Patent GB-675174-A (GB)
Title: Improvements in lubricating composition
IPC: C10M159/18
Filed: 1948-02-05
Abstract: Salts of acidic reaction products obtained by reacting an organic hydroxy compound with a reagent containing both phosphorus and sulphur or selenium are employed as additives in lubricating compositions (see Group III).  The acidic reaction products are preferably obtained by the reaction of phosphorus pentasulphide, phosphorus trisulphide, phosphorus pentaselenide or phosphorus triselenide with cycloaliphatic alcohols.  Cycloaliphatic alcohols mentioned include cyclohexanol, hydrocarbonsubstituted cyclohexanols, cyclic alcohols of the naphthenyl type, hydroxy derivatives of the terpenes, menthenes and menthanes such as the terpineols, menthol, camphor (which reacts in the enol form) and hydroxy derivatives of pinene, limonene or camphene, sterols and hydrogenated phenolic compounds.  Lists of suitable cycloaliphatic alcohols, and of substituent groups which may be present in their molecules, are given.  Mixtures of cycloaliphatic alcohols, such as those obtained by the hydrogenation of commercial cresol, may also be employed.  The salt of the acidic reaction product may be an organic or inorganic salt, but the salts of zinc, cadmium, magnesium, calcium, barium, strontium, aluminium, chromium, cobalt, nickel or copper are preferred.  In the examples, P2S3-treated methyl cyclohexanol or P2Se5-treated methyl cyclohexanol is converted to its zinc or cadmium salt by reaction with zinc oxide or cadmium oxide.  The Specification as open to inspection under Sect. 91, refers to the treatment of methyl cyclohexanol with P2S5 and the conversion of the acidic reaction product thus obtained to its zinc salt by first neutralizing with caustic soda and then adding zinc chloride solution.  This subject-matter does not appear in the Specification as accepted.ALSO:A lubricating composition especially suitable for the lubrication of internal combustion engines, whether of the spark-ignition or of the diesel type, comprises a major proportion of a hydrocarbon lubricating oil together with (a) a detergent which is an oil-soluble organic compound containing the radicle XM, where M is a metal and X is oxygen, sulphur or selenium and (b) a salt of an acidic reaction product obtained by reacting an organic hydroxy compound with a reagent containing both phosphorus and sulphur or selenium.  The use of the zinc salts of the reaction products of phosphorus pentasulphide with cycloaliphatic alcohols as ingredient (b) is excluded.  The hydrocarbon lubricating oil may be of mineral or synthetic origin.  Detergents mentioned are metallic alcoholates, phenates, carboxylates and the corresponding thio compounds, salt-esters of sulphuric and sulphurous acids and the corresponding thio acids, and the salts of phosphonic, phosphinic, sulphonic and sulphinic acids and the corresponding thio acids.  The detergent may have the general formula R (n-2a-b) XaY (X1M)b where R is a radicle selected from the class consisting of R1-and R1-X11 in which R1 is an organic radicle; X, X1 and X11 are the same as different elements of the class consisting of oxygen, sulphur and selenium, X when present being connected to Y by a double bond; M is a metal such as calcium, magnesium, barium, berylbum, strontium, aluminium, chromium, zinc, cadmium, cobalt, tin, nickel or copper; Y is an acid-forming element such as phosphoros, arsenic, sulphur, selenium, silicon or boron; n is the valency of Y, a is an integer which may be zero; b is an integer which is at least one; and (n-2a-b) is at least one.  Lists of suitable radicles R1 and of specific detergents are given. As regards ingredient (b), the acidic reaction products are preferably obtained by the reaction of phosphorus pentasulphide, phosphorus trisulphide, phosphorus pentaselenide or phosphorus triselenide with cycloaliphatic alcohols.  Cycloaliphatic alcohols mentioned include cyclohexanol, hydrocarbon - substituted cyclohexanols, cyclic alcohols of the naphthenyl type, hydroxy p  derivatives of the terpenes, menthenes and menthanes such as the terpineols, menthol, camphor (which reacts in the enol form) and hydroxy derivatives of pinene, limonene or camphene, sterols and hydrogenated phenolic compounds.  Lists of suitable cycloaliphatic alcohols, and of substituent groups which may be present in their molecules, are given.  Mixtures of cycloaliphatic alcohols, such as those obtained by the hydrogenation of commercial cresol, may also be employed. Ingredient (b) may be an organic or inorganic salt of the acidic reaction product, but the salts of zinc, cadmium, magnesium, calcium, barium, strontium, aluminium, chromium, cobalt, nickel or copper are preferred.  In the examples, mineral lubricating oil compositions are described containing the calcium, magnesium or cadmium salt of P2S5-treated cyclohexanol, the calcium or magnesium salt of P2S5-treated amyl cyclohexanol, the calcium, magnesium or zinc salt of P2S5-treated octyl alcohol, the zinc salt of P2S5-treated butanol, the zinc salt of P2S5-treated isoamyl alcohol or the zinc salt P2S5-treated lauryl alcohol together with (i) calcium p-cetyl phenate with or without calcium cetyl phosphate, (ii) aluminium n-butoxide and calcium cetyl phosphate or calcium mahogany sulphonate, (iii) calcium mahogany sulphonate with or without the calcium phenate of p-t-amyl phenol monosulphide or the calcium salt of a formaldehyde-p-t-amyl phenol condensation product, (iv) calcium salt of a carboxylic acid obtained by the oxidation of a petroleum fraction and the calcium phenate of p-t-amyl phenol monosulphide, (v) magnesium phenate of lauryl salicylate, (vi) calcium 10-phenyl stearate (vii) cobaltuns 10-p-chlorphenyl stearate.  In further examples, mineral lubricating oil compositions are described containing (A) zinc salt of P2S3-treated methylcyclohexanol and calcium p-cetyl pherate, (B) cadmium salt of P2S5-treated methyl-cyilohexanol and calcium mahogany sulphonate (C) cadmium salt of P2S3-treated methylcyclohexanol and magnesium phenate of lauryl salicylate (D) zinc salt of P2Se5-treated methylcyclohexanol and calcium p-cetyl phenate and (E) cadmium salt of P2Se5-treated methylcylclohexanol and calcium mahogany sulphonate. Specification 665,107 is referred to.  The Specification as open to inspection under Sect. 91, refers to a lubricating composition comprising a major proportion of a hydrocarbon lubricating oil together with (a) a detergent and (b) a salt of an acidic reaction product obtained by reacting an organic hydroxy compound with a reagent containing both phosphorus or arsenic and sulphur or selenium.  The use of the zinc salt of P2S5-treated methylcyclohexanol as ingredient (b) is mentioned.  This subject-matter does not appear in the Specification as accepted.