Patent GB-774119-A (GB)
Title: Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof
IPC: C07F1/00
Filed: 1954-03-09
Abstract: Complex alkoxy metal salts are prepared by heating an oil-soluble organic acid with an alcoholate of a metal of Group I or II derived from a monohydroxy saturated aliphatic alcohol having from 1 to 20 carbon atoms in a proportion such as to supply to the reaction between 2 and 6 equivalents of metal alcoholate based on the equivalent of the acid-hydrogen content of the organic acid.  The complex salts derived from organic acids other than sulphonic acids are novel.  The reaction is conducted by heating together a solution of the organic acid in a solvent such as a mineral lubricating oil, light naphtha, kerosene, toluene or xylene, and an alcohol solution of the metal alcoholate at 50-200 DEG  C., preferably 120-175 DEG C., for one to six hours, the temperature used being sufficient to effect the removal of the excess alcohol without removing the solvent.  The organic acids include aliphatic carboxylic acids having 10-24 carbon atoms such as decanoic, lauric, stearic, oleic, linoleic and arachidic acids; the aromatic and naphthenic carboxylic acids having an aliphatic substituent containing 10-24 carbon atoms, such as alkyl-substituted benzoic, salicylic and phthalic acids, and abietic acid; phenolic acids, such as alkyl-substituted phenols, naphthols, resorcinols, catechols, hydroquinols and pyrogallols wherein the alkyl portion contains at least 10 carbon atoms, e.g. wax phenol, dinonyl catechol, and hexadecyl hydroquinone; organic phosphorus-containing acids, such as alkyl, alkaryl and aralkyl-substituted phosphoric, phosphonic and phosphinic acids, e.g. dodecyl phenyl phosphoric acid, octadecyl phosphonic acid and diamyl phosphinic acid; organic sulphur-containing acids, such as alkyl, alkaryl and aralkyl-substituted sulphonic acids and alkyl sulphuric acids, e.g. dodecyl phenyl sulphonic acid, wax benzene sulphonic acid, petroleum sulphonic acid and octadecyl sulphuric acid; organic phosphorus- and sulphur-containing acids, such as alkyl, alkaryl and aralkyl-substituted thiophosphoric, thiophosphonic and thiophosphinic acids, e.g. wax phenyl dithiophosphoric acid, didodecyl thiophosphonic acid and dihexadecyl phosphinic acid.  The metal alcoholates used include those of potassium, sodium, calcium, strontium, barium, zinc and magnesium, such as sodium methylate, calcium methylate, barium methylate, magnesium methylate, calcium butylate, potassium caprylate, barium decylate, calcium dodecylate, magnesium tetradecylate, zinc hexadecylate, and magnesium octadecylate. Detailed examples are given of the preparation of complex magnesium methoxy salts of tall oil acid, a complex calcium methoxy salt of tall oil acid, complex zinc methoxy salts, a complex barium methoxy salt and a complex magnesium methoxy salt of naphthenic acid, a complex magnesium methoxy salt of wax phenol, a complex sodium butoxy salt of wax phenol, a complex magnesium methoxy salt of wax-b -naphthol, a complex barium methoxy salt of petroleum sulphonic acid, a complex barium methoxy, complex calcium methoxy, complex sodium methoxy, complex magnesium methoxy, and complex potassium butoxy salts of wax benzene sulphonic acids, a complex magnesium methoxy salt of dodecylphenyl phosphoric acid and a complex magnesium methoxy salt of wax phenyl dithiophosphoric acid.  The complex salts may be used as additives for petroleum oil fractions (see Group III) and in the manufacture of detergents and dispersants. The preparation of the following intermediates is described in detail:  Wax phenol.  A C20-C24 paraffin wax is chlorinated and then reacted with phenol in the presence of aluminium chloride. Wax-benzene sulphonic acid.  A C24 paraffin wax is chlorinated then reacted with benzene in the presence of aluminium chloride to form a wax-benzene which is then sulphonated with oleum and the product is blended with a mineral oil.  Dodecylphenyl phosphoric acid. Dodecylphenol is heated with phosphorus pentoxide at 150 DEG  C. for 3 hours.  Wax phenyl dithiophosphoric acid.  An oil blend containing a wax phenol and a mineral oil is stirred with phosphorus pentasulphide at 170 DEG  C. for 5 hours.ALSO:Mineral oil compositions contain a minor proportion of a complex alkoxy metal salt prepared by heating an oil-soluble organic acid with an alcoholate of a metal of Group I or II derived from a monohydroxy saturated aliphatic alcohol having 1 to 20 carbon atoms, in a proportion such as to supply to the reaction between 2 and 6 equivalents of metal alcoholate based on the equivalent of the acid hydrogen of the organic acid.  The mineral oil may be a lubricating oil, a fuel oil or a gasoline. Suitable organic acids are aliphatic carboxylic acids having 10-24 carbon atoms; aromatic or naphthenic carboxylic acids having an aliphatic substituent containing 10-24 carbon atoms; phenolic acids, such as alkyl-substituted phenols, naphthols, resorcinols, catechols, hydroquinols and pyrogallols wherein the alkyl position contains at least 10 carbon atoms; organic phosphorus-containing acids, such as alkyl, alkaryl-and aralkyl-substituted phosphoric, phosphonic and phosphinic acids; organic sulphur-containing acids such as alkyl, alkaryl- and aralkyl-substituted sulphonic acids and alkyl sulphuric acids; and organic phosphorus-and sulphur-containing acids, such as alkyl-, alkaryl- and aralkyl-substituted thiophosphoric, thiophosphonic and thiophosphinic acids.  The metal may be sodium, potassium, calcium, strontium, barium, magnesium or zinc.  Detailed examples describe the preparation of blends of kerosene or solvent-refined mineral oil containing magnesium methoxy salts or calcium methoxy salts of tall oil; zinc methoxy salts, barium methoxy salts, or magnesium methoxy salts of naphthenic acid; a magnesium methoxy salt or sodium butoxy salt of wax phenol; a magnesium methoxy salt of waxb -naphthol; a barium methoxy salt of petroleum sulphonic acid; a barium methoxy sodium methoxy salt, magnesium methoxy salt or potassium butoxy salt of wax-benzene sulphonic acid; a magnesium methoxy salt of dodecylphenyl phosphoric acid; or a magnesium methoxy salt of wax phenyl dithiophosphoric acid. Concentrates containing 20 to 50 per cent of complex alkoxy metal salt thus prepared are effective in concentrates ranging from 0.01 per cent as anti-rust agents in gasoline, and in concentrations ranging from 0.5 to 2.0 per cent as antioxidants and detergents in lubricating oils.  The mineral oils may also contain viscosity index improvers, extreme pressure agents, and pour point depressants.