Patent GB-449081-A (GB)
Title: Improvements in the manufacture and production of washing, wetting, emulsifying and like agents
Filed: 1934-12-10
Abstract: Products having wetting, washing, and emulsifying properties are obtained by the reaction of primary or secondary amines, containing at least one aliphatic or cycloaliphatic radicle of at least six carbon atoms linked directly to nitrogen, with polycarboxylic acids or their derivatives while providing that the products formed contain at least one free or merely neutralized carboxylic group derived from the polycarboxylic acid or derivative.  Suitable amines are (a) amines corresponding to the acids of palm-kernel oil, coconut oil, soya bean oil, rapeseed oil, poppy-seed oil, tallow, train oil or tall oil, such as octylamine, dodecylamine, myristylamine, cetylamine or oleylamine, (b) the N-methyl, N-ethyl, N-hydroxyalkyl and N-benzyl derivatives of such amines, and (c) cycloaliphatic amines such as cyclohexylethylamine, abietylamine or amines corresponding to the naphthenic acids.  Amines in which the carbon chain is interrupted by an oxygen or sulphur atom or by a group such as --NX--, --CONX--, where X is hydrogen or an organic radicle, --SO2NH--, --NHCONH--, or --NHCSNH-- or (according to the Provisional Specification) --SO2--, --OSO2--, --NHC(: NH)NH--, or --C(O)O--, may also be used, as well as amines substituted by halogen atoms or hydroxy groups or (according to the Provisional Specification) nitro groups; the use of amines containing sulphuric ester groups is excluded.  Specified polycarboxylic acids are oxalic, maleic, malonic, succinic, citric, adipic, diglycollic, thiodiglycollic, ethylene-bis-glycollic, dilactic and phthalic acids; instead of the acids, their acid salts or derivatives such as their esters or anhydrides may be used; when esters are taken, the products must be saponified to produce the free or neutralized carboxylic group. The reaction may be effected by heating the components, generally in equimolecular proportions or with the acid or its derivative in excess, to 60--250 DEG  C. in the presence or absence of a solvent or diluent, a number of which are specified.  The products may be used as free acids or as alkali, ammonium or hydroxyalkylamine salts, and alone or together with protective colloids, such as glue or albuminous degradation products, or salts such as sodium carbonate, sodium phosphate, sodium pyrophosphate, perborates or waterglass.  Reference is made to the use of the products for emulsifying oils, fats and waxes, as softening agents for textiles, for washing wool, and as additions to dyeing and fulling baths and baths for degumming silk.  In the examples: (1) oleylmethylamine and diethyl oxalate are heated together, and the product is treated with caustic soda to saponify the carboxylic ester group; oleylmethyloxamic acid is obtained, as sodium salt; (2) the bromides of the alcohols obtained from the acids of palm-kernel oil are reacted with methylamine, and the amine mixture is condensed with diethyl oxalate as in example 1; (3) an amine mixture obtained from the alcohols of sperm oil is heated with diethyl oxalate, and the carboxylic ester group in the product is saponified with triethanolamine; (4) the bromides of the alcohols obtained from the acids of coconut oil are reacted with methylamine, and the amine mixture is condensed with maleic anhydride; (5) dicyclohexylamine and phthalic anhydride are heated together, and the product is neutralized with caustic potash; the potassium salt of dicyclohexylphthalamic acid is obtained; (6) an amine mixture obtained by the catalytic hydrogenation of lauronitrile in the presence of methylamine is condensed with diethyl oxalate as in example 1; (7) the amine C12H25OCH2 CH2NHCH2CH2OH (obtained from ethanolamine and the sulphuric ester of ethylene glycol monododecyl ether) is condensed with diethyl oxalate as in example 1; the corresponding aminothioether, obtained by treating dodecyl mercaptan with an equimolecular proportion of ethylene oxide, and reacting the sulphuric ester of the product with ethanolamine, may be similarly treated; (8) monooleylethylenediamine is condensed with diethyl oxalate as in example 1; (9) an amine obtained by reacting oleyl alcohol sulphuric ester with triethylene tetramine is condensed with diethyl oxalate as in example 1; (10) an amine obtained by hydrogenating oleic nitrile is condensed with diethyl oxalate as in example 1; (11) the amine taken in example 10 is condensed with thiodiglycollic anhydride; (12) oleylamine is condensed with diglycollic anhydride or (example 13) ethylene-bis-glycollic anhydride (obtained by heating ethylene-bis-glycollic acid with acetic anhydride); (14) stearylamine or dodecylamine is condensed with ethylene-bis-glycollic anhydride; (15) dodecylmethylamine is condensed with diglycollic anhydride; (16) the nitriles of hydrogenated train oil acids are hydrogenated, and the amine mixture so obtained is condensed with dilactic anhydride.  