Patent GB-655325-A (GB)
Title: Improvements in or relating to lubricants and additives therefor
IPC: C10M135/02
Filed: 1947-12-22
Abstract: Lubricant additives are prepared by reacting an organic compound having an aliphatic double bond and/or a carbonyl radical with hydrogen sulphide in the presence of ammonium hydrosulphide and the absence of ammonium sulphide.  Preferred compounds include stilbene, oleic acid, ammonium, potassium, and ethyl oleates, ammonium and ethyl undecylenates, methyl ricinoleate, cottonseed, rapeseed, peanut, dehydrated castor, and tall oils, wax olefins, cinnamyl alcohol, pentanedione-2,4, saturated and unsaturated high molecular weight ketones, diacetone alcohol, mesityl oxide, ethyl cinnamate, cinnamaldehyde, and isophorone bottoms comprising unsaturated cyclic ketones of at least 12, and preferably more than 18 carbon atoms. The following classes of compounds are also exemplified: aliphatic hydrocarbons including olefins, cycloolefins and cyclo-dienes; aromatic hydrocarbons which may be substituted by alkyl, hydroxy, amino, nitro, nitroso, halogen, carboxyl or mercapto; cyclic terpenes and heterocyclic compounds which may be substituted; alcohols; phenolic compounds (eugenol); acids; esters; ethers, desirably vinyl allyl, and crotonyl ethers; aldehydes; ketones; natural fats, oils, and waxes; metal salts and organic base salts of any acidic materials listed above. Isophorone bottoms are obtained by alkali condensation of acetone, distillation, and purification of the residue.  They may be fractionated and each fraction reacted separately.  A fraction may be hydrolysed with caustic soda, distilled, and the bottoms purified and used as such or after topping.  Crude isophorone bottoms may also be condensed over sodium hydroxide to give resinous fractions.  The unsaturated ketones may be hydrogenated before reacting with hydrogen sulphide-ammonium hydrosulphide. The reaction may be effected in a solvent at room temperature for 1 week to 1 month or more or at elevated temperature up to 100 DEG  C. for 5 hours or more.  The product may be treated with a phosphorus sulphide and/or a sulphurizing agent, e.g. P2S5, P4S3, elementary sulphur, SCl2, S2Cl2, and alkali metal sulphides or polysulphides, at about 100-200 DEG  C. The products are added to oils preferably in amount of 0.1-2 per cent by weight.  In examples: (1) isopropyl alcohol is saturated with ammonia followed by hydrogen sulphide, a solution of topped, crude isophorone bottoms in isopropyl alcohol added, the solution saturated with hydrogen sulphide, and the container closed and left for a week. The product is filtered, solvent removed, and extracted with a non-aromatic hydrocarbon. It is heated with phosphorus sulphide at 60 DEG  C. rising to 160 DEG  C. and the product extracted with hydrocarbon; (2) an initial product is prepared as in (1), reaction time being 1 month; (3) the initial reaction is effected in an autoclave at 96-101.5 DEG  C. and the product treated with sulphur; (4) and (5) 3,5,5-trimethyl p  cyclohexene-2-one-1 and ethyl oleate are reacted as in (1).  The Specification as open to inspection under Sect. 91 comprises reaction products of organic compounds generally with hydrogen sulphide and ammonium hydrosulphide, compounds specified including aromatic hydrocarbons, alcohols, both saturated and unsaturated, monohydric and polyhydric, phenols and petroleum hydrocarbons. This subject-matter does not appear in the Specification as accepted.ALSO:Lubricant additives are prepared by reacting an organic compound having an aliphatic double bond and/or a carbonyl radical with hydrogen sulphide in the presence of ammonium hydrosulphide and the absence of ammonium sulphide.  Preferred compounds include stilbene, oleic acid, ammonium, potassium, and ethyl oleates, ammonium and ethyl undecylenates, methyl ricinoleate, cottonseed, rapeseed, peanut, dehydrated castor, and tall oils, wax olefins, cinnamyl alcohol, pentanedione-2,4, saturated and unsaturated high molecular weight ketones, diacetone alcohol, mesityl oxide, ethyl cinnamate, cinnamaldehyde and isophorone bottoms comprising unsaturated cyclic ketones of at least 12, and preferably more than 18 carbon atoms.  The following classes of compounds are also exemplified; aliphatic hydrocarbons including olefins, cyclo-olefins and cyclo-dienes; aromatic hydrocarbons which may be substituted by alkyl, hydroxy, amino, nitro, nitroso, halogen, carboxyl or mercapto; cyclic terpenes and heterocyclic compounds which may be substituted; alcohols; phenolic compounds (eugenol); acids; esters; ethers, desirably vinyl, allyl, and crotonyl ethers; aldehydes; ketones; natural fats, oils, and waxes; metal salts and organic base salts of any acidic materials listed above.  The product may be treated with a phosphorus sulphide and/or a sulphurizing agent, e.g. P2S5,P4S3, elementary sulphur, SCl2, S2Cl2, and alkali metal sulphides or polysulphides, at about 100 DEG  to 200 DEG  C. The products are added to mineral lubricating oils or synthetic lubricants of hydrocarbon or non-hydrocarbon origin, preferably in amount of 0.1-2 per cent by weight.  Other additions include blooming agents; pour point depressants; anti-foaming agents; detergents comprising metal or organic base salts of fatty, chlorinated fatty, resin, and aromatic acids, diphenols, sulphonic acids, sulphuric mono-esters, phosphoric, arsonic and antimony acid mono- and di-esters, alkaline earth phosphate di-esters and diphenolates, phosphatides, and especially the calcium salts of petroleum sulphonic acids and alkali salts of alkyl phenol-aldehyde condensation products; anti-