Patent GB-783605-A (GB)
Title: Soluble aluminium glycolates and derivatives thereof, and process for their manufacture
IPC: C09D7/63
Filed: 1953-12-18
Abstract: Aluminium glycolates or acid derivatives thereof which are soluble in organic solvents, may be produced by reacting at elevated temperature, if desired only partially, aluminium or an aluminium alcoholate of an aliphatic monohydric alcohol containing up to 6 carbon atoms with an aliphatic glycol containing 4-18 carbon atoms and which contains at least one secondary hydroxyl group unless the carbon chain is interrupted by oxygen atoms, and, if desired, reacting the resultant aluminium glycolate with up to 2 mols. of carboxylic and/or sulphinic acid for each gram-atom of aluminium. The reaction of the glycols with aluminium or an aluminium alcoholate may be carried out at a temperature in the range 80-200 DEG  C. in the presence or absence of inert solvents such as benzene, toluene, xylene, ligroin or chlorinated hydrocarbons.  When aluminium is used activating agents such as iodine, mercuric chloride, aluminium chloride and hydrochloric acid may be advantageously used. Superficially amalgamated aluminium may be used instead of aluminium. When aluminium alcoholates are used the displaced alcohol and any solvent used are distilled off during or after the addition of the glycols.  The reaction of the glycols with aluminium gives glycolates of the probable formula <FORM:0783605/IV (a)/1> in which R represents the hydrocarbon chain of the glycol.  When the glycols are reacted with an aluminium alcoholate an intermediate product of formula <FORM:0783605/IV (a)/2> in which A represents the hydrocarbon chain of the monohydric alcohol, may be found.  By reacting the final product with 2 mols. of a carboxylic or sulphinic acid a product of formula <FORM:0783605/IV (a)/3> in which S represents an acyl or sulphinic radical, is obtained. Suitable glycols are, for example, 1,3-butylene glycol, 2-ethyl-hexandiol-(1,3), 2,4-hexandiol, 2,5-hexandiol, 2-methyl-pentandiol - (2,4), 2,9 - dimethyl - decandiol - (3,8) and 1,2-octadecandiol, diglycol, 1-methyl-diglycol, 1,4-dimethyl-diglycol, 1,6-dimethyl-triglycol and 1,4,6-trimethyl-triglycerol.  Suitable alcoholates are, for example, aluminium ethylate, isopropylate, butylate and 2-ethyl-butanolate. Suitable carboxylic acids are formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, oleic acid, cyclohexane carboxylic acid, benzoic acid, salicylic acid and naphthoic acid, and suitable sulphinic acids are ethane sulphinic acid, cyclohexane sulphinic acid, benzene sulphinic acid and sulphinic acids obtained from sulphochlorides of Diesel oils, sperm oil fatty acid, naphthenic acids and resin acids.  Hydroxy carboxylic acids such as hydrogenated castor oil fatty acid and 2,3-hydroxynaphthoic acid may also be used.  The products may be stabilized against decomposition by moisture by means of aliphatic compounds containing at least one hydroxy group or a group capable of desmotropic rearrangement into an aci-form, e.g. aliphatic hydroxy-carboxylic acid esters, oximes, acetyl-acetone, acetoacetic ester, nitromethane, nitropropane, malonic acid dinitrile, malonic acid esters and butyroin.  In the examples: (a) aluminium-2,5-hexandiolate is obtained by heating aluminium with 2,5-hexandiol in the presence of iodine, mercuric chloride and aluminium chloride; (b) aluminium-2-ethyl-hexandiolate is obtained similarly when 2-ethylhexandiol-(1,3) is used as starting material; (c) aluminium isopropylate is reacted with 2,5-hexandiol to give aluminium 2,5-hexandiolate; (d) aluminium 2,5-hexandiolate is dissolved in benzene and stearin is added to give a compound of formula Al(C17H35COO)(C6H12O2); (e) aluminium isopropylate is reacted with diglycol to give a mixed alcoholate of formula Al2(C3H7O)4(C4H8O3); (f) aluminium 2-ethyl-butanolate is reacted with 1,3-butylene glycol to give Al2(C4H8O2)(C6H13O)4; (g) aluminium isopropylate is reacted with 1,12-octadecanediol to give Al2(C3H7O)4(C18H36O2); (h) aluminium isopropylate is reacted with 2,9-dimethyl-decandiol-(3,8) to give Al2(C3H7O)4(C12H24O2); (j) to the product of (g) is added commercial stearic acid to give Al2(C3H7O)3(C18H36O2) (C18H35O2); and (k) aluminium-2,5-hexandiolate is reacted with stearic acid.