Patent GB-666227-A (GB)
Title: Improvements in or relating to lubricating compositions
IPC: C10M159/12
Filed: 1948-08-19
Abstract: Cyclic ketone fractions having at least 12 C atoms in the molecule are reacted at 170-350 DEG  F. with a sulphur-free phosphorizing agent and the product thus made is reacted in a substantially inert atmosphere at 250-450 DEG  F. with a sulphurizing agent.  The final product may be converted to a salt by treatment with a metal or a basic substance.  The ketone fractions may be obtained from isophorone bottoms during its synthesis from acetone and are then unsaturated.  Thus acetone may be condensed in 30-60 per cent caustic alkali at 260-338 DEG  F. and 300-500 p.s.i., the product distilled to remove ketones containing less than 12 C atoms and to obtain a residue which may be purified and/or fractionated before or after hydrolysis with dil.NaOH or hydrogenation.  Other cyclic ketones specified are a condensation product of diisobutyl ketone containing more than 12 C atoms, dibutyl cyclohexanone and alkyl substituted carvomethones, menthones, pulegones, carvones and camphors having at least 12 C atoms.  Phosphorizing agents specified are phosphorus, phosphorus halides, oxyhalides, oxides, metallic phosphides, e.g. sodium or tin phosphide, phosphoric acid anhydride especially when used with acetyl chloride, and phosphoric acid.  Phosphorus and its pentoxide are preferred.  An inert solvent may be used and reaction effected under inert conditions.  The preferred temperature range is 200-300 DEG  F. and initially the temperature should be raised slowly.  Mol. ratios of phosphorizing agent to ketone quoted are 1 : 2 to 1 : 8.  The product may be purified before sulphurization. Sulphurization agents specified are sulphur, flowers of sulphur, sulphur halides, alkali polysulphides, ammonium hydrogen sulphide-hydrogen sulphide and sulphur dioxide.  Mol. ratios quoted for sulphurizing agent/phosphorized product are 0.5/1 to 1/1. Depending on the quantity of sulphurizing agent used all or part of the phosphorus in the phosphorized ketone may be replaced although in the former instance phosphorus remains entrained in the final product.  The latter may be treated with a hydroxide, oxide or carbonate of an alkaline earth metal, alkali metal, heavy metal, e.g. Al, Cr, Fe and Sn or other basic reagents such as ammonia, alkyl or aryl amines and quatammonium compounds.  Preferred reagents are compounds of Ca, Ba, Mg, Na, K, Al and Zn.  The products are used as oil additives; stabilizers and anti-oxidants for rubber, fuels, fatty oils and greases (cf. Groups III and V).  In examples (1) a mixture of cyclic unsaturated ketones containing at least 15 C atoms in the molecule obtained by tapping crude isophorone bottoms at a still lead temperature of 284 DEG  F. and 10 m.ms.  Hg pressure are heated for 5 hours initially at 140 DEG  F. and then at 300 DEG  F. in CO2 with P2O5, the product extracted with a non-aromatic hydrocarbon and solvent removed in a current of CO2 when the phosphorized product is dispersed in a light hydrocarbon oil and reacted with sulphur for 2-4 hours at 350-400 DEG  F., the sludge formed is removed and the product recovered by extraction; (2) is a repeat of (1) using phosphorus in place of P2O5 and in (3) the reaction product of (2) dissolved in mineral lubricating oil is treated at about 190-212 DEG F. with lime and after heating for 2-3 hours is filtered and reheated at 250-270 DEG  F. whilst nitrogen is passed through to remove foreign matter and a calcium salt concentrate is thus obtained suitable for use on dilution as a lubricant additive.  Specifications 653,913 and 655,325 are referred to.ALSO:Lubricant and fuel stabilizers are made by phosphorizing and sulphurizing cyclic ketones containing at least 12 C atoms in the molecule.  The process consists in reacting the ketone with a sulphur-free phosphorizing agent at 170-350 DEG F and treating the product thus obtained with a sulphurizing agent at 250-450 DEG F.  The final product may be converted to a salt by treatment with a metal or basic substance. For details of the preparation (see Group IV(b)).  Ketones specified are fractions derived from isophorone manufacture, preferably having at least 18 C atoms per molecule, a condensation product of di-isobutyl ketone, dibutyl cyclohexanone and alkyl substituted carvomenthenes, menthones, carvones and camphors having more than 12 C atoms per molecule.  Oils listed include mineral lubricating oils and synthetic lubricants of hydrocarbon and non-hydrocarbon origin and those specified are heavy-duty, motor, diesel, aviation and synthetic oils.  The additives may be used in amounts of up to 5 per cent, e.g. 0.1-2.0 per cent of the base lubricant.  They are multi-functional and have antiring sticking, antiwear and detergent properties and inhibit corrosion and oxidation.  They may be used in conjunction with other additives many of which are listed, representative being oil-soluble detergents, e.g. metal and organic base salts of detergent-forming acids, alkaline earth phosphate di-esters and alkaline earth diphenolates, lecithin, cephalin, rapeseed oil, voltolized fatty or mineral oils and alkaline metal salts of alkyl phenol-aldehyde condensation products; anti-oxidants, e.g. alkyl phenols, amino-phenols and amines; corrosion inhibitors, e.g. dicarboxylic acids of 16 or more carbon atoms per molecule, salts of sulphonic or fatty acids and organic compounds containing an acidic radicle close to a nitrile, nitro or nitroso group; extreme pressure agents, e.g. esters of phosphorus acids, neutral aromatic sulphur compounds, sulphurized fatty oils or esters of fatty acids, sulphurized long chain olefines, sulphurized phosphorized fatty oils or acids, phosphorus acid esters with sulphurized p  organic radicles, chlorinated hydrocarbons and chlorinated esters of fatty acids with the chlorine atom not in the alpha position; other compounds present may be oil-soluble urea or thiourea derivatives; polyisobutylenes and unsaturated polymerized esters of fatty acids and monohydric alchohols.  The additional additives may be used in amounts of 0.01-2.0 per cent, e.g. 0.1-0.5 per cent.  Specifications 653.913 and 655.325 are referred to.