Patent GB-700552-A (GB)
Title: Complex aluminum soaps as new compounds and as additives for grease compositions
Filed: 1950-08-24
Abstract: The invention comprises an aluminium soap having at least one hydroxyl anion and at least two unlike substantially hydrocarbonaceous organo-anions, one organo-anion that of an organic acid the aluminium di-soap of which has a solubility in white oil of at least 5 per cent. at 400 DEG F., and another organo-anion that of an organic acid (which may be carboxymethylcellulose) the aluminium di-soap of which acid has a solubility in white oil of less than 1 per cent at 400 DEG F.  The aluminium di-soaps of each of the organo-anions are insoluble in water.  Suitable anions of greater solubility are anions of aliphatic (saturated and unsaturated), aromatic, aralkyl, and cyclo-aliphatic carboxylic acids, and organo-acids of sulphur and/or phosphorus.  The aliphatic carboxylic acids may contain 8 - about 30, preferably 12 - 18 C atoms. Aliphatic substituents in the cyclic carboxylic acids may contain at least 4 C atoms in the aliphatic group attached to the ring.  Cyclic carboxylic acids preferably contain about 16 C atoms.  This anion may also be derived from phenols, e.g. an alkyl phenol containing at least 4 C atoms in the alkyl groups, such as cetyl phenol. Preferably, the organo-acids of sulphur and phosphorus contain at least 14, preferably at least 20 C atoms in the organo substituent. Substituents, e.g. hydroxy, amino and alkoxy groups, may be present. Representative of many specified acids are capric, lauric, palmitic; 12 - hydroxy - stearic, arachidic, oleic, hexyl-benzoic, phenyl decanoic, cetyl benzene sulphonic, cetyl thiophosphoric and naphthenic acids.  Stearic acid, hydroxystearic acids and naphthenic acids of M.Wt. above about 250 are preferred.  For preparation of the salts (see Group IV (b)).ALSO:The invention comprises aluminium soaps having at least one hydroxyl ion and at least two unlike substantially hydrocarbonaceous organo-anions, one organo-anion that of an organic acid the aluminium di-soap of which has a white ore solubility of at least 5 per cent. at 400 DEG F. and another organo-anion that of an organic acid the aluminium di-soap of which has white oil solubility of less than 1 per cent. at 400 DEG F. The aluminium di-soaps of each of the organo anions are insoluble in water.  Suitable anions of greater solubility are anions of aliphatic (saturated and unsaturated), aromatic, aralkyl, and cyclo-aliphatic carboxylic acids, and organo-acids of sulphur and/or phosphorus.  The aliphatic carboxylic acids may contain 8-about 30, preferably 12-18 carbon atoms.  Aliphatic substituents in the cyclic carboxylic acids may contain at least 4 C atoms in the aliphatic group attached to the ring.  Cyclic carboxylic acids preferably contain about 16 carbon atoms.  This anion may also be derived from phenols, e.g. an alkyl phenol containing at least 4 C atoms in the alkyl groups, e.g. cetyl phenol.  Preferably the organo-acids of sulphur and phosphorus contain at least 14, preferably at least 20 C atoms in the organo substituent. Substituents, e.g. hydroxy, amino and alkoxy groups may be present.  Representative of specified acids are capric, lauric, palmitic, 12-hydroxy stearic, arachidic, oleic, hexyl, benzoic, phenyl decanoic acid, cetyl benzene sulphonic, cetyl thiophosphoric and naphthenic acids.  Stearic acid, hydroxy stearic acids and naphthenic acids of M Wt. above about 250 are preferred.  Suitable anions of lesser solubility are those of aliphatic (saturated and unsaturated), phenyl, phenyl-alkyl, alkyl-phenyl, and cycloaliphatic mono- and polycarboxylic acids. Acids with up to 2 carboxy groups are preferred, especially monocarboxylic acids.  Aliphatic mono-carboxylic acids may contain 4-7 C atoms.  When the acid contains 2 carboxy groups it has at least 2, preferably 8-11 C atoms or up to 20 C atoms.  The alkyl groups of the phenyl-alkyl and alkyl-phenyl acids contain up to 4 non-aromatic and have a total of not more than 10, preferably 8, C atoms.  Representative of specified acids are benzoic, ethyl benzoic, phenyl propionic, oxalic, malonic, adipic, phthalic, salicylic and polyacrylic acids and carboxymethylcellulose. Benzoic, azelaic and toluic acids are preferred.  Inorganic acids of phosphorus, boron and silicon, e.g. phosphoric, boric and silicic acids, and phenols containing no more than 3 C atoms in an alkyl substituent may also provide less soluble ions. Preferably anions of aliphatic and aromatic carboxylic acids are used, e.g. aluminium benzoate stearate and toluate stearate.  The soaps are used in greases the ratio of the anions of varying solubilities then ranging from 1 : 5 to 5 : 1, preferably 1 : 3 to 3 : 1.  This ratio may vary from 1 : 10 to 10 : 1 for other uses. At least 1, preferably about 1 to about 1 - 5, free hydroxyl groups must be present per atom of A1.  Complex soaps such as the benzoate, stearate, caprylate may be made.  