Patent GB-693422-A (GB)
Title: Improvements in lubricant improving agent and lubricant containing same
IPC: C10M159/12
Filed: 1948-02-05
Abstract: An additive for lubricating oils (see Group III) is obtained by reacting an unsaturated hydrocarbon or hydrocarbon material with a phosphorus-and sulphur-containing compound at an elevated temperature and then stabilizing the reaction product by treatment with alcohols or with basic materials such as metallic oxides and alkalies (metallic bases) or by treatment with halogen.  The reaction product may also be stabilized by carrying out the reaction in the presence of alkali and may be further improved by physical steps such as washing, air-blowing, distilling and filtering either separately or in combination.  A long list of suitable unsaturated hydrocarbons is given and this includes polymerized olefines, e.g. polymerized allene, polymerized butadiene, and polymerized methyl-butadienes and acetylenes.  The phosphorus-and sulphur-containing compound is preferably a sulphide of phosphorus, e.g. the sesquisulphide, trisulphide, heptasulphide, disulphide, and especially the pentasulphide, but the following may also be used:-compounds of phosphorus, sulphur, and halogen, e.g. the thio chlorides (PSCl2 and PSCl), thio bromides, thio fluoride, and thio bromochloride (PSBrCl2); compounds of phosphorus, sulphur and oxygen, e.g. the sulphoxide (P4S4O6), compounds of phosphorus, sulphur, and elements other than oxygen or halogen, e.g., the thiocyanate or the thioamide PS(NH2)3; inorganic thio-acids of phosphorus, e.g. mono-(di, tri- or tetra-) thio-phosphoric acid, and the mono-, di-, and tri-thio-phosphorous acids; organic thio acids of phosphorus, e.g. thio-phosphonic and thiophosphinic acids.  The phosphorus-and sulphur-containing compound may be added directly to the hydrocarbon or the hydrocarbon, the compound, or both, may be dissolved in or diluted with an inert solvent.  If the reaction is endothermic one of the following substances may be added as catalyst: anhydrous aluminium or ferric chloride, boron trifluoride, hydrogen fluoride, iodine, hydrogen iodide, sulphuric acid, sulphur trioxide, phosphoric acid, and phosphorus pentoxide, or a mixture thereof.  The stabilized products may be added to a hydrocarbon lubricating oil which may be a mineral lubricating oil or a synthetic hydrocarbon oil.  The lubricating oil composition may also contain a detergent and conventional pour-point depressors and extreme pressure additives. Specifications 597,338 and 693,421, [Group IV (b)], are referred to. The Specification as open to inspection under Sect. 91 include the stabilization treatment as an optional feature and includes the following additional methods of stabilizing the reaction product:-treatment with acids, benzyl chloride, phosphorus, phosphorus chlorides, sulphur, sulphur chlorides, metals, or with metallic sulphides.  It is also stated that the lubricating oil base may be any lubricating oil.  This subject-matter does not appear in the Specification as accepted.ALSO:An additive for lubricating oils (see Group III) is obtained by reacting an unsaturated hydrocarbon or hydrocarbon material with a phosphorus-and-sulphur-containing compound at an elevated temperature and then stabilizing the reaction product by treatment with alcohols or with basic materials such as metallic oxides and alkalies (metallic bases) or by treatment with halogen.  The reaction product may also be stabilized by carrying out the reaction in the presence of alkali and may be further improved by physical steps such as washing, air-blowing, distilling and filtering either separately or in combination.  The preferred unsaturated hydrocarbons are the unsaturated cycloaliphatic hydrocarbons and particularly the unsaturated bridge ring hydrocarbons, especially the cyclic terpenes, e.g. turpentine and alpha-pinene.  A long list of suitable unsaturated hydrocarbons is given and this includes acyclic hydrocarbons, comprising mono-olefines, poly-olefines (e.g. di-olefines), polymerized olefines (see Group IV (a)) and acetylenes; cyclic hydrocarbons comprising cycloaliphatic hydrocarbons, derivatives of menthane, e.g. p-menthenes, cyclic terpenes, e.g. m- and p-menthadienes, bridged ring hydrocarbons, e.g. the bicyclic terpenes, condensed ring hydrocarbons, hydro-aromatic hydrocarbons, aromatic hydrocarbons, and naturally occurring or commercially available complex compositions consisting principally of hydrocarbons, including products derived from petroleum containing a high proportion of unsaturated hydrocarbons, e.g. those which may be extracted from petroleum fractions by distillation or solvent extraction or by cracking or dehydrogenation, e.g. by halogenation followed by dehydrohalogenation.  Hydrocarbon materials of non-mineral origin, e.g. hydrocarbon products of vegetable origin such as certain oils obtained from the distillation of wood, e.g. retene oil, turpentine and pine oil, may also be used.  