Patent GB-437104-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
Filed: 1934-03-16
Abstract: Products stated to be useful as emulsifying, wetting, cleansing and dispersing agents in the textile, leather and paper industries are obtained by introducing low molecular radicles containing carboxylic groups or groups capable of being readily converted into carboxylic groups into amines containing at least two amino groups and at least one alkyl or aliphatic acyl radicle containing at least six carbon atoms attached to one of the nitrogen atoms. The amines may be prepared by condensing a polyamine with a compound containing the desired aliphatic radicle and the introduction of the carboxylic group may take place prior to, p  simultaneously with or following the condensation.  Suitable amino compounds may be prepared from amines such as ethylenediamine, propylene diamine, sym. dimethylethylenediamine, diethylenetriamine, triethylenetetramine, o-, m- and p-phenylenediamine, toluylenediamine, benzidine and diamino diphenylamine.  The radicle containing a chain of at least six carbon atoms may be hydrocarbon radicles or may be substituted by hydroxy, amino, nitro, ester or ether groups, or by halogens, especially chlorine, and may also be interrupted by --NH--, --N alkyl--, --O--, --S--, or --CO--bridges; amino or hydroxy group substituents may also be substituted, e.g. oleic amides of glycocoll or sarcosine, or stearic acid esters of lactic acid may be condensed with the polyamines.  Suitable amino compounds may be prepared by reacting polyamines with sulphuric acid esters of alcohols of high molecular weight or with alkyl halides, e.g. cetyl bromide, the acid sulphuric acid ester of octodecyl alcohol and derivatives of alcohol mixtures obtained by the catalytic hydrogenation of naturally occurring fats and oils.  Other alcohol derivatives are those of octyl, dodecyl, cetyl, octodecyl and oleyl alcohols, myristol, montanol, abientinol and octodecanediol.  The polyamines may also be reacted with carboxylic acids of high molecular weight, their halides, anhydrides or esters, e.g. valeric acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, abietic acid, montanic acid and napthenic acids and mixtures of such acids, especially those obtainable by saponification from coconut oil, palm kernel oil, soya bean oil, train oils or tallow, or by the oxidation of paraffin hydrocarbons.  The amines are preferably reacted with at least one molecular proportion of the aliphatic compounds.  Suitable amino compounds may also be prepared by the catalytic hydrogenation of nitriles of amino acids containing a radicle of at least six carbon atoms or by hydrogenating mixtures of nitriles of the formula R.NH.CH2.CH2.CN (where R is the radicle contained in the fatty acids of natural oils or fats) in the presence of ammonia and hydrogen at elevated pressure and temperature, e.g. 325 DEG  C. using basic cobalt carbonate as catalyst.  The carboxylic group may be introduced in the form of the nitrile, carboxylic ester or chlorcarbonic ester groups, or by reaction with low molecular aliphatic halogen acids or polybasic acids or their esters, e.g. monochlor acetic acid, monochlorpropionic acid, malonic acid, adipic acid, or their monoesters.  The carboxylic group may be linked to the amino group through a hetero atom such as nitrogen, e.g. monochloracetic acid may be reacted with glycocoll and the resulting compound reacted with the polyamine. Hydroxyalkyl groups or polyglycol ether radicles may also be introduced to improve the water-solubility of the products, e.g. by reaction with ethylene oxide, propylene oxide, polyhydric alcohols, polyglycols or polyglycerines or their halogen compounds, or the compounds may be sulphonated.  According to examples: (1) a wetting agent is obtained by treating the amide obtained by reacting equimolecular proportions of coconut oil fatty acid and trimethylene tetramine with monochloracetic acid and neutralizing with caustic soda; (2) the amides from diethylene triamine and stearic acid are treated with chloracetic acid.  The product is useful for imparting a soft touch to viscose and copper oxide ammonia artificial silk; (3) chloracetic acid is reacted with the product obtained by treating stearic acid with triethylene tetramine and the product neutralized with caustic soda.  It prevents the precipitation of calcium salts when alkali is added to hard water and disperses calcium soaps.  It also possesses a high levelling power, particularly for vat or sulphur dyestuffs, e.g. when dyeing on cotton with Indanthrene Brilliant Violet RR or Hydrone Blue RR.  The amide may be treated with two moles of ethylene oxide before reaction with chloracetic acid. The product is stable in acid baths.  30 pts. of a 50 per cent paste of the above product (or a product derived from oleic acid) 50 pts. titanium dioxide and 20 pts. water gives a composition which imparts a dull lustre to artificial silk.  