Patent GB-666695-A (GB)
Title: Improvements in or relating to lubricating compositions
IPC: C10M159/12
Filed: 1948-08-19
Abstract: Compounds which may contain halogen, sulphur and phosphorus are made by reacting a cyclic organic compound having an aliphatic double bond and a carbonyl radicle with hydrogen sulphide in the presence of ammonium hydrosulphide and treating the resulting product with an inorganic compound containing both phosphorus and halogen at an elevated temperature.  Preferably the final reaction is effected with a peroxide catalyst many of which are specified, including hydrogen-, benzoyl-urea- and alkali and alkaline earth metal peroxides and ascaridole.  Compounds containing a carbonyl radicle are those having the group >C = O and include ketones and acids and their esters and salts.  Many of these compounds are specified, representative being: cinnamic and abietic acids, cinnamaldehyde, pulegone, isophorone and bottoms obtained in the manufacture thereof and tall oil.  Esters used may be derived from alcohols or phenols and the salts may be metallic or derived from organic bases.  Preferred compounds are tall oil, ethyl cinnamate, cinnamaldehyde and isophorone bottoms, the latter being obtained as high molecular weight unsaturated ketonic residues containing at least 12 and preferably at least 18 carbon atoms in the molecule from the production of isophorone by condensing acetone in a caustic alkali solution, they may be further fractionated, e.g. to give a topped fraction containing at least 15 carbon atoms in the molecule or chemically treated, e.g. hydrolysed with dilute caustic alkali and acetone and isophorone so formed removed.  The hydrolysed product may be fractionated to give a topped product.  Many inorganic compounds containing both phosphorus and halogen are specified, representative being: PCl3, PFBr2, POF3, POFCl2, P2O3Cl4, PSCl3 and P2I4.  The first stage of the reaction is advantageously effected at room temperature or temperatures not exceeding 100 DEG  C. for one week to one month.  Proportions of hydrogen sulphide and ammonium hydrosulphide used should saturate the cyclic compound.  The ratio of the two sulphides may vary widely, the former preferably being in excess.  The molar ratio of sulphurized product to inorganic compound may vary widely, e.g. 1 : 1 to 1 : 8, the preferred ratio being 1 : 4, and in the final reaction specified temperatures are 100-200 DEG  C., preferably 150-170 DEG  C.  Inert solvents may be used. They are used as lubricant additives, c.f. Group III Abridgment. In examples, topped crude isophorone bottoms are reacted with hydrogen sulphide and ammonium hydrosulphide to give a product which is treated in the presence of di-tert.-butyl peroxide with (1) phosphorus pentachloride; and (2) phosphorus oxy-chloride. p Specifications 653,913 and 655,325 are referred to.  The Specification as open to inspection under Sect. 91 relates to the preparation of the derivatives from any organic compound and further classes of compounds are specified, e.g. acyclic, cyclic and aromatic hydrocarbons, cyclic terpenes, heterocyclic compounds, unsaturated and saturated aliphatic alcohols, aromatic alcohols, polyhydric aliphatic alcohols, cyclic alcohols, naturally occurring alcohols and synthetic alcohols, phenols, aliphatic acids and esters, aliphatic saturated and unsaturated and cyclic and poly ethers, aliphatic aldehydes and ketones, natural fats, oils and waxes and their derivatives and miscellaneous compounds such as petroleum fractions. Many compounds are specified in the above classes.  This subject-matter does not appear in the Specification as accepted.ALSO:A lubricating composition comprises a major proportion of a lubricating oil and a minor proportion, sufficient to stabilize the oil against deterioration, of a reaction compound having an alyhatic double bond product made by reacting a cyclic organic and a carbonyl radicle with hydrogen sulphide in the presence of ammonium hydrosulphide and treating the resulting product with an inorganic compound containing both phosphorus and halogen at an elevated temperature.  Compounds containing a carbonyl radicle are those with the group >C=O and include ketones and acids and their esters and salts.  Many of these compounds are specified, representative being cinnamic and abietic acids, tall oil, cinnamaldehyde, pulegone, and isophorone and bottoms obtained in the manufacture thereof by the condensation of acetone in the presence of caustic alkali.  The bottoms are of high molecular weight, are unsaturated cyclic ketones containing at least 12 and preferably at least 18 carbon atoms per molecule and may be fractionated or chemically treated, e.g. hydrolyzed, before conversion to an additive.  Many compounds containing both phosphorus and halogen are specified, representative being PCI3, PFBr2, POF3, POFCI2, P2O3CI4, PSCI3, P2I4.  The preparation of the additives is in Group IVb.  Lubricating oils indicated are mineral lubricating oils, oleaginous substances and synthetic lubricants of hydrocarbon or non-hydrocarbon origin. Preferred additives are derived from isophorone bottoms, ethyl cinnamate, tall oil and cinnamaldehyde.  The additives are multifunctional and have detergent, anti-ring sticking, anti-wear and extreme pressure properties and also inhibit oxidation and corrosion. They may be used in combination 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 diesters and alkaline earth diphenolates, lecithin, cephalin, rapeseed oil, voltolized fatty or mineral oils, and alkaline earth 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 and 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 fatty acid esters, sulphurized long chain olefines, sulphurized phosphorized fatty oils or acids, phosphorus acid esters with sulphurized organic radicles, chlorinated hydrocarbons and chlorinated esters of fatty acids the chlorine atom not being 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 alcohols.  Generally 5 per cent, preferably 0.1-2.0 per cent, of the additive is used in the composition and 0.01-2 per cent, e.g. 0.1-0.5 per cent, of other additive may be added.  Specifications 653,913 and 655,325 are referred to.  The Specification as open to inspection under Sect. 91 relates to the preparation of the derivatives from any organic compound and further classes of compounds are specified, e.g. acyclic, cyclic and aromatic hydrocarbons, cyclic terpenes, heterocyclic compounds, unsaturated and saturated aliphatic alcohols, aromatic alcohols, polyhydric aliphatic alcohols, cyclic alcohols, naturally occurring and synthetic alcohols, phenols, aliphatic acids, esters, aldehydes and ketones, aliphatic saturated and unsaturated and cyclic and poly ethers, natural fats, oils and waxes and their derivatives and miscellaneous compounds such as petroleum fractions. Many compounds are specified from the above classes.  This subject-matter does not appear in the Specification as accepted.