Patent GB-446498-A (GB)
Title: Improvements in or relating to agents for modifying the surface tension of liquids
Filed: 1934-09-25
Abstract: Hydrogenated organic hydroxy or amino compounds which contain at least 12 carbon atoms, at least 2 carbon rings and are substituted at the hydroxy or amino group by a residue containing a water solubilizing group are added to aqueous liquids used for the treatment of textiles, leather, fur and other fibrous materials. These compounds which may be entirely or partly hydrogenated are stated to have wetting, emulsifying, impregnating, stabilizing, levelling, foaming and cleansing properties.  They may also be used in preparing dye pastes, in aftersoaping dyeings and printings made with azo dyes, in dyeing with vat and acid wool dyestuffs, in spinning and fulling, in preparing finishes containing hard wax, in preparing sizes containing glycerol and gum arabic and in bleaching with hydrogen peroxide.  The water solubilizing groups are defined as sulphonic, carboxylic and quaternary ammonium groups and sulphuric, phosphoric and thiosulphuric ester groups.  Groups formed by reacting with many molecular proportions of ethylene oxide or glycide may also be used to effect solubility.  The compounds may be used in conjunction with alkali carbonates, trisodium phosphate, alkali ortho, pyro, poly, meta and hypophosphates, alkali silicates, alkali borates, e.g. borax, sodium sulphate, sodium naphthalene sulphonate, hydrogen peroxide, peroxides, perborates, persulphates, percarbonates, perphosphates, perhydrophosphates, hydrocarbons, alcohols, superfatting agents, urease and pancreatin.  In examples: (1) perhydro-p-benzyl-phenyloxy-acetic acid is prepared by condensing the sodium compound of perhydro-p-benzyl-phenol (obtained by hydrogenating p-benzyl-phenol) with chloracetic acid in decahydronapthalene; in place of p-benzylphenol, cyclohexylphenols, p - hydroxydiphenyl, 1 - benzyl - 2 - naphthol, di(p - hydroxyphenyl) methane, cyclohexylidenecyclohexanone, a -di (4 - hydroxyphenyl)ethane, b  - di(4 - hydroxyphenyl) propane and condensation products of cresols with cyclohexylchloride or cyclohexene (obtained by dehydrating cyclohexanol with phosphorous pentoxide in the presence of aluminium chloride or perchloric acid) may be used; the corresponding amino compounds, e.g. perhydrocarbazols, and compounds containing higher substituents in the nuclei such as ethyl, propyl, butyl and isobutyl groups are also mentioned; cyclic ketones, e.g. cyclohexanone may be converted into resinous condensation products by means of alcoholic potash, and, after reduction a residue containing a water solubilizing group introduced into the hydroxy group; (2) a mixture of perhydrogenated hydroxybenzylphenoloxyacetic acid and methanedicyclohexyloxyacetic acid is prepared by condensing sodium chloracetate, in decahydronaphthalene, with the sodium compound of perhydrodihydroxydiphenylmethane (obtained by hydrogenation of dihydroxydiphenylmethane); ketonic compounds such as benzoyl-o-cresol, phenacetyl-o-cresol, b -phenylpropionyl-o-cresol, b -phenylacetylnaphthols, naphthoyl-o-cresols, isopropyl-benzoylnaphthols and isobutylnaphthoyl cresols may be subjected to reduction and used as starting materials; (3) perhydromenaphthylcresoloxyacetic acid is prepared by condensing sodium chloracetate with the sodium compound of perhydromenaphthylcresol (obtained by hydrogenation of the product of the condensation of cresol and menaphthylchloride); the same compound may be obtained by condensing the sodium compound of perhydromenaphthylcresol with chloraceticethylester in butylether; residues containing water solubilizing groups may also be introduced into products obtained by condensing phenol or cresol with chlorinated tetrahydro or decahydro naphthalenes; a mixture of mono-and di-chlordecahydronaphthalenes obtained by chlorination may be separated by fractional distillation; the monochlor compound when condensed with cresol gives decahydronaphthyl cresol while the dichlor compound yields octahydronaphthylcresol.  Anthracene and phenanthrene derivatives may be used by treating the hydrocarbons with formaldehyde and hydrochloric acid and condensing with phenols. Phenanthrene derivatives may be obtained from colophonium; a resin alcohol is obtained by reduction, the hydroxy group replaced by chlorine and the product condensed with a phenol.  