Patent GB-717201-A (GB)
Title: Lubricating compositions
Filed: 1952-05-22
Abstract: Phosphorized terpene compounds are employed as ingredients of lubricating compositions (see Group III).  The expression "terpene compound" is used to include not only monoterpenes but also the higher terpenes such as sesquiterpenes, diterpenes, and polyterpenes, and the oxygenated derivatives of all such terpenes.  Suitable terpene compounds include alpha- and beta-pinene, dipentene, terpinolene, menthene, alpha-terpineol, camphene, limonene, turpentine, pine oil, camphor oil, terpenes obtained as a by-product in the manufacture of synthetic camphor, carene, fenchene, terpinene, camphoric acid and abietic acid.  The phosphorizing agents used for the preparation of the phosphorized terpene compounds may be such that sulphur or selenium in addition to phosphorus is introduced into the terpene compound.  Suitable phosphorizing agents are P2S5, P4S3, P2Se5, P2Se3, P, P2O5, POCl3, PCl3, PCl5, PSCl3 and H3PO4.  The terpene compounds can also be first reacted with a sulphurizing or selenizing agent, e.g. SCl2, S2Cl2, sodium polysulphide, SeCl2 or SeCl4, and thereafter retreated with a phosphorizing agent, e.g. P2O5, P2S5 or phosphoric acid, so that the final reaction product contains both sulphur or selenium and phosphorus.  If desired, the terpene compound may be first treated with a phosphorizing agent and then with a sulphurizing or selenizing agent.  The final reaction product may be refined by solvent treatment or neutralized with a nitrogen base.  Suitable organic nitrogen bases are amines, quaternary ammonium compounds, morpholine and piperidine.  Examples are given of the phosphorizing of turpentine and alphapinene with P2S5.ALSO:A lubricating composition, particularly suitable for use in aviation engines, comprises a lubricating oil having incorporated therein a minor proportion of a phenol or thiophenol which is substituted by organic radicals at the ortho and para positions, at least one of the ortho substituents being an alkyl radical which is linked to the aromatic nucleus by a tertiary carbon atom, and a minor proportion of a phosphorized terpene compound.  The lubricating oil may be a hydrocarbon oil or it may be a mineral oil blended with a fixed oil, such as castor oil or lard oil, and/or with a synthetic lubricating oil, such as polymerized olefins, copolymers of alkylene glycols and oxides, esters of polybasic organic and inorganic acids (e.g. di- (2-ethylhexyl) sebacate, dioctyl phthalate and trioctyl phosphate), polymeric tetrahydrofuran and silicone polymers (e.g. dimethyl silicone polymer).  If desired, such synthetic lubricating oils may be used as the lubricating oil base either above or mixed with fixed oils. The expression "terpene compound" is used to include not only monoterpenes but also the higher terpenes such as sesquiterpenes, diterpenes, and polyterpenes, and the oxygenated derivatives of all such terpenes.  Suitable terpene compounds include alpha- and betapinene, dipentene, terpinolene, menthene, alphaterpineol, camphene, limonene, turpentine, pine oil, camphor oil, terpenes obtained as a byproduct in the manufacture of synthetic camphor, carene, fenchene, terpinene, camphoric acid and abietic acid.  The phosphorizing agents used for the preparation of the phosphorized terpene compounds may be such that sulphur or selenium in addition to phosphorous is introduced into the terpene compound. Suitable phosphorizing agents are P2S5, P4S3, P2Se5, P2Se3, P, P2O5, POCl3, PCl3, PCl5, PSCl3 and H3PO4.  The terpene compounds can also first be reacted with a sulphurizing or selenizing agent, e.g. SCl2, S2Cl2, sodium polysulphide, SeCl2 or SeCl4, and thereafter re-treated with a phosphorizing agent, e.g. P2O5, P2S3 or phosphoric acid, so that the final reaction product contains both sulphur or selenium and phosphorus.  If desired, the terpene compound may be first treated with a phosphorizing agent and then with a sulphurizing or selenizing agent.  The final reaction product may be refined by solvent treatment or neutralized with a nitrogen base.  Suitable organic nitrogen bases are amines, quaternary ammonium compounds, morpholine and piperidine.  The lubricating composition may contain additional ingredients such as blooming agents, pour point depressants, viscosity improvers, extreme pressure agents, anti-foaming agents and detergents and a number of such ingredients are specified.  The lubricating compositions may also be used as motor oils, turbine oils, steam cylinder oils, marine engine oils and refrigeration oils, and used for various lubrication purposes other than engine lubrication, such as slushing and flushing oils, rust inhibiting oils, quenching and drawing oils, greases and wax compositions.  In the examples, mineral lubricating oil compositions are described wherein the phenol is 2, 6-ditert.-butyl-4-methylphenol or 2, 21-methylene bis (4-methyl-6-tert.-butyl phenol) and the phosphorized terpene compound is P2S5-turpentine or P2S5-alpha-pinene reaction product.