Patent GB-732781-A (GB)
Title: Improvements in or relating to oil-soluble derivatives of basic barium alkylated aryl sulphonates and lubricating and fuel oils containing the same
IPC: C10L1/24
Filed: 1951-12-27
Abstract: The invention comprises an oil-soluble carbonated compound obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of an oil-soluble basic barium salt of an aryl sulphonic acid possessing an alkyl substituent containing at least 8 carbon atoms, the said reaction being accompanied by the elimination of water of condensation.  The basic barium salts employed as starting materials may be represented by the general formula HO-Ba-SO3-R-(alkyl)n where R is an aromatic hydrocarbon residue derived from a group such as phenyl, tolyl, cumyl, tert.-butylphenyl, xylyl, cymyl, diphenylyl or naphthyl, "alkyl" is an alkyl group containing at least 8 carbon atoms and n is an integer not greater than 5.  The preferred alkyl substituent is a petroleum wax residue, especially one having a chain of 20 to 30 carbon atoms.  The desired products are obtained by dissolving a basic barium salt of an alkyl-substituted aryl sulphonic acid containing at least eight carbon atoms in the alkyl substituent in an inert organic dioxide and removing the water formed as by-product and the solvent also if the carbonated product is to be isolated.  In an example a basic barium salt of a di-wax alkylated benzene sulphonic acid is treated, in mineral oil solution, at reduced pressure and elevated temperature with carbon dioxide and the removal of the water formed is completed by further heating at reduced pressure.  About one mole of carbon dioxide is absorbed per two moles of the basic barium salt of the di-wax-alkylated benzene sulphonic acid.  The starting material is obtained by chlorinating paraffin wax containing an average of 23 carbon atoms in the molecule with gaseous chlorine at elevated temperature and treating benzene, in the presence of aluminium chloride with the product at elevated temperature.  The di-wax-alkylated benzene obtained is sulphonated with oleum, water and mineral oil are added and after further heating the oily layer is separated.  The latter is then heated with barium hydroxide octahydrate and the water is removed.  The product is further diluted with mineral oil.  Other carbonated products may be produced similarly by alkylating aromatic hydrocarbons such as benzene, toluene, cumene, xylene, diphenyl or naphthalene with other alkyl halides containing at least 8 and preferably not more than 30 carbon atoms, e.g. chlorkerosene and octadecyl chloride, sulphonating the product, forming the basic barium sulphonate and carbonating the latter.  The products are employed in lubricating and fuel oil compositions (see Group III).  Oil-soluble sulphurized and phosphorized dicyclic terpenes which may be used p  in the compositions are obtained by heating a dicyclic terpene such as pinene, camphene, fenchene and similar terpenes containing one double bond in the molecule and comprising two ring systems with a phosphorus sulphide, e.g. phosphorus pentasulphide is added to a heated mixture of pinene and mineral oil.ALSO:An oleaginous composition comprises a lubricating oil or hydrocarbon distillate oil and the oil-soluble carbonated compound obtained by reacting carbon dioxide with an oil-soluble basic barium salt of an aryl sulphonic acid possessing an alkyl substituent containing at least 8 carbon atoms with the elimination of water (see Group IV (b)).  The composition may include an oil-soluble phosphorized- and sulphurized-dicyclic terpene.  The basic barium salts used to prepare the carbonated compounds are represented by the general formula HO-Ba-SO3-R-(alkyl)n, where R is an aromatic hydrocarbon residue derived from a group such as phenyl, tolyl, cumyl, tert.-butylphenyl, xylyl, cymyl, diphenylyl or naphthyl, "alkyl" is an alkyl group containing at least 8 carbon atoms and n is an integer not greater than 5.  The preferred alkyl substituent is a petroleum wax residue especially one having a chain of 20 to 30 carbon atoms.  The lubricating oils employed may be mineral lubricating oils of the type normally used in internal combustion engines.  Hydrocarbon distillates derived from paraffinic, naphthenic, asphaltic or mixed base crudes as well as synthetic oils and white oils may also be used.  Mineral oil fractions used as fuel oils and Diesel fuels are mentioned.  Other agents which may be added to the lubricating compositions include dyes, pour-point depressants, soaps, corrosion inhibitors, antioxidants such as the zinc salts of dialkyl thiophosphonic acids, sulphurized phenols, thickeners, viscosity index improvers, defoamants, resins and graphite.  In examples: lubricant compositions are prepared containing di-wax alkylated benzene sulphonic acid and the basic barium salt thereof and are compared with similar compositions containing the product obtained by treating the basic barium sulphonate in mineral oil with carbon dioxide.  Mixtures of commercial oxidation inhibitors are also present in the compositions, e.g. a mineral oil solution of a phosphorus pentasulphide-pinene reaction product.  An oil soluble sulphurized and phosphorized dicyclic terpene is prepared in mineral oil and employed in mineral oil compositions containing the carbonated basic barium salt of the di-wax alkylated benzene sulphonic acid and a commercial oxidation inhibitor activator.