Patent GB-789474-A (GB)
Title: Improvements in or relating to metal salts of phosphosulphurized hydrocarbons
IPC: C07F9/04
Filed: 1955-08-19
Abstract: A metal salt of a phosphosulphurized hydrocarbon is obtained by heating a phosphosulphurized hydrocarbon with an aqueous acidic solution of a halide of a metal lying between lead and magnesium inclusive in the Electromotive Series of the metals for a period of time sufficient to form an anhydrous salt of the metal with the phosphosulphurized hydrocarbon.  The preferred phosphosulphurized hydrocarbons are those derived from mono-olefin polymers having a molecular weight ranging from 100 to 50,000 and obtained by the polymerization of low molecular weight olefins (see Group IV (a)) but other phosphosulphurized hydrocarbons may be used, e.g. those derived from olefins, diolefins, acetylenes, aromatics, alkyl aromatics, alicyclics, petroleum fractions such as lubricating oil distillates, petrolatums, cracked cycle stocks and solvent extracts, of petroleum fractions.  The phosphosulphurization may be carried out in the conventional manner and if desired catalysts such as organic or inorganic peroxides may be present and the reaction product may be further treated by blowing with steam, alcohol or ammonia at an elevated temperature of 200 DEG  to 600 DEG  F. to improve the odour thereof.  The metal halides used in the process are preferably the chlorides although other halides, e.g. the bromides or iodides, may be used. The preferred metals are tin, zinc, cobalt and nickel, but other metals are also specified, viz. magnesium, aluminium, manganese, chromium, iron, cadmium and lead.  The acid used to form the aqueous acidic solution of the metal halide is preferably a halogen acid such as hydrochloric acid and the reaction of the aqueous acidic metal halide with the phosphosulphurized hydrocarbon is preferably carried out in the presence of a diluent, e.g. a petroleum lubricating oil, and at a temperature in the range of 140 DEG  to 300 DEG  F. until most of the water has been driven off, after which the temperature may be raised to from 350 DEG  to 500 DEG F. to complete the reaction and to eliminate all the water.  A small amount of halogen derived from the metal halide or from the acid may remain in the final product.  When an excess of the polyvalent metal halide is employed mixed salts can be obtained which contain both halogen and the phosphorus-containing group joined to the metal. Examples are given for the preparation of the zinc, tin and cobalt salts respectively of P2S5-treated polyisobutylene.  The products are stated to be useful as additives for lubricants and other mineral oils (see Group III), as fungicides and insecticides (see Group VI) and as flotation agents.ALSO:A metal salt obtained by heating a phosphosulphurized hydrocarbon with an aqueous acidic solution of a halide of a metal lying between lead and magnesium inclusive in the Electromotive Series of the metals for a period of time sufficient to form an anhydrous salt of the metal with the phosphosulphurized hydrocarbon (see Groups IV (a) and IV (b)) may be used as an additive for lubricating oils.  Specified metals whose salts may be employed are tin, zinc, cobalt, nickel, magnesium, aluminium, manganese, chromium, iron, cadmium, and lead.  The phosphosulphurized hydrocarbon is preferably derived from a mono-olefin polymer having a molecular weight in the range 100 to 50,000 and obtained by the polymerization of a low molecular weight olefin such as ethylene, propylene, isobutylene, or amylene but other phospho-sulphurized hydrocarbons may be used, e.g. those derived from olefines, diolefines, acetylenes, aromatic, alkyl aromatic and alicyclic hydrocarbons, petroleum fractions such as lubricating oil distillates, petrolatums, cracked cycle stocks, and solvent extracts of petroleum fractions.  The lubricating oil may be a mineral lubricating oil or a synthetic lubricating oil, e.g. a single ester such as an ester of a C8oxo alcohol with a C8 oxo acid or an ester of a C13 oxo alcohol with octanoic acid, a diester such as di-2-ethyl hexyl sebacate- or di-nonyl adipate, a complex ester, a phosphoric acid ester, e.g. the ester formed by contacting three mols. of the monomethyl ether of ethylene glycol with one mol. of phosphorus oxychloride, halocarbon oils, e.g. the polymer of chlorotrifluoroethylene containing twelve recurring units, alkyl siloxanes, sulphite esters, carbonates, formals, mercaptals, polyglycols, and synthetic oils prepared by the polymerization of olefines or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or coal products.  