from ricinoleic acid; (11) the p dibutyloxy derivative of coconut oil acid is esterified with butyl alcohol, and the carboxylic ester group is then reduced to an alcohol group with sodium and alcohol; (12) the dichlorinated acid of linseed oil is treated with sodium ethylate and then reduced as in the preceding example; the product is then sulphonated; (13) ricinoleic acid is treated to replace the hydroxyl group by chlorine and then condensed with sodium ethylate; the product is reduced to yield the monoethyl ether of the dihydric alcohol derivable from ricinoleic acid; (14) the ether-alcohol obtained in example 11 (this paragraph) is sulphonated to yield a sulphuric ester; (15) the carvacryloxystearic acid obtained in example 8 (this paragraph) is esterified with ethyl alcohol and then reduced with hydrogen, sodium and alcohol to yield an ether-alcohol; (16) the carvacrol derivative obtained in example 15 is etherified with glycerol and then sulphonated to yield a sulphuric ester; (17) the nonsulphonated carvacrolglycerol ether obtained in example 16 is treated successively with hydrochloric acid and ammonia, and the ami