Patent GB-456517-A (GB)
Title: Improvements in the manufacture and production of washing, wetting, emulsifying, softening and like agents
IPC: C11D1/88
Filed: 1935-04-05
Abstract: High molecular polyether carboxylic acids, containing at least two ether oxygen atoms and not more than three alkyleneoxy groups directly connected together are prepared by introducing at least one carboxylic group, by the following methods, into polyethers derived from aliphatic polyhydric alcohols having from 2-4 carbon atoms and containing at least one aliphatic, cycloaliphatic or mixed aromaticaliphatic radicle having at least 8 carbon atoms attached to the ether radicle by means of oxygen, nitrogen or sulphur: (a) when the polyethers contain a mineral acid residue they are treated with hydrocyanic acid or its salts and the resulting nitriles saponified; (b) when the polyethers contain a terminal CH2OH group, they are oxidized to the corresponding carboxylic acid or are converted into the alkali alcoholate and condensed with low molecular halogen carboxylic acids or are esterified with polycarboxylic acids to give ester-acids; (c) when the polyethers contain an amino group they are reacted with a mineral acid ester of a hydroxycarboxylic acid or a polycarboxylic acid.  The same products are obtained by treating polyether carboxylic acids which contain hydroxy or amino groups with high molecular carboxylic acids or their halides, alcohols of high molecular weight or alkylated phenols, and also by treating polyether dicarboxylic acids with amines or alcohols of high molecular weight. The products are stated to be wetting, washing, softening, foaming and emulsifying agents.  In examples: (1) sodium monochloracetate is condensed with sodium dodecyltriethyleneglycolether and with the sodium compound of a polyhydroxyethylated octodecylalcohol; (2) bis-ethyleneglycollic acid anhydride is reacted with dodecyl alcohol and with oleylamine; (3) dodecyl triethyleneglycolether is oxidized to the carboxylic acid with nitric acid; (4) oleic acid chloride is condensed with the substituted glycocoll obtained from the sulphuric ester of diethyleneglycolmonoethylether and glycocoll; (5) octodecyltriethyleneglycolchlormethylether, obtained from hydrochloric acid, trioxymethylene and octodecyltriethyleneglycol, is treated with cuprous cyanide and the nitrile saponified; (6) phthalic anhydride is reacted with (a) diethyleneglycolmono dodecyl, octodecenyl or naphthenyl ether, (b) the acid amide obtained by condensing hardened train oil fatty acids with ethanolamine and treating with ethylene oxide and (c) the amine obtained by condensing methylamine with the sulphuric ester of diethylene glycolmonododecylether.  Maleic, chlormaleic, succinic, adipic, diglycollic, thiodiglycollic and oxalic acids are specified polycarboxylic acids which may be used. Diethyleneglycol - b dodecylether - b <1> - N - methylaminoacetic acid, diethyleneglycol - b  - octodecylether - b <1> - N - benzylaminomaleicmonoamide and diethyleneglycol -b  - octadecenylether - b <1> - phthalic acid monoester are products which are mentioned.  Samples have been furnished under Sect. 2 (5) as follows: (1) phthalic acid monoester of iso dodecylmethylcyclohexylpolyethyleneglycol obtained from iso-dodecylhexahydrocresol and ethylene oxide; (2) phthalic acid monoester of iso - dodecyltolylpolyethyleneglycol; (3) the sodium compound of dodecyl mercaptan is condensed with b -chlorethyldiethylenglycol and the product converted into the monoester of phthalic acid; (4) b -b <1>-diiododiethylether is converted into the Grignard compound and treated with ethyleneoxide; dihydroxydibutylether is obtained on saponification and its sodium compound by condensation with sodium dodecyl sulphate yields an ether-alcohol which is esterified with phthalic acid.ALSO:High molecular polyether carboxylic acids, containing at least two ether oxygen atoms and not more than three alkyleneoxy groups directly connected together which are stated to be emulsifying agents, are prepared by introducing at least one carboxylic group, by the following methods, into polyethers derived from aliphatic polyhydric alcohols having from 2--4 carbon atoms and containing at least one aliphatic, cycloaliphatic or mixed aromatic-aliphatic radicle having at least 8 carbon atoms attached to the ether radicle by means of oxygen, nitrogen or sulphur: (a) when the polyethers contain a mineral acid residue they are treated with hydrocyanic acid or its salts and the resulting nitriles saponified; (b) when the polyethers contain a terminal CH2 OH group, they are oxidized to the corresponding carboxylic acid or are converted into the alkali alcoholate and condensed with low molecular halogen carboxylic acids or are esterified with polycarboxylic acids; (c) when the polyethers contain an amino group they are reacted with a mineral acid ester of a hydroxycarboxylic acid or a polycarboxylic acid.  The same products are obtained by treating polyether carboxylic acids which contain hydroxy or amino groups with high molecular carboxylic acids or their halides, alcohols of high molecular weight or alklyated phenols, and also by treating polyether dicarboxylic acids with amines or alcohols or high molecular weight.  In examples:  (1) sodium monochloracetate is condensed with sodium dodecyltriethyleneglycolether and with the sodium compound of a polyhydroxyethylated octodecylalcohol; (2) bis-ethyleneglycollic acid anhydride is reacted with dodecyl alcohol and with oleylamine; (3) dodecyltriethyleneglycolether is oxidized to the carboxylic acid with nitric acid; (4) oleic acid chloride is condensed with the substituted glycocoll obtained from the sulphuric ester of diethyleneglycolmonoethylether and glycocoll; (5) octodecyltriethyleneglycolchlormethylether, obtained from hydrochloric acid, trioxymethylene and octodecyltriethyleneglycol is treated with cuprous cyanide and the nitrile saponified; (6) phthalic anhydride is reacted with (a) diethyleneglycolmono dodecyl-, octodecenyl- or naphthenyl-ether, (b) the acid amide obtained by condensing hardened train oil fatty acids with ethanolamine and treating with ethylene oxide, and (c) the amine obtained by condensing methylamine with the sulphuric ester of diethylene glycolmonododecylether.  Maleic, chlormaleic, succinic, adipic, diglycollic, thiodiglycollic and oxalic acids are specified poly carboxylic acids which may be used. Diethyleneclycol-b -dodecylether-b <1>-N-methylaminoacetic acid, diethyleneglycol-b -octodecylether-b <1>-N-benzylamino -maleicmonoamide and diethyleneglycol - b  - octadecenylether - b <1>-phthalic acid monoester are products which are mentioned.  Samples have been furnished under Sect. 2 (5) as follows: (1) phthalic acid monoester of iso-dodecylmethyl - cyclohexylpolyethyleneglycol; (2) phthalic acid monoester of isododecyltolylpolyethyleneglycol; (3) the sodium compound of dodecylmercaptan is condensed with b -chlorethyldiethyleneglycol and the product is converted into the monoester of phthalic acid; (4) b -b <1>-di-iododiethylether is converted into a Grignard compound and treated with ethyleneoxide, to give after saponification dihydroxydibutylether; the sodium compound of the latter is treated with sodium dodecylsulphate and the resulting polyetheralcohol esterified with phthalic acid.