A levelling agent is obtained by treating triethylene tetramine with benzyl chloride, acting on the free base with coconut oil fatty acid chloride and then treating with chloracetic acid; (4) N-octodecylpropylenediamine is treated with monochlorpropionic acid The product is soluble in acid and alkaline dye baths, and also imparts a soft touch to artificial silk; (5) the product obtained by treating propylenediamine with the bromide or sulphate of the alcohols obtained by the catalytic hydrogenation of palm kernel fat is added to sodium chloracetate solution.  Condensation occurs by heating to 90 DEG  C. and stirring; (6) sym. dimethylethylene diamine is added to aqueous formaldehyde solution and hydrocyanic acid led in till saturated.  Caustic soda is added and the nitrite saponified. The dimethylethylenediamine acetic acid is condensed in alkaline medium with coconut oil fatty acid chloride.  The product is a wetting agent and is resistant to calcium salts.  The products may be used alone or in conjunction with other wetting, dispersing or levelling agents, e.g. turkey red oils, sulphuric esters of high molecular aliphatic alcohols, sulphonated fatty acids, sulphonated mineral oils, alkylated aromatic sulphonic acids, condensation products of high molecular fatty acids and hydroxy or aminoalkylsulphonic acids or albumen degradation products, reaction products of ethylene oxide and compounds containing hydroxy, carboxylic or amino groups and sulphite cellulose waste liquor.  They may also be employed with glue, gelatine, gum arabic solvents, e.g. cyclohexanol, benzyl alcohol or carbon tetrachloride, and inorganic salts, e.g. Glauber's salt, alkali metal phosphates, waterglass and borates. The products also find application as protective colloids; as additions to spinning masses or liquids in the artificial silk industry; in the cosmetic and pharmaceutical industries; as additions to vulcanization accelerators; as superfatting agents and as protective colloids for increasing the resistance to lime in soaps; in flotation processes and as assistants for attacking plant pests.ALSO:Products stated to be useful as emulsifying, wetting, cleansing and dispersing agents in the textile, leather and paper industries are obtained by introducing low molecular radicles containing carboxylic groups or groups capable of being readily converted into carboxylic groups into amines containing at least two amino groups and at least one alkyl or aliphatic acyl radicle containing at least six carbon atoms attached to one of the nitrogen atoms. The amines may be prepared by condensing a polyamine with a compound containing the desired aliphatic radicle and the introduction of the carboxylic group may take place prior to, simultaneously with or following the condensation.  Suitable amino compounds may be prepared from amines such as ethylenediamine propylene diamine, sym. dimethylethylenediamine, diethylenetriamine, triethylenetetramine, o-, m-, and p-phenylenediamine, toluylenediamine, benzidine and diaminodiphenylamine.  The radicle containing a chain of at least six carbon atoms may be hydrocarbon radicles or may be substituted by hydroxy, amino, nitro, ester or ether groups, or by halogens, especially chlorine, and may also be interrupted by --NH--, --N alkyl--, --O--, --S--, or --CO-- bridges; amino or hydroxy group substituents may also be substituted, e.g. oleic amides of glycocoll or sarcosine, or stearic acid esters of lactic acid may be condensed with the polyamines.  Suitable amino compounds may be prepared by reacting polyamines with sulphuric acid esters of alcohols of high molecular weight or with alkyl halides, e.g. cetyl bromide, the acid sulphuric acid ester of octodecyl alcohol and derivatives of alcohol mixtures obtained by the catalytic hydrogenation of naturally occurring fats and oils.  Other alcohol derivatives are those of octyl, dodecyl, cetyl, octodecyl and oleyl alcohols, myristol, montanol, abientinol and octodecanediol. The polyamines may also be reacted with carboxylic acids of high molecular weight, their halides, anhydrides or esters, e.g. valeric acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, abietic acid, montanic acid and naphthenic acids and mixtures of such acids, especially those obtainable by saponification from coconut oil, palm kernel oil, soya bean oil, train oils or tallow or by the oxidation of paraffin hydrocarbons. The amines are preferably reacted with at least one molecular proportion of the aliphatic compounds. Suitable amino compounds may also be prepared by the catalytic hydrogenation of nitriles of amino acids containing a radicle of at least six carbon atoms or by hydrogenating mixtures of nitriles of the formula R.NH.CH2.CH2.CN (where R is the radicle contained in the fatty acids of natural oils or fats) in the presence of ammonia and hydrogen at elevated pressure and temperature, e.g. 325 DEG  C., using basic cobalt carbonate as catalyst.  The carboxylic