Patent GB-761536-A (GB)
Title: The production of synthetic drying oils
IPC: C09F5/00
Filed: 1952-07-11
Abstract: Aluminium containing synthetic drying oils are prepared by heating one or more aluminium alcoholates dissolved in an inert solvent with the enolic form of a keto-enol tautomeric compound thereby forming a solution of aluminium enol compounds and condensing this solution with a solution in an inert solvent of one or more saturated or unsaturated aliphatic carboxylic acids having at least 8 carbon atoms in the molecule and/or carbocyclic carboxylic acids having aliphatic side chains, in the absence of water or substances which during the condensation generate water, the solutions being used in such proportions that the amount of aluminium-enol compound is substantially smaller by weight than that of the acid present.  In the first reaction, at least part of the alcohol combined in the alcoholate is replaced by the enolic compound.  Specified keto-enol compounds include acetone, acetoacetic ester, malonic acid diethyl ester and laevulinic acid methyl ester.  The specified acid reactants are C10-20 fatty acids and tall oil or its carboxylic acid components.  The condensation reaction may be effected with or without the aid of heat.  The solutions of the invention are film-forming and may be used for lacquers, paints and varnishes and for the impregnation of textile fabrics, paper and other fibrous material.  According to examples: (1) a solution of aluminium-enol compounds is formed by preparing a solution of aluminium n-butanolate in benzine (see Group IV (b)) and refluxing this solution with a mixture of acetone and acetoacetic ethyl ester; (2) an acid solution is formed by dissolving unrefined tall oil in benzine, if desired with addition of beeswax; (3) a drying oil is then formed by dissolving a little iron hydroxide in 7 vols. of the acid solution of (2) which is then stirred into 1 vol. of the enolate solution of (1); a small amount of benzine-soluble alkyd resin is then dissolved in the resulting oil to give a lacquer; (4) another drying oil is obtained by refluxing 1 vol. of the enolate solution of (1) with 1 vol. of the acid solution used in (3), cooling the product and adding a further 6 vols. of the acid solution. Aluminium iso-amylate is also specified as a reagent.  Reference has been directed by the Comptroller to Specifications 718,283 and 718,359.ALSO:Aluminium-containing organic compounds are prepared by heating one or more aluminium alcoholates dissolved in an inert solvent, with the enolic form of a keto-enol tautomeric compound thereby forming a solution of aluminium-enol compounds and condensing this solution with a solution in an inert solvent of one or more saturated or unsaturated aliphatic carboxylic acids having at least 8 carbon atoms in the molecule and/or carbocyclic carboxylic acids having aliphatic side chains, in the absence of water and substances which during the condensation generate water, the solutions being used in such proportions that the amount of the enolic aluminium compound is substantially smaller by weight than that of the acid present.  In the reaction of the aluminium alcoholate with the enol-compound, at least part of the alcohol combined in the alcoholate is declared by the enol-compound. Specified keto-enol compounds are acetone, acetoacetic ester, malonic acid di-ethyl ester and laevulinic acid methyl ester; reference is also made to the keto-enol compounds included in these classes of compounds: diketones, diketocarboxylic acid esters, dicarboxylic acid esters, b -keto-esters and keto-dialdehydes, the enol-forming carbonyl groups preferably being in the b -position to the next functional groups. The specified acid-reactants are fatty acids having between 10 and 20 carbon atoms, tall oil and the carboxylic acid contained therein; these acids may be used dissolved in a hydrocarbon solvent.  The condensation may be effected with or without the aid of heat.  The solutions of the invention are film-forming drying oils and may be used for lacquers, paints and varnishes (see Group III), and for the impregnation of textile fabrics, paper and other fibrous material. According to examples: (1) a solution of aluminium alcoholate is prepared by heating aluminium chips with n-butanol in presence of mercuric chloride as catalyst to 100 DEG  C. and then adding a mixture of additional butanol with benzine at the same temperature and thereafter distilling off unchanged butanol; (2) the resulting solution of aluminium alcoholate is refluxed with a mixture of acetone and acetoacetic ethyl ester yielding, after removal of unchanged acetone, a solution containing aluminium in the form of alcoholate, aceto acetic ester enolate, acetone enolate and the enolates of condensation products; (3) an acid solution is prepared by dissolving unrefined tall oil, if desired together with a minor amount of beeswax, in benzine; (4) a ready drying oil is prepared by dissolving a small amount of iron hydroxide in 7 volumes of the enolate solution of (3) which is then stirred into a volume of the enolate solution of (2); (5) a drying oil yielding more elastic films than the oil of (4) is prepared by refluxing 1 volume of the enolate solution of (3) with 1 volume of the enolate solution used in (4), then cooling and adding a further 6 volumes of the enolate solution. Aluminium iso-amylate is also specified as a reagent.  Reference has been directed by the Comptroller to Specifications 718,283 and 718,359, [Group IV (a)].ALSO:Aluminium containing drying oils are prepared by heating one or more aluminium alcoholates dissolved in an inert solvent, with the enolic form of a keto - enol tautomeric compound thereby forming a solution of aluminium - enol compounds and condensing this solution with a solution in an inert solvent of one or more saturated or unsaturated aliphatic carboxylic acids having at least 8 carbon atoms in the molecule and/or carbo cyclic carboxylic acids having aliphatic side chains, in the absence of water or substances which generate water during the condensation, the solutions being used in such proportions that the amount of aluminium - enol compound is substantially smaller by weight than that of the acid present.  Specified keto - enol compounds include acetone, aceto acetic ester, laevulinic acid methyl ester and malonic acid diethyl ester and specified acid reactants are C10-20 fatty acids and tall oil and its carboxylic acid components.  The condensation reaction may be effected with or without the aid of heat.  The solutions obtained may be used for lacquers, paints and varnishes and for the impregnation of textile fabrics, paper and other fibrous material. According to examples: (1) a solution of aluminium - enol compounds is made by forming a benzine solution of aluminium n - butylate (see Group IV(b)) and refluxing the solution with a mixture of acetone and aceto acetic ethyl ester; (2) an acid solution is formed by dissolving tall oil in benzine, if desired together with some beeswax; (3) a drying oil is obtained by dissolving a little iron hydroxide in 7 vols. of the acid solution which is then stirred into 1 vol. of the enolate solution of (1); some alkyd resin is finally dissolved in the resulting oil to give a lacquer; (4) equal volumes of the acid solution used in (3) and the enolate solution are refluxed and then a further 6 vols. of the acid solution are added to give an oil providing elastic films on drying.  Reference has been directed by the Comptroller to Specifications 718,283 and 718,359 [both in Group IV(a)].