Patent GB-790624-A (GB)
Title: Manufacture of organic aluminium compounds
IPC: D06M13/188
Filed: 1954-05-26
Abstract: Organic aluminium compounds are obtained by reacting an organic aluminium compound containing one or more organic radicals bound in alcoholate- or phenolate-like manner, there being a total of up to one equivalent of the said organic radical or radicals bound in an alcoholate- or phenolate-like manner per equivalent of aluminium, with a salt of aluminium with a monobasic organic compound of acid nature.  The process may be carried out in the presence or absence of an inert organic solvent and, if desired, part of each of the components may be reacted at a low temperature and then heated to a higher temperature, e.g. 50-200 DEG  C. with the addition of the remainder of the reactants, or the entire reaction may be carried out at the higher temperature.  The products are oily, semi-solid, waxy, or resinous in character and may be crosslinked or straight-chained according to the temperatures and the starting materials employed. Particularly valuable products are obtained by reacting 1 mol. of an aluminium alcoholate with about 1/10 to 1 mol. of a tertiary-aluminium salt of a fatty acid containing 10 to 30 carbon atoms or with 1/3 to 2 mols. of a mixed tertiary-aluminium salt containing about 0.5 to 1.5 mols. of difficultly volatile fatty acid radicals of high molecular weight and 1.5 to 2.5 mols. of easily volatile fatty acid radicals of low molecular weight or with about 1/3 to about 2 mols. of basic aluminium salts of C10-C30 fatty acids containing about 1 to 2 fatty acid radicals per aluminium atom, or with salt-like reaction products of aluminium alcoholates with 1 to 2 mols. of monobasic carboxylic acids.  Specified aluminium alcoholates include aluminium ethylate, propylate, isopropylate, butylate, isobutylate, amylate, hexylate, octylate, 2-ethyl-butylate and 2-ethyl-hexylate, mixtures thereof, mixed aluminium alcoholates, alpha-aluminium ethyl ate, alcoholates of aliphatic keto-enol compounds, e.g. aluminium tri-acetoacetic ester and aluminium triacetyl acetone, and aluminium compounds containing per equivalent of aluminium less than 1 equivalent of organic radicals bound in an alcoholate or phenolate-like manner.  Such organic radicals may be aliphatic, alicyclic, aromatic, araliphatic, or heterocyclic, which may be substituted by nonacid groups, e.g. by keto, amino, or ester groups, or by halogen atoms, e.g. chlorine, or the carbon chains of which may be interrupted by hetero atoms such as oxygen, sulphur, or nitrogen.  Specified radicals are methyl, ethyl, chloroethyl, dimethylamino-ethyl, isopropyl, butyl, octyl, octadecyl, cyclohexyl, phenyl, naphthyl, benzyl, phenylethyl, and furfurylmethyl.  The remaining valencies of the aluminium may be satisfied by oxygen linked in chain fashion to further aluminium atoms, or by halogen atoms, hydroxy groups, or acyloxy groups, e.g. acetoxy.  Such compounds include those obtained by thermal or hydrolytic treatment of normal aluminium alcoholates with splitting off of part of the alkoxy groups and usually with the linking together of aluminium atoms in chain fashion through oxygen atoms.  Various aluminium alcoholates of this type are specified including the compounds Al2(OC2H5)4O, Al4(OC2H5)6O3, Al(OH)(C2H5O)2 and the aluminium dihydroxycyclohexanolate obtained by heating aluminium cyclohexanolate at 275 DEG  C. Aluminium alcoholates containing halogen atoms are also mentioned including those of the formula AlHal(OR)2 and Al2Hal3(OR)3, wherein R is a C1-C4 aliphatic radical, e.g. AlCl(OC2H5)2 and those alcoholates obtainable by reacting a theoretically insufficient quantity of an alcohol with an aluminium halide in the presence of ammonia or an amine or by reacting aluminium halides with alkylene oxides, e.g. the compound AlCl(OC2H4Cl)2.  There may also be used carboxylates of complex aluminium alcoholates of the formula AlSx(OR)yOz wherein R is alkyl, S is acyloxy and the sum of x, y and z is 2.5 to 3, e.g. the compound Al(OC2H5)(CH3COO)O0,5.  The alcoholates may be used in the form of their addition products with carbon dioxide or sulphur dioxide, or there may be used aluminium alcoholates which have been stabilized by treatment with volatile organic compounds capable of forming complex compounds with the alcoholates, said volatile organic compounds being aliphatic hydroxycarboxylic acid esters, e.g. tartaric acid diethyl ester, oximes, e.g. acetoneor acetaldehyde-oxime, compounds containing a group capable of desmotropic rearrangement to the enolic or aci-form, e.g. acetyl acetone, ethyl acetoacetate, malonic acid dinitrile, nitromethane and nitropropane; compounds containing a reactive methylene group, e.g. malonic acid esters; hydroxy-oxo compounds such as butyroin and aliphatic nitriles such as acetonitrile.  