Patent GB-818326-A (GB)
Title: Process for the preparation of oil-soluble basic polyvalent salts of organic acids
IPC: C10M159/20
Filed: 1956-04-20
Abstract: Oil-soluble basic polyvalent metal salts, the basicity of which is at least partly not of the oxide, hydroxide or carbonate type, of general formula RpMeq.XMe1rZs where RpMeq is a salt of an organic acid, which is oil-soluble per se, and Me1rZs is oil-insoluble per se, R being an organic acid radical and Me and Me1 being metals, which may be the same or different, Z an arbitrary group, p, q, r and s integers depending upon the valencies of the components of the salts, and X an arbitrary number, which is not necessarily an integer, are used in paint driers and lubricants and liquid fuels. The oil-soluble polyvalent metal salt may be derived from aliphatic, cycloaliphatic, aromatic or alkyl aromatic acid (preferably containing at least 12 carbon atoms in the alkyl substituent) such as sulphonic acids, especially petroleum sulphonic acids, alkyl salicylic acids, petroleum naphthenic acids, phosphorus acids, e.g. those derived from tri- and penta-valent phosphorus, and the corresponding thio acids.  The basic component of the salt may be provided by the sulphide, or sulphite of a metal.  The salts may contain one or more of the following metals: calcium, magnesium, zinc, lead, aluminium, copper, tin, cobalt, nickel, and manganese, and may also contain monovalent metals (e.g. sodium, potassium or lithium), or ammonium.  Examples are given of salts containing calcium and the following radicals, diC14-C18 alkyl salicylic acids, sulphite, and oxalate.  The basic polyvalent metal salts may be incorporated in petroleum fractions from gasoline up to lubricating oil.  Specifications 743,842 and 818,323 are referred to.ALSO:The invention comprises a process for the preparation of an oil-soluble basic polyvalent metal salt of an organic acid, the basicity of which is at least partly not of the oxide hydroxide or carbonate type, by reacting an oil-soluble polyvalent metal salt of an organic acid, dissolved in an oil, in the presence of water and/or a water-miscible oxygen containing organic liquid, with an oil-insoluble metal compound, other than an oxide, hydroxide or carbonate, which is formed in situ in the reaction mixture.  The oil-soluble polyvalent metal salt may be derived from aliphatic, cycloaliphatic, aromatic or alkyl aromatic acids (preferably containing at least 12 carbon atoms in the alkyl substituent) such as sulphonic acids, especially petroleum sulphonic acids, alkyl salicylic acids, petroleum naphthenic acids, phosphonic acids, e.g. those derived from tri and pentavalent phosphones, containing acids, and the corresponding thio acids.  The salt used as starting material may be a basic one which has been prepared by the process of the invention, and may be subjected one or more times again to this process, in order to increase its basicity.  The oil-soluble polyvalent metal salt or mixtures of such used as starting material may be first formed in situ, in the reaction mixture by reacting the free organic acid or a salt thereof with a compound of the desired polyvalent metal, such as an oxide hydroxide, carbonate or chloride.  This salt is dissolved in an oil generally having a dielectric constant of 10 or less such as benzene, toluene, xylene, pentane, heptane and petroleum fractions from gasoline up to lubricating-oil fractions, preferably those fractions having a viscosity of 100-400 S.S.U. at 38 DEG  C., and the concentration of salt may be from 10-70 per cent by weight.  Suitable water-miscible oxygen containing organic liquids which may be present in the reaction medium are methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, cyclo hexanone, diisopropyl ether, monomethyl and monoethyl ethers of glycol, 1.3 dioxane, 1.4 dioxane, ethyl acetate, ethyl lactate, ethyl propionate, n-propylacetate and isopropyl acetate.  When used alone, water should generally be present in at least 2 per cent by weight, based on the solution of the oil-soluble polyvalent metal salt of the organic acid and the oxygen-containing liquid, in at least 5 per cent by weight.  Water may be formed during the course of the reaction.  The oil solution and the water and/or water-miscible oxygen containing organic liquid may be present in the form of one homogeneous liquid phase or in the form of two separate liquid phases (which are preferably thoroughly mixed).  The oil-insoluble metal compound which is formed in situ in the reaction mixture may be e.g. a sulphide, sulphite or a salt of an organic acid, and may be formed in any suitable way, e.g. by the addition of Ca(OH)2 or NaOH either in the dry state or dissolved or suspended in water or an alcohol to the reaction mixture and the passing in of sulphur dioxide. The process may be carried out between 20 DEG -150 DEG  C. at atmospheric or superatmospheric pressure. After the reaction, the reaction mixture may be dried, e.g. by heating to 135 DEG -160 DEG  C. and may then be air blown and filtered, the solvent being removed e.g. by distillation.  The basic salts prepared may contain monovalent metals, e.g. sodium, potassium and lithium, and the ammonium radical as well as polyvalent metals such as alkaline earth metals (particularly calcium), magnesium, zinc, lead, aluminium, copper, tin, cobalt, nickel and manganese. Examples are given of the preparation of salts containing calcium and the following radicals, di C14-C18, alkyl salicylic acids, sulphite, and oxalate.  Specifications 743,842, 818,323 and U.S.A. Specifications 2,616,905 and 2,623,016 are referred to.