Patent GB-586512-A (GB)
Title: An improved manufacture of petroleum hydrocarbon oil compositions
IPC: C10M137/10
Filed: 1943-07-08
Abstract: The tendency of petroleum hydrocarbon oils to deteriorate at elevated temperature or in the presence of oxygen is inhibited by incorporating in the oil a small proportion of a polyvalent metal salt of an acid of trivalent phosphorus which contains an organic substituent and also sulphur, selenium or tellurium therein. Suitable metal salts are calcium, barium, zinc, magnesium, aluminium, tin, cobalt or nickel salts of thiophosphorus acids which contain organic substituent groups such as alkyl, aryl, alkaryl, aralkyl or heterocyclic groups, and among the metal salts specified the following are typical: zinc di(para-isooctyl phenyl) monothiophosphite, zinc dicyclohexyl monothiophosphite, cobalt naphthenyl monothiophosphite, barium dicetyl dithiophosphite and calcium di-n-octyl trithiophosphite.  The petroleum hydrocarbon oil may be a hydrogenated oil or white oil and may be blended with animal, vegetable or fish oils or their hydrogenated or voltolized products.  The petroleum hydrocarbon oil compositions, which may be crankcase lubricants, extreme pressure lubricants, spindle oils, textile oils, metal cutting oils, engine flushing oils, turbine oils, insulating oils, transformer oils, steam cylinder oils, slushing compositions, greases, motor fuels, Diesel fuels or kerosene compositions, may also contain additional ingredients such as dyes, pour depressors, heat thickened fatty oils, sulphurized fatty oils, organometallic compounds, metallic or other soaps, sludge dispersers, antioxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, voltolized waxes, colloidal solids such as graphite or zinc oxide, esters, ketones, alcohols and aldehydes.  Alcohols mentioned are octyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, naphthenic alcohols, phenyl octyl alcohol, octadecyl benzyl alcohol, alcohols obtained from woolfat or sperm oil and alcohols obtained by the oxidation of petroleum hydrocarbons such as paraffin wax or petrolatum, while, instead of the alcohols themselves, substances such as woolfat or sperm oil which contain alcohols may be employed.  In examples, mineral lubricating oil compositions are described which contain barium dioctyl monothiophosphite, calcium diamylmonothiophosphite, calcium dioctyl monothiophosphite or calcium dioctyl dithiophosphite.  For comparison purposes mineral lubricating oil compositions containing nickel oleate or calcium dioctyl dithiophosphate are described.  Preparation of zinc di(para-isooctyl phenyl) monothiophosphite.  A solution of isooctyl phenol in mineral lubricating oil is heated with phosphorus trisulphide and then zinc oxide is added.  Upon filtering, a solution of zinc di(para-isooctyl phenyl) monothiophosphite in mineral lubricating oil is obtained.  The Specification as open to inspection under Sect. 91 refers to an organic composition containing a small quantity of a polyvalent metal salt of an organo substituted acid of phosphorus containing an element of the group consisting of sulphur, selenium and tellurium.  Oil compositions having a basis of synthetic oils prepared for example by the polymerization of olefins or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or its products and oil compositions having a basis of cracking coal tar fractions, coal tar or shale oil distillates, or animal, vegetable or fish oils or their hydrogenated or voltolized products are described.  Polyvalent metal salts of acids of pentavalent phosphorus containing sulphur, selenium or tellurium and an organic substituent are also described and among such metal salts specified the following are typical: barium dioctyl diothiophosphate, magnesium monolauryl monothiophosphate and zinc dioctadecyl trithiophosphate. This subject-matter does not appear in the Specification as accepted.ALSO:Polyvalent metal salts of acids of phosphorus containing sulphur, selenium or tellurium and an organic substituent are employed as anti-oxidants in petroleum hydrocarbon oils.  In examples of the preparation of suitable salts, (1) 2-ethyl hexanol-1 is heated with phosphorus trisulphide to give di(2-ethyl-n-hexyl) monothiophosphorous acid and this acid is converted to its sodium salt by neutralisation with alcoholic sodium hydroxide; the sodium salt is reacted with barium bromide to give barium di(2-ethyl-n-hexyl)monothiophosphite or with calcium chloride to give calcium di (2-ethyl-n-hexyl) monothiophosphite; (2) amyl alcohol is reacted with phosphorus trisulphide and calcium carbonate to give calcium di-n-amyl monothiophosphite and (3) stearyl alcohol is heated with phosphorus trisulphide and magnesium oxide is then added to give magnesium di-n-octadecyl monothiophosphite.  The Specification as open to inspection under Sect. 91 refers to the employment of polyvalent metal salts of organo substituted acids of phosphorus containing an element of the group consisting of sulphur, selenium and tellurium as anti-oxidants.  In examples of the preparation of suitable salts: (1) 2-ethyl hexanol is heated with phosphorus pentasulphide to give dioctyl dithiophosphoric acid and the acid is converted to its sodium salt by neutralisation with alcoholic sodium hydroxide; the sodium salt is reacted with barium bromide to give barium dioctyl dithiophosphate and (2) octyl alcohol, phosphorus pentasulphide and sodium carbonate are heated together and the reaction product treated with calcium nitrate to give calcium dioctyl dithiophosphate.  It is stated that the metal salts may be used as anti-oxidants in any organic materials subject to deterioration by atmospheric oxygen and organic materials mentioned include asphalts, road oils, waxes, fatty oils of animal or vegetable origin, soaps, plastics and natural and synthetic rubber.  This subject-matter does not appear in the Specification as accepted.