Patent GB-1081311-A (GB)
Title: Metal salts of organic phosphorus acid mixtures
IPC: C07F9/02
Filed: 1965-07-13
Abstract: A lubricating, fuel oil, or gasoline composition comprises a major proportion of a lubricating oil, fuel oil or gasoline and a minor proportion by weight of a metal salt of a mixture of (A) a dihydrocarbon phosphorothioic acid having at least 3 aliphatic carbon atoms in each hydrocarbon group, and (B) a diphenyl, halo-phenyl or alkylphenyl phosphinothioic acid wherein the alkyl group has up to 6 carbon atoms, in which mixture the molar ratio of (A) to (B) is between 1 : 2 and 1 : 0.05 and the ratio of aliphatic carbon atoms to phosphorus atoms is at least 6 to 1. The lubricating oils may be of synthetic, animal, vegetable or mineral origin; the use of poly(alkyleneglycol) oils and synthetic polyester oils such as didodecyladipate and dioctyl sebacate is also mentioned.  Other additives may be present in these compositions, e.g. supplemental detergents of the ash-containing type, sulphurized and phosphosulphurized fatty acid esters, polysulphides, hindered phenols, phosphites, and metal phenates. Many such additives are specified.  The ash-containing detergents are exemplified by oil-soluble-neutral and basic salts of alkali or alkaline earth metals with sulphonic acids, carboxylic acids, or organic phosphorus acids, the last-named being characterized in having at least one direct carbon to phosphorus bond.ALSO:The invention comprises metal salts of a mixture of (A) a dihydrocarbon phosphorothioic acid having at least 3 aliphatic carbon atoms in each hydrocarbon radical, and (B) a diaryl, or substituted aryl, phosphinothioic acid, wherein each aryl or substituted aryl group is phenyl, halophenyl, or alkylphenyl having up to 6 carbon atoms in the alkyl substituents wherein the molar ratio of (A) to (B) is between 1:2 and 1:0.05, and the ratio of aliphatic carbon atoms to phosphorus atoms is at least 6 to 1. Suitable hydrocarbon groups include polypropylene and polybutylene-substituted phenyl groups.  The phosphorothioic acids are obtained by reacting the corresponding polypropylene- or polybutylene - substituted phenol with phosphorus pentasulphide. In the Examples (21) a barium salt of a mixture of di(polyisobutylene (molecular weight of 1000)-substituted phenyl) phosphorodithioic acid and ditolyl phosphinodithioic acid is formed and (26) the zinc salt of a mixture of di(polyisobutylene (molecular weight 50,000)-substituted phenyl) phosphorodithioic acid and di(bromophenyl) phosphinodithioic acid is formed.  Alkali or alkaline earth metal salts of phosphorus acids having at least one carbonphosphorus bond are prepared by phosphorizing olefin polymers, such as polyisobutylene having a molecular weight of 1000, with PCl3, P2S7, P2S5, PCl3 and S, white phosphorus and a sulphu halide, or phosphorothioic chloride.  A basic barium salt of a phosphorus acid is prepared by reacting P2S5 with polyisobutylene of molecular weight 50,000, hydrolysing the product, mixing with mineral oil, barium hydroxide, and phenol and carbonating the mixture.ALSO:Novel metal salts of a mixture of (A) a dihydrocarbon phosphorothioic acid having at least 3 aliphatic carbon atoms in each hydrocarbon radical, and (B) a diphenyl, halophenyl or alkyl phenyl phosphinothioic acid, wherein each alkyl group has up to 6 carbon atoms, in which mixture the molar ratio of (A) to (B) is between 1: 2 and 1: 0.05, and the ratio of aliphatic carbon atoms to phosphorus atoms is at least 6: 1, are prepared by reacting a mixture of the phosphorus acids (A) and (B) with a metal or an hydroxide, oxide, carbonate, bicarbonate, hydride, mercaptide, or sulphide of a metal.  The hydrocarbon radicals include alkyl, cycloalkyl, aralkyl, and alkaryl radicals; included in the last-named class are polypropylene and polyisobutylene substituted phenyl groups.  The dithioic acids (A) are prepared by reacting 1 mol. of P2S5 with 4 mols. of an alcohol or alkylphenol at 50-250 DEG  C. Dithioic acids (B) are prepared by reacting an aromatic hydrocarbon with P2S5, preferably in the presence of a Friedel-Crafts catalyst at 60 DEG -250 DEG  C.  The monothioic acids (A) and (B) are prepared by hydrolysing the corresponding lithioic acids.  The preparation of certain additives for use in lubricant compositions containing the above metal salts as antioxidants and stabilizers is also described, thus a basic sulphonate detergent is prepared by heating a mineral oil, water, heptylphenol, barium mahogany sulphonate, and barium hydroxide together, followed by carbonation; a calcium sulphonate is prepared by heating a mineral oil, sodium petroleum sulphonate, and water mixture, with further heating with calcium chloride and lime, followed by the addition of methyl alcohol and carbonation-the product is mixed with mineral oil, methyl alcohol, isobutyl alcohol and amyl alcohol and heated, and calcium hydroxide added to the resulting mixture which is carbonated, heated and filtered to yield a product having a metal ratio of 12.2.