Patent GB-809309-A (GB)
Title: Improvements relating to aluminium alcoholate derivatives
IPC: C09D7/63
Filed: 1956-03-21
Abstract: Hydroxy-alkoxy- and hydroxy-aryloxy-aluminium acylates are converted into condensation products by heating, for example, above about 160 DEG  C.  The acylate radical may be derived from any monocarboxylic acid, e.g. stearic acid, oleic acid, naphthenic acids, hexahydrobenzoic acid, benzoic acid, phenyl acetic acid, abietic acid, other rosin acids or from mixtures of such acids. The hydroxyalkoxy and hydroxyaryloxy groups may be derived from normal, secondary or iso-alcohols or from phenols.  The starting materials are obtained by heating an aluminium alcoholate, phenolate or mixed alcoholate-phenolate with a carboxylic acid or its anhydride in approximately equimolecular proportions distilling off approximately one mol. of alcohol or phenol per mol. of alcoholate or phenolate and further heating in the presence of water until a further mol. of alcohol or phenol has distilled off.  Alternatively, a glycol, e.g. butane diol, may be used instead of water.  The polycondensates obtained may be used in coatings or plastics.  In the examples: (a) hydroxy-isopropopoxy aluminium oleate is heated at 200 DEG  C. for 30 minutes to give a viscous oil having wetting and suspending properties for pigments; (b) a condensation product is obtained by heating hydroxy - isopropoxy - aluminium benzoate to 200 DEG  C.; (c) hydroxy-isopropoxy-aluminium oleate is heated to 200 DEG  C. to give a condensation product; (d) the hydroxy-isopropoxyaluminium acylate obtained from linseed fatty acids is heated to 180 DEG  C. to give a viscous oil which dries in the air after the addition of 1 per cent paint drier to give a hard high water resistant glossy coating; (e) hydroxy-isopropoxy-aluminium stearate is heated to 210 DEG  C. to give a condensate; (f) the product obtained by adding cresol, water and oleic acid to aluminium isopropoxide is heated to give a viscous condensate which is soluble in mineral spirits and dries in the air to give a hard glossy film; (g) a compound obtained by reacting together aluminium isopropoxide, stearic acid and octylene glycol is heated to 240 DEG  C. to give a clear resinous product; and (h) the hydroxy isopropoxy-aluminium acylate of linseed fatty acids is heated to give a clear viscous oil which dries rapidly by oxidation after the addition of paint driers.ALSO:The invention comprises hydroxy alkoxy- and hydroxyaryloxy-aluminium acylates.  They may be prepared by heating an aluminium alcoholate, phenolate or mixed alcoholate-phenolate with a monocarboxylic acid, or its anhydride, in approximately equimolecular proportions and distilling off approximately one mol. of alcohol or phenol per mol. of alcoholate or phenolate, and further heating in the presence of water until approximately a further mol. of alcohol or phenol has distilled off and an hydroxyalkoxy- or hydroxy aryloxy-aluminium acylate is formed. The preferred starting material is aluminium isopropoxide but other suitable materials are, for example, the ethoxide, the n-propoxide, the normal, iso- and sec.-butoxides and pentoxides, the phenoxides and cresoxides of aluminium.  The acid reactant may be any monocarboxylic acid, e.g. oleic acid, formic to stearic acids, naphthenic acids, hexahydrobenzoic acid, benzoic acid, phenylacetic acid, abietic acid or mixtures of such acids.  It is desirable to carry out the reaction at 80-100 DEG  C. as long as the hydroxyhydrocarbon formed distils off easily and then to raise the temperature.  If the hydroxy alkoxy- or hydroxyaryloxy-aluminium acylate is further heated to, for example, a temperature above 160 DEG  C. a condensation product is obtained.  Instead of water a glycol may be used coupling the aluminium atoms together.  In the examples: (a) aluminium isopropoxide is dissolved in mineral spirits, the solution is mixed with oleic acid and the temperature is raised to 60-70 DEG  C.; the mixture is slowly heated to 100 DEG  C. and the aluminium di-iso propoxy oleate obtained is cooled; water and isopropanol are added, the mixture is heated to 150 DEG  C. and hydroxy-isopropoxy aluminium oleate is obtained; if this compound is further heated to 200 DEG  C. a condensation product is obtained; (b) hydroxy-isopropoxy-aluminium stearate is obtained by a similar process to that of (a) using stearic acid instead of oleic acid; (c) propoxy-phenoxy aluminium octoate is obtained by treating aluminium isopropoxide with phenol and treating the product with octoic acid; it is heated with water to 150 DEG  C. to give hydroxy-phenoxy aluminium octoate; (d) aluminium isopropylate is mixed with benzoic acid and heated to 150 DEG  C. to give di-isopropoxy-aluminium benzoate which is mixed with water and heated to 200 DEG  C. to give a condensation product; (e) p-tert.-amyl-phenoxy aluminium di-isopropoxide is prepared by heating aluminium isopropoxide with p-tert.-amylphenol; it is heated to 100 DEG  C. with acetic acid to give isopropoxy-amylphenoxy aluminium acetate which is treated at 100 DEG  C. with water to give a gelatinous precipitate which is heated in vacuo to give hydroxy-amylphenoxy-aluminium acetate; (f) aluminium isopropoxide is dissolved in xylene and heated to 100 DEG  C.; oleic acid and water are added; the mixture is heated to 130 DEG  C. and the temperature is then raised to 200 DEG  C. to give a viscous oil of formula H(OAIX)3OR in which R is the alcohol residue and X is the acid residue; (g) aluminium isopropoxide is dissolved in xylene and heated to 100 DEG  C.; linseed fatty acids dissolved in water are added and the temperature is raised to 180 DEG  C. to give a clear viscous oil; (h) aluminium isopropoxide is dissolved in xylene and heated to 120 DEG  C.; stearic acid and water are added and the temperature is raised first to 135 DEG  C. and then to 210 DEG  C.; (j) a solution of aluminium isopropoxide in xylene is mixed at 120 DEG  C. with a solution of oleic acid, cresol and water to give a viscous liquid; (k) a solution of aluminium isopropoxide in xylene is added at 120 DEG  C. to a solution of stearic acid and octylene glycol; the temperature is raised to 140 DEG  C. and more stearic acid is added; the mixture is then heated to 240 DEG  C. to give a resinous product; and (1) a solution of linseed acids and water in isopropanol is added to a solution of aluminium isopropoxide in xylene at 120 DEG  C.; the temperature is raised to 150 DEG  C. and a clear viscous oil is obtained.