Examples of each of the above classes of hydrocarbons are given, the cyclic hydrocarbons specified including cyclobutene, cyclopentene, cyclopentadiene, carvomenthene, p-menthene-3, p-menthene-1(7), p-menthene-4(8), terpinenes, phellanthrenes, terpinolene, dipentene, carvestrene, sylvestrene, alpha- and beta-pinenes, bornylene, camphenes, alpha- and beta-fenchenes, fenchylene, thujenes, sabinene, carenes, sautene, camphenilene, benzene, diphenyl, naphthalene, anthracene, phenanthrene, and styrene.  The phosphorus-and-sulphur-containing compound is preferably a sulphide of phosphorus, e.g. the sesquisulphide, trisulphide, heptasulphide, disulphide, and especially the pentasulphide, but the following may also be used:-compounds of phosphorus, sulphur, and halogen, e.g. the thiochlorides (PSCl3 and PSCl), thiobromides, thiofluoride, and thiobromochloride (PSBrCl2); compounds of phosphorus, sulphur and oxygen, e.g. the sulphoxide (P4S4O6), compounds of phosphorus, sulphur, and elements other than oxygen or halogen, e.g. the thiocyanate or the thioamide PS(NH2)3; inorganic thio-acids of phosphorus, e.g. mono-(di-, tri, or tetra-)-thio-phosphoric acid, and the mono-, di-, and tri-thio-phosphorous acids; organic thio-acids of phosphorus, e.g. thiophosphonic and thiophosphinic acids.  The phosphorus-and-sulphur-containing compound may be added directly to the hydrocarbon or the hydrocarbon, the compound, or both, may be dissolved in or diluted with an inert solvent.  If the reaction is endothermic one of the following substances may be added as catalyst:-anhydrous aluminium- or ferric-chloride, boron trifluoride, hydrogen fluoride, iodine, hydrogen iodide, sulphuric acid, sulphur trioxide, phosphoric acid, and phosphorus pentoxide, or a mixture thereof.  In examples: (1) turpentine is heated and phosphorus pentasulphide then added gradually and the reaction product heated for a further period and then diluted with light mineral oil and a filter aid material consisting of a fine white powder of silica gel then added and the resulting oil concentrate filtered white hot.  The reaction product may be stabilized by treatment with a minor amount, e.g. from 0.1 to 10 per cent by weight of a normal alcohol having at least four carbon atoms or by alkali treatment; (2) turpentine is heated with phosphorus pentasulphide and after cooling the product to 70-75 DEG  C. butanol is added with stirring and the product is then filtered from light mineral oil using a filter aid as in (1); (3) turpentine is mixed with pellets of caustic soda, the mixture heated and phosphorus pentasulphide added gradually, the product being then diluted with light mineral oil and filtered with the aid of a filter aid material as in (1); similar results may be obtained by first forming the reaction product in the absence of alkali and then treating with alkali and in this case the reaction product may be diluted with mineral oil before treatment with caustic alkali; (4) a saturated wax hydrocarbon is chlorinated with dry chlorine gas under strong light and the chlorowax then dehydrochlorinated with a suitable dehydrochlorination catalyst, e.g. pumice stone, at elevated temperature to yield an unsaturated wax product.  The latter is then heated with phosphorus pentasulphide and the product cooled and filtered through a thin layer of filter aid; the product is then stabilized by one of the methods defined.  When the reaction products are stabilized by treatment with halogen it is preferred to use chlorine, e.g. by bubbling chlorine gas through the product at 20-100 DEG  C., the product being preferably chlorinated so as to contain from 5 to about 20 per cent by weight of combined chlorine and the chlorination step is preferably followed by treatment such as air blowing and alkali washing for removing any excess chlorine or hydrogen chloride.  The product of example (4) above is particularly suitable for such chlorination treatment. Specifications 597,338 and 693,421 are referred to.  The Specification as open to inspection under Sect. 91 includes the stabilization treatment as an optional feature and includes the following additional methods of stabilizing the reaction product:-treatment with acids, benzyl chloride, phosphorus, phosphorus chlorides sulphur, sulphur chlorides, metals, or with metallic sulphides, whilst the list of materials which may be reacted with the phosphorus-and-sulphur-containing compounds includes alphasantalol.  This subject-matter does not appear in the Specification as accepted.ALSO:A lubricating composition comprises a hydrocarbon lubricating oil and an additive obtained by reacting an unsaturated hydrocarbon or hydrocarbon material with a phosphorus-and-sulphur-containing compound at an elevated temperature and then stabilizing the reaction product by treatment with alcohols or with basic materials such as metallic oxides and alkalies (metallic bases) or by treatment with halogen.  The reaction product may also be stabilized by carrying out the reaction in the presence of alkali and may be further i