The resin alcohol and phenol may be condensed directly by means of perchloric acid. One molecule of a phenol may be condensed with two molecules of a chlorinated aromatic compound, e.g. menaphthyl chloride, the product hydrogenated and a residue containing a water-solubilizing group introduced into the hydroxy group.  This may be done by condensing with ethylene or glycerol chlorhydrin and sulphonating. Alternatively, the hydroxy group may be replaced by chlorine and the product condensed with primary, secondary or tertiary amines, e.g. secondary methyl taurine.  The residues carrying the water solubilizing groups may enter the amino or hydroxy group in the ether or ester form or in the amino or amido form.  Acids, their anhydrides or halides substituted by water solubilizing groups may be reacted with the amino or hydroxy group or acids containing chlorine may be used and the esters or amides treated with sodium sulphite or sodium thiosulphate or the chlorine replaced by a quaternary ammonium group. It is also possible to amidify or esterify polybasic acids semilaterally with the amino or hydroxy groups.  Specification 425,239 is referred to.ALSO:Hydrogenated organic hydroxy or amino compounds which contain at least 12 carbon atoms, at least 2 carbon rings and are substituted at the hydroxy or amino group by a residue containing a water solubilizing group are stated to have emulsifying properties.  The water solubilizing groups are defined as sulphonic, carboxylic and quaternary ammonium groups and sulphuric, phosphoric and thiosulphuric ester groups.  Groups formed by reacting with many molecular proportions of ethylene oxide or glycide may also be used to effect solubility.  The compounds may be used in conjunction with alkali carbonates, trisodium phosphate, alkali ortho, pyro, poly, meta and hypophosphates, alkali silicates, alkali borates, e.g. borax, sodium sulphate, sodium naphthalene sulphonate, hydrogen peroxide, peroxides, perborates, persulphates, percarbonates, perphosphates, perhydrophosphates, hydrocarbons, alcohols, superfatting agents, urease and pancreatin.  In examples: (1) perhydro-p-benzylphenyloxy-acetic acid is prepared by condensing the sodium compound of perhydro-p-benzylphenol with chloracetic acid; cyclohexylphenol, p-hydroxydiphenyl, 1-benzyl-2-naphthol, di (p-hydroxyphenyl) methane, cyclohexylidenecyclohexanone di (4-hydroxyphenyl) ethane, di (4-hydroxyphenyl) propane and condensation products of cresols with cyclohexylchloride or cyclohexene are also mentioned as starting materials as well as the corresponding amino compounds, e.g. perhydrocarbazols, and compounds containing higher substituents in the nuclei such as ethyl, propyl, butyl and isobutyl groups; cyclic ketones, e.g. cyclohexanone may be converted into resinous condensation products by means of alcoholic potash, and, after reduction a residue containing a water solubilizing group introduced into the hydroxy group; (2) a mixture of perhydrogenated hydroxybenzlyphenoloxyacetic acid and methanedicyclohexyloxyacetic acid is prepared by condensing sodium chloracetate with the sodium compound of perhydrodihydroxydiphenylmethane; ketonic compounds such as benzoyl-o-cresol, phenacetyl-o-cresol, b -phenylpropionyl-o-cresol, b - phenylacetylnaphthols, naphthoyl - o-cresols, isopropylbenzoylnaphthols and isobutylnaphthoyl cresols may be subjected to reduction and used as starting materials; (3) perhydromenaphthylcresoloxyacetic acid is prepared by condensing sodium chloracetate with the sodium compound of perhydromenaphthylcresol; residues containing water solubilizing groups may also be introduced into products obtained by condensing phenol or cresol with chlorinated tetrahydro or decahydro naphthalenes.  Anthracene and phenanthrene derivatives may be used by treating the hydrocarbons with formaldehyde and hydrochloric acid and condensing with phenols.  Phenanthrene derivatives may be obtained from colophonium; a resin alcohol is obtained by reduction, the hydroxy group replaced by chlorine and the product condensed with a phenol.  The residues carrying the water solubilizing groups may enter the amino or hydroxy group in the ether or ester form or in the amino or amido form.  Acids, their anhydrides or halides substituted by water solubilizing groups may be reacted with the amino or hydroxy group or acids containing chlorine may be used and the esters or amides treated with sodium sulphite or sodium thiosulphate or the chlorine replaced by a quaternary ammonium group.  It is also possible to amidify or esterify poly basic acids semilaterally with the amino or hydroxy groups.