Representative of specified soaps are aluminium benzoate oleate, benzoate 12 - hydroxystearate, benzoate naphthenate, benzoate hydrogenated resin, benzoate dodecyl benzene sulphonate, phosphate benzoate stearate the azelate stearate toluate stearate and benzoate stearate are preferred especially the last.  They are made by co-precipitation.  Thus aqueous solutions of the water-soluble (e.g. sodium) soaps are admixed with an aqueous solution of an aluminium salt or a fatty acid such as stearic acid, may be added to a mineral oil solution of an aluminium alcoholate, e.g. the butoxide.  In Examples (1) 13.5 pts. commercial stearic and 10 pts. azelaic acids are dissolved in water and added to an aqueous solution of 24.9 pts. of aluminium sulphate octadecahydrate and aluminium azelate stearate precipitated; (2) 28.6 pts. of toluic and 27 pts. of commercial stearic acids and 18 pts. of sodium hydroxide are dissolved in water and added to an aqueous solution of 50 pts. of aluminium sulphate hydrate to precipitate aluminium toluate stearate; (3) 12.2 pts. of benzoic and 27.1 pts. of commercial stearic acids and 16.8 pts. of potassium hydroxide are dissolved in water and added to an aqueous solution of 33.3 pts. of aluminium sulphate hydrate to precipitate aluminium benzoate stearate; (4) 28.8 pts. sodium benzoate, 48 pts. 12-hydroxy stearic acid and 13.6 pts. sodium hydroxide are dissolved in water and added to an aqueous solution of 68 pts. aluminium nitrate to precipitate aluminium benzoate hydroxy-stearate; (5) 15.4 pts. sodium benzoate, 31 pts. naphthenic acid and 8 pts. sodium hydroxide are dissolved in water and added to an aqueous solution of 37.5 pts. aluminium nitrate to precipitate aluminium benzoate naphthenate; (6) 14.4 pts. sodium benzoate, 74.6 pts. of sodium alkyl benzene sulphonate (70 per cent. sodium di-docecyl benzenesulphonate, 30 per cent. unsulphonated di-dodecyl benzene) and 4 pts. of sodium hydroxide were dissolved in water and added to an aqueous solution of 33.3 pts. aluminium nitrate to precipitate the aluminium benzoate alkyl benzene sulphonate; (7) 8.2 pts. benzoic acid, 18.0 pts. commercial stearic acid, 8.4 pts. trisodium phosphate and 13 pts. potassium hydroxide are dissolved in water and added to an aqueous solution of 40 pts. aluminium to precipitate aluminium benzoate phosphate stearate and (16) 7 pts. toluic acid, 55 pts. sodium alkyl benzene sulphonate (43 per cent. sodium didodecyl benzene sulphonate, 57 per cent. unsulphonated di-dodecyl benzene) and 5.6 pts. potassium hydroxide are dissolved in aqueous ethanol and added to an aqueous solution of 19 pts. aluminium nitrate to precipitate aluminium toluate di-dodecyl benzene sulphonate.ALSO:The invention comprises aluminium soaps which are used in lubricating grease compositions and paints and which have at least one hydroxyl anion and at least two unlike substantially hydrocarbonaceous organo-anions, one organo-anion that of an organic acid the aluminium di-soap of which has a solubility in white oil of at least 5 per cent. at 400 DEG F., and another organo-anion that of an organic acid the aluminium di-soap of which has a solubility in white oil of less than 1 per cent. at 400 DEG  F.  The aluminium di-soaps of each of the organo-anions are insoluble in water. Suitable anions of greater solubility are anions of aliphatic (saturated and unsaturated, aromatic, aralkyl, and cyclo-aliphatic carboxylic acids, and organo-acids of sulphur and/or phosphorus.  The aliphatic carboxylic acids may contain 8-about 30, preferably 12-18 C atoms.  Aliphatic substituents in the cyclic carboxylic acids may contain at least 4 C atoms in the aliphatic group attached to the ring.  Cyclic carboxylic acids preferably contain about 16 C atoms. This anion may be derived from phenols, e.g. an alkyl phenol containing at least 4 C atoms in the alkyl groups, e.g. cetyl phenol. Preferably the organo-acids of sulphur and phosphorus contain at least 14, preferably at least 20 C atoms in the organo substituent. Substituents, e.g. hydroxy, amino and alkoxy groups may be present. Representative of many specified acids are capric, lauric, palmitic, 12-hydroxy-stearic, arachidic, oleic, p  hexyl-benzoic, phenyl-decanoic, cetyl benzene sulphonic, cetyl thiophosphoric and naphthenic acids.  Stearic acid, hydroxy-stearic acids and naphthenic acids of M.Wt. above about 250 are preferred.  Suitable anions of lesser solubility are those of aliphatic (saturated and unsaturated), phenyl, phenyl-alkyl, alkyl-phenyl, and cycloaliphatic mono-and poly-carboxylic acids. Acids with up to 2 carboxy groups are preferred, especially mono-carboxylic acids.  Aliphatic mono-carboxylic acids may contain 4-7 C atoms.  When the acid contains 2 carboxy groups it has at least 2, preferably 8-11, C atoms or up to 20 C atoms. The alkyl groups of the phenyl-alkyl and alkyl-phenyl acids contain up to 4 non-aromatic and have a total of not more than 10, preferably 8, C atoms.  Representative of specified acids are benzoic, ethyl benzoic, phenyl propionic, oxalic, mal