Vegetable, animal and fish oils or their hydrogenated or voltolized products may be employed in admixture with the synthetic or mineral lubricating oils. Other conventional lubricating oil additives may also be present, e.g. dyes, pour depressors, heat-thickened fatty oils, sulphurized fatty oils, organo metallic compounds, metallic or other soaps, sludge dispersers, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltolized waxes and colloidal solids such as graphite or zinc oxide, solvents, and assisting agents such as esters, ketones, alcohols, aldehydes, and halogenated or nitrated compounds. Specified metal salts are the zinc, tin and cobalt salts of P2S5-treated polyisobutene and an example is given of a composition comprising a mineral lubricating oil of viscosity 43 S.U.S. at 210 DEG  F. and a minor amount of the zinc salt of P2S5-treated polyisobutene and of polymerized isobutylene (molecular weight 14000) and P2S5-treated a -pinene.ALSO:A metal salt of a phosphosulphurized hydrocarbon, e.g. a phosphosulphurized mono-olefin polymer, is obtained by heating the phosphosulphurized hydrocarbon with an aqueous acidic solution of a halide of a metal lying between lead and magnesium inclusive in the Electro-motive Series of the metals for a period of time sufficient to form an anhydrous salt of the metal with the phosphosulphurized hydrocarbon.  The phosphosulphurized hydrocarbon is preferably derived from a monoolefin polymer having a molecular weight in the range of 100 to 50,000 and obtained by the polymerization of a low molecular weight olefin such as ethylene, propylene, isobutylene, or acrylene.  The phosphosulphurization may be carried out in the conventional manner, if desired in the presence of an organic or inorganic peroxide catalyst, and the reaction product may be further treated by blowing with steam, alcohol, or ammonia, at a temperature of 200 DEG  to 600 DEG  F. to improve the odour thereof.  The metal halides are preferably the chlorides but other halides, e.g. the bromides or iodides may also be used.  The preferred metals are tin, zinc, cobalt, and nickel.  Other metals specified are magnesium, aluminium, iron, manganese, cadmium, chromium, and lead.  The acid used to form the aqueous acidic solution of the metal halide is preferably a halogen acid such as hydrochloric acid.  The reaction of the metal halide solution with the phosphosulphurized hydrocarbon is preferably carried out in the presence of a diluent, e.g. a petroleum lubricating oil, and at a temperature in the range of 140 DEG  to 300 DEG  F. until most of the water has been driven off, after which the temperature may be raised to from 350 DEG  to 500 DEG  F. to complete the reaction and to eliminate all the water.  Examples are given for the preparation of the zinc, tin, and cobalt salts respectively of P2S5-treated polyisobutylene, an aqueous solution of the corresponding metal chloride acidified with hydrochloric acid being used in each case.  The products are stated to be useful as additives for lubricants and other mineral oils (see Group III), as fungicides and insecticides (see Group VI), and as flotation agents.ALSO:Pesticidal compositions comprise a metal salt obtained by heating a phosphosulphurized hydrocarbon with an aqueous solution of a halide of a metal lying between lead and magnesium inclusive in the Electromotive Series of the metals for a period of time sufficient to form an anhydrous salt of the metal with the phosphosulphurized hydrocarbon (see Groups IV (a) and IV (b)), dispersed or dissolved in water, an organic solvent such as kerosene, light petroleum or a gas oil, or an inert solid such as clay.  Specified metals are tin, zinc, cobalt, nickel, magnesium, aluminium, manganese, chromium, iron, cadmium and lead.  The phosphosulphurized hydrocarbons may be derived from olefins, diolefins, acetylenes, aromatic, alicyclic, or alkyl aromatic hydrocarbons and particularly from monolefin polymers having a molecular weight in the range 100 to 50,000.  Specified metal salts are the zinc, tin and cobalt salts of P2S5-treated polyisobutene.