Samples have been furnished under Sect. 2(5) of products prepared as follows: (1) the sulphuric esters of the alcohols obtained from palm kernel oil acids are heated with sodium sulphite, and the sulphonic acids so obtained are converted into sulphochlorides by reaction with phosphorus pentachloride; the sulphochlorides are condensed with an excess of ethylenediamine, and the product is reacted with phthalic anhydride; (2) stearyl isocyanate (from stearylamine hydrochloride and phosgene) is treated with ethylene diamine to form the urea derivative C18H37NHCONHCH2CH2NH2, which is condensed with phthalic anhydride; (3) cyclohexyl thiocyanate is treated with an excess of ethylene diamine to yield a thiourea derivative, which is condensed with phthalic anhydride; (4) N-stearyl-N-aminoethylmethylamine (from stearylmethylamine and ethanolamine sulphuric ester) is condensed with phthalic anhydride; (5) oleic acid chloride is condensed with bromethylmethylamine, and the product is treated with methylamine to form the amine C17H33CON(CH3)CH2CH2NHCH3, which is then condensed with diethyl oxalate as in example 1.ALSO:Products having washing and emulsifying properties are obtained by the reaction of primary or secondary amines, containing at least one aliphatic or cycloaliphatic radicle of at least six carbon atoms linked directly to nitrogen, with polycarboxylic acids or their derivatives while providing that the products formed contain at least one free or merely neutralized carboxylic group derived from the polycarboxylic acid or derivative. Suitable amines are (a) amines corresponding to the acids of palm-kernel oil, coconut oil, soya bean oil, rapeseed oil, poppy-seed oil, tallow, train oil or tall oil, such as octylamine, dodecylamine, myristylamine, cetylamine or oleylamine, (b) the N-methyl, N-ethyl, N-hydroxyalkyl and N-benzyl derivatives of such amines, and (c) cycloaliphatic amines such as cyclohexylethylamine, abietylamine or amines corresponding to the naphthenic acids.  Amines in which the carbon chain is interrupted by an oxygen or sulphur atom or by a group such as -NX-, -CONX-, where X is hydrogen or an organic radicle, -SO2NH-, -NHCONH-, or -NHCSNH- or (according to the Provisional Specification) -SO2-, -OSO2-, -NHC(:NH)NH-, or -C(O)O-, may also be used, as well as amines substituted by halogen atoms or hydroxy groups or (according to the provisional Specification) nitro groups; the use of amines containing sulphuric ester groups is excluded.  Specified polycarboxylic acids are oxalic, maleic, malonic, succinic, citric, adipic, diglycollic, thiodiglycollic, ethylene-bis-glycollic, dilactic and phthalic acids; instead of the acids, their acid salts or derivatives such as their esters or anhydrides may be used; when esters are taken, the products must be saponified to produce the free or neutralized carboxylic group.  The products may be used as free acids or as alkali, ammonium or hydroxyalkylamine salts, and alone or together with protective colloids, such as glue or albuminous degradation products, or salts such as sodium carbonate, sodium phosphate, sodium pyrophosphate, perborates or waterglass.  Reference is made to the use of the products for emulsifying oils, fats and waxes, for washing wool, and as additions to fulling baths and baths for degumming silk.  In the examples: (1) oleylmethylamine and diethyl oxalate are heated together, and the product is treated with caustic soda to saponify the carboxylic ester group; oleylmethyloxamic acid is obtained, as sodium salt; (2) the bromides of the alcohols obtained from the acids of palm-kernel oil are reacted with methylamine, and the amine mixture is condensed with diethyl oxalate as in example 1; (3) an amine mixture obtained from the alcohols of sperm oil is heated with diethyl oxalate, and the carboxylic ester group in the product is saponified with triethanolamine; (4) the bromides of the alcohols obtained from the acids of coconut oil are reacted with methylamine and the amine mixture is condensed with maleic anhydride; (5) dicyclohexylamine and phthalic anhydride are heated together and the product is neutralized with caustic potash; the potassium salt of dicyclohexylphthalamic acid is obtained; (6) an amine mixture obtained by the catalytic hydrogenation of lauronitrile in the presence of methylamine is condensed with diethyl oxalates as an example 1; (7) the amine C12H25OCH2CH2NHCH2CH2OH is condensed with diethyl oxalate as in example 1; the corresponding aminothioether may be similarly treated; (8) monooleylethylenediamine is condensed with diethyl oxalate as in example 1; (9) an amine obtained by reacting oleyl alcohol sulphuric ester with triethylene tetramine is condensed with diethyl oxalate as in example 1; (10) an amine obtained by hydrogenating oleic nitrile is condensed with diethyl oxalate as in example 1; (11) the amine taken in example 10 is condensed with thiodiglycollic anhydride; (12) oleylamine is condensed with diglycollic anhydride or (example 13) ethylene-bis-glycollic anhydride; (16) steary