Patent GB-795657-A (GB)
Title: Basic polyvalent metal salts of organic acids
Inventor: HARTLEY JAMES
IPC: F02B3/06
Filed: 1955-06-07
Abstract: Polyvalent metal basic salts of organic acids are prepared in oil solution by treating a solution of a neutral or basic salt of the organic acid and an alkali metal carbonate in the oil, which may be any water-immiscible liquid, with an aqueous solution of a water-soluble polyvalent metal salt and removing the water from the resulting mixture.  The neutral or basic salt used is preferably an alkali metal salt.  The oil solution may be prepared by dissolving in the oil the organic acid or salt thereof, preferably its alkali metal salt, adding an aqueous solution of the alkali metal carbonate in amounts sufficient to ensure excess alkali metal carbonate and then distilling off the water. Reaction of the oil solution with the aqueous polyvalent metal salt solution may be effected at between 60 DEG  and 160 DEG  C.  The product contains polyvalent metal in the form of its carbonate; preferably the oil solution used also contains alkali metal hydroxide whereby the product contains polyvalent hydroxide and carbonate.  The soluble polyvalent metal salt and alkali metal carbonate (with hydroxide, if used) may be employed in equal numbers of equivalents, say 1-20, based on the organic acid salt but preferably a small excess of soluble polyvalent metal salt is used.  Thereafter, the oil phase of product may be separated from the aqueous phase by settling or distilling off the water.  The product may have a basicity of up to 1500 per cent or higher and may be isolated from solution by removal of the oil.  The process may be used to form basic alkaline earth metal, zinc, magnesium, copper, iron, nickel, cobalt, chromium, manganese and lead salts of carboxylic, thiocarboxylic, sulphonic, sulphamic, sulphinic, thiosulphonic, phosphonic and phosphinic acids, phenols and partial esters of sulphuric acid and phosphorus oxy- and thio-acids including palmitic acid, hydroxy- and chloro-stearic acids, nitro-lauric acids, alkylated naphthoic and salicylic acids, naphthenic acids, di-octyl cyclopentane carboxylic acids, petroleum sulphonic acids, alkylated aromatic, cycloaliphatic and heterocyclic sulphonic acids, e.g. cetyl chlorbenzene sulphonic acids, cetyl phenol sulphonic acids and octyl-phenol-disulphide sulphonic acids, di-isopropyl phenols, di-capryl dithiophosphoric acid and di-(methyl cyclohexyl) dithiophosphorous acid.  The products may be used as additives in lubricating or fuel oils.  In typical examples: (1) aqueous solutions of NaOH and Na2CO3 are added to a xylene solution of C14-18 alkylsalicylic acids, the mixture is heated to remove the water and the resulting basic oil solution is reacted with aqueous CaCl2 at 90 DEG  C. and then dried and filtered yielding a xylene solution of basic calcium alkyl-salicylates; (2) as in (1), the oil solution containing also isopropanol and being treated with the aqueous CaCl2 in a counter-current contacting apparatus; (3) a xylene solution of mono- and di-lauryl phosphates is mixed with aqueous solutions of NaOH and Na2CO3, dried, reacted with aqueous ferric chloride solution at 90 DEG  C. and then dried and filtered.  The polyvalent metal chlorides may be replaced by the nitrates, sulphates, acetates or formates and other specified oils include various petroleum oils, polymerized olefines, alkylated aromatic hydrocarbons, liquid polysiloxanes and fluorocarbons, fatty oils, ester-type lubricating oils, iso-octane, decyl alcohol and diamyl ether.  Specifications 586,461, [Group IV], 790,471 and 795,172 are referred to.ALSO:Lubricating oils and fuel oils comprise, as detergent additive or corrosion inhibitor respectively, a basic polyvalent metal salt of an organic acid prepared by treating a solution of a neutral or basic salt of the organic acid, an alkali metal carbonate and, if desired, an alkali metal hydroxide in a water-immiscible liquid with an aqueous solution of a water-soluble polyvalent metal salt and removing the water from the resulting mixture.  The basic product is obtained in solution in the water-immiscible liquid and need not be isolated before use as additive.  The water-immiscible liquid may be a hydrocarbon, e.g. benzene, a mineral lubricating oil, kerosene, gas oil, diesel oil, a residual fuel oil or a polymerized olefine, an ester-type lubricating oil, a fatty oil, a liquid polysiloxane or fluorocarbon, decyl alcohol or diamyl ether. Examples describe xylene solutions of basic calcium C14-18 alkyl-salicylates and of basic ferric mono- and di-lauryl phosphates. Other basic salts mentioned are the alkaline earth metal, magnesium, zinc, copper, nickel, cobalt, chromium, manganese and lead salts of carboxylic, thiocarboxylic, sulphonic, sulphamic, sulphinic, thio sulphonic, phosphonic and phosphinic acids, phenols and partial esters of sulphuric acid and phosphorus oxy- and thio-acids and numerous examples of these acids are listed.  Specifications 586,461, 790,471 and 795,172 are referred to.