Patent GB-693421-A (GB)
Title: Improvements in lubricating oil compositions and additives therefor
IPC: C10M159/12
Filed: 1948-02-05
Abstract: A product derived from a pinene by reacting it with a phosphorus sulphide is employed as a lubricating oil ingredient (see Group III). The pinene may be alpha-pinene or beta-pinene or turpentine (which is a mixture of alpha- and beta-pinenes), while the phosphorus sulphide may be P4S3, P2S3, P4S7, PS2 or P2S.  The reaction with a phosphorus sulphide may be carried out in the presence of a phosphosulphurization catalyst such as anhydrous aluminium chloride, anhydrous ferric chloride, boron trifluoride, hydrogen fluoride, iodine, hydrogen iodide, sulphuric acid, sulphurtrioxide, phosphoric acid, phosphorus pentoxide or mixtures of such catalysts.  The product may be improved by washing, air-blowing, distilling or filtering, or it may be modified by treatment with alcohols, acids, benzyl chloride, phosphorus, phosphorus chlorides, halogen, sulphur, sulphur chlorides, metals, metallic sulphides, metallic oxides, alkalis or other basic materials.  Such modifying treatment may, if desired, be effected prior to the final washing, distillation or filtering operations.  In an example, turpentine is heated with P2S and the reaction product, after dilution with light mineral oil and addition of a filter aid, is filtered.  The product of this example, however, decomposes when maintained at an elevated temperature.  A stabilized product is obtained if (i) butanol is added to the reaction product before dilution with light mineral oil, (ii) caustic soda is present during the reaction between turpentine and P2S or (iii) caustic soda is added after dilution with light mineral oil. The Specification as open to inspection under Sect. 91 gives a list of additional materials which may be used in modifying the phosphorus sulphide-pinene reaction product.  This subject-matter does not appear in the Specification as accepted.ALSO:A composition which, when employed as a lubricant in internal combustion engines, has a reduced tendency to cause corrosion or produce deleterious deposits or to deteriorate through oxidation, comprises a hydrocarbon lubricating oil solution of (a) a product derived from a pinene by reacting such pinene with a phosphorus sulphide and (b) an oil-soluble metal salt of a sulphonic acid. The pinene employed in preparing ingredient (a) may be alphapinene beta-pinene or turpentine (which is a mixture of alpha- and beta-pinenes), while the phosphorus sulphide may be P4S3, P2S3, P4S7, PS2 or P2S5.  The reaction with a phosphorus sulphide may be carried out in the presence of a phosphosulphurization catalyst such as anhydrous aluminium chloride, anhydrous ferric chloride, boron trifluoride, hydrogen fluoride, iodine, hydrogen iodide, sulphuric acid, sulphur trioxide, phosphoric acid, phosphorus pentoxide or mixtures of such catalysts.  Ingredient (a), before incorporating in the lubricating oil solution, may be improved by washing, air-blowing, distilling or filtering, or it may be modified by treatment with alcohols, acids, benzyl chloride, phosphorus, phosphorus chlorides, halogen, sulphur, sulphur chlorides, metals, metallic sulphides, metallic oxides, alkalis or other basic materials.  Such modifying treatment may, if desired, be effected prior to the final washing, distillation or filtering operations.  Ingredient (b) may be a salt of calcium, magnesium, barium, strontium, aluminium, chromium, zinc, cadmium, cobalt, nickel, tin, silver or copper, and it may be a mahogany sulphonate. Alternatively, ingredient (b) may consist of mixed salts or of polyvalent metal salts in which the metal is combined with a plurality of differing negative radicles.  Examples of such salts are:-  <FORM:0693421/III/1> where R, R1 and R11 are the same or different organic radicles, M is a divalent metal, X, X1, X11 and X111 are selected from the group consisting of oxygen, sulphur and selenium.  A specific example of such a mixed salt is the calcium sulphonate-phenate derived from a petroleum sulphonic acid and a wax-substituted phenol.  The hydrocarbon lubricating oil may be a mineral lubricating oil or a synthetic hydrocarbon lubricating oil. The lubricating oil composition may contain additional ingredients such as pour-point depressors and extreme pressure additives.  In an example a mineral lubricating oil composition containing P2S5-treated turpentine and calcium mahogany sulphonate is described.  The Specification as open to inspection under Sect. 91 gives lists of (i) additional materials which may be used in modifying ingredient (a), (ii) additional sulphonic acids from which ingredient (b) may be prepared and (iii) radicles R and X present in the molecule of the sulphonate <FORM:0693421/III/2> which may be employed as ingredient (b).  Organic nitrogenous radicles are included in the list of radicles X.  It is also stated that animal or vegetable oils may be employed instead of hydrocarbon lubricating oil in the composition. This subject-matter does not appear in the Specification as accepted.