Patent GB-670077-A (GB)
Title: Improved oxidation resisting compositions comprising mineral lubricating oils, and hydrocarbon polymers, synthetic rubbers and waxes
IPC: C10M137/10
Filed: 1948-08-31
Abstract: Cuprous thiophosphates of formula <FORM:0670077/IV (b)/1> where R and R1 are organic radicals which may be hydrocarbon, halogen-substituted hydrocarbon or nitro-substituted hydrocarbon radicals, the sum of the carbon atoms in aliphatic or cycloaliphatic groups in R and R1 being not less than 10 and X is oxygen or sulphur, are prepared by treating the corresponding thiophosphoric acid with cuprous oxide, preferably in the presence of a reducing agent and/or in an inert atmosphere. The thiophosphoric acid may be prepared by treating an appropriate alcohol, phenol, mercaptan or thiophenol with phosphorus pentasulphide.  Alcohols mentioned are 2-ethylhexanol, methyl cyclohexanol, a mixture of C12 to C16 alcohols, normal straight-chain alcohols, alcohols derived from natural waxes or from the oxidation of petroleum hydrocarbons, lauryl, stearyl and oleyl alcohols, wool-fat alcohols, and sperm oil alcohols; alkylated phenols and naphthols such as amyl and octyl phenols, wax-alkylated phenols and petroleum phenols are also mentioned.  The corresponding mercaptans and thiophenols may also be used, as well as a mixture of alcohols, such as a mixture of isopropanol and 2-ethylhexanol.  In one example, 2-ethylhexanol is heated with phosphorus pentasulphide for 1 1/2 hours at 90 DEG  C.  After filtration the acid is added to a slurry of cuprous oxide and sodium hydrosulphite in benzene.  The product is filtered, the filtrate is dissolved in mineral oil, and the benzene and water are removed by heating.  The preparation of cuprous nonyl, octyl, methylcyclohexyl, isopropyl, ethyl-hexyl and C12-C16 alkyl secondary butyl thiophosphates is also described.  Specification 601.586 is referred to.ALSO:Hydrocarbon products are mixed with a small proportion of a compound of formula <FORM:0670077/III/1> where R and R1 are organic radicals which may be hydrocarbon, halogen-substituted hydrocarbon and nitro substituted hydrocarbon radicals, the sum of the carbon atoms in aliphatic or cycloaliphatic groups in R and R1 being not less than 10, and where X is oxygen or sulphur.  The tendency of the products to corrode metal surfaces and to undergo atmospheric oxidation is thus reduced.  The hydrocarbon products may be hydrocarbon lubricating oils, hydrocarbon fuels such as Diesel fuel and kerosene, synthetic rubbers and hydrocarbon waxes. The hydrocarbon oils may be mineral oils or synthetic oils such as those prepared by the polymerisation of olefins, and mixtures of mineral oils with animal, vegetable and fish oils may also be used. The alcohol from which the thiophosphoric acid is derived may be 2-ethylhexanol, methylcyclohexanol, a mixture of C12 to C16 alcohols, normal straight-chain alcohols, alcohols derived from natural waxes or from the oxidation of petroleum hydrocarbons, lauryl, stearyl and oleyl alcohols, wool-fat alcohols and sperm oil alcohols; alkylated phenols and naphthols such as amyl and octyl phenols, wax-alkylated phenols and petroleum phenols are also mentioned.  The corresponding mercaptans or thiophenols may also be used.  Additives specified are cuprous methylcyclohexyl, 2-ethylhexyl, nonyl, octyl, isopropyl-ethylhexyl and C12-C16 alkyl - secondary butyl thiophosphates.  These compounds are compared in their effects with sodium, potassium and calcium ethylhexyl thiophosphates.  From 0.02 to about 3 per cent of the additives may be used.  Detergents such as soaps, sulphonates, phenates, alcoholates, carboxylates, alkyl phenol sulphides, organo phosphates, other thiophosphates, phosphites and thiophosphites, salicylates, xanthates, thioxanthates, thiocarbamates, amines, reaction products of phenates and sulphur or phosphorus sulphides may also be added to the compositions.  Examples of such detergents include barium tert. octyl phenol sulphide, nickel oleate, aluminium naphthenate, calcium phenyl stearate, calcium petroleum sulphonate and zinc methyl cyclohexyl thiophosphate.  In the case of hydrocarbon lubricating compositions, other optional ingredients are dyes, pour point depressors, heat-thickened fatty oils, sulphurised fatty oils, organo-metallic compounds, sludge - dispersers, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber olefin polymers, voltolized fats, voltolized mineral oils or voltolized waxes, graphite, zinc oxide, solvents and assisting agents.  Assisting agents particularly mentioned are the higher alcohols, for example octyl, lauryl, cetyl, stearyl, heptadecyl, oleyl, napthenic, phenyl octyl and octadecyl benzyl alcohols, wool fat and sperm oil alcohols, and alcohols produced by the oxidation of petroleum hydrocarbons.  Specification 601,586 is referred to.