Specified types of monobasic organic compounds of acid character are monocarboxylic acids, sulphinic acids, sulphonic acids, monoesters of sulphuric acid, sulphamic acids, monobasic phosphonic acids, monobasic phosphoric acid esters, and diacylamides containing carboxyl and/or sulphonyl residues, and mixtures thereof.  These compounds may be aliphatic, alicyclic, aromatic, or heterocyclic and may contain inert substituents, e.g. halogen atoms, or hydroxy, mercapto, ether, thioether, ester, carboxylic acid amide, or urea groups and their carbon chains may be interrupted by hetero atoms such as oxygen, nitrogen or sulphur atoms.  Several acidic substances are mentioned, including formic, acetic, and stearic acids, resin acids, e.g. abietic acid or colophony, acrylic, crotonic, methoxyacetic, chloracetic, thioglycollic, and thiolactic acids, malonic acid monoethyl ester, the semi-amide of malonic acid, hydantoic acid, glycollic acid, lactic acid, maleic acid monoethyl ester, propyl sulphonamido acetic acid, cyclohexane carboxylic acid, hexahydrosalicylic acid, benzoic acid, orthochlorobenzoic acid, alpha-naphthoic acid, alphanaphthoxy-acetic acid, cinnamic acid, phthalic acid monoethyl ester, salicylic acid, methoxy benzoic acid, phenoxy acetic acid, 2 : 4-dichloro phenoxy acetic acid, the semi-amide of heterocyclic acids including pyromucic acid, nicotinic acid, thiophene-alpha-carboxylic acid, pyrrolealpha-carboxylic acid and beta indolyl acetic acid.  Other monobasic acidic organic compounds specified with typical examples of such compounds are sulphinic acids, e.g. ethane, cyclohexane, and benzene sulphinic acids, sulphonic acids, e.g. propane-, cyclohexane-, benzene-, toluene, and naphthalene sulphonic acids, hydroxyethane-, phenol-, and naphthol sulphonic acids, 2-hydroxy-carbazole-7-sulphonic acid, and thiophene-alpha sulphonic acid; amides and imides of the sulphonic acids, e.g. benzene and dodecane sulphonamides and sulphonimides; monosulphuric acid esters, e.g. the monoethyl, monobenzyl, and monophenyl esters, sulphamic acids, e.g. ethyl-, cyclohexyl-and phenyl-sulphamic acids; monobasic cyclic imides, e.g. benzoic acid sulphonimide and ethyl barbituric acid; monoesters of phosphonic acids, e.g. the ethyl ester of hexane- or phenylphosphonic acid; and monobasic phosphoric acid esters, e.g. the diethyl, dibenzyl or dicyclohexyl ester of phosphoric acid. The reaction products may be stabilized against moisture by treating with a volatile organic compound as defined above which is capable of forming a complex compound with the products and the volatile organic compound may be added before, during, or after the reaction.  In examples: (1) a soft resin is obtained by heating aluminium diacetate monostearate with aluminium isopropylate under reflux in the presence of xylene, similar products are obtained when the aluminium salt starting material is derived from sperm oil fatty acids instead of stearic acid and propionic acid instead of acetic acid; (2) basic aluminium stearate obtained by reacting aluminium sulphate with sodium stearate in aqueous medium and of the approximate composition Al(C18H35O2)1,6OH1,4 is reacted with aluminium isopropylate (or ethylate) as in (1) to form a viscous oil which forms a waxy solid on cooling; (3) and (4) a soft resin or waxy product is formed by heating aluminium isopropylate with aluminium tristearate or by heating alminium butylate with aluminium tribenzoate or aluminium tri-(12-hydroxystearate) and allowing the product to cool; (5) aluminium monoisopropylate dibenzoate (obtained by reacting aluminium isopropylate with benzoic acid) is heated with aluminium isopropylate at 200 DEG  C. to form a viscous oil which on cooling solidifies to a wax-like product; (6) aluminium monoisopropylate-distearate (obtained by reacting aluminium isopropylate with stearic acid) is heated with aluminium isopropylate to form an oil; (7) aluminium isobutylate-di-benzene sulphonate (obtained by heating aluminium triisobutylate, isobutyl alcohol and benzene sulphonic acid) is heated with aluminium triisobutylate to yield an oil which solidifies on cooling to form a viscous resin; (8) aluminium isobutylate is heated with the tertiary aluminium salt of di-dodecyl phosphoric acid ester, the latter being obtained by heating aluminium isobutylate, isobutyl alcohol, and didodecyl phosphate) to yield a viscous oil which solidifies to a soft resin on cooling; (9) aluminium triisobutylate is heated with aluminium-monoisobutylate-di-dodecylsulphinate to yield a viscous oil which solidifies to a soft resin on cooling.  The products are stated to be useful in the lubricant, fuel, and lacquer or varnish industries and are especially suitable for imparting water-repellent properties to fibrous materials (see Group VIII). Specification 772,480 is referred to.ALSO:Organic aluminium compounds are obtained by reacting an organic aluminium compound containing one or more organic radicals bound in alcoholate- or phenolate-like manner, there being a total of up to one equivalent of the said organic radical or radicals per equivalent of aluminium, with a salt of aluminium with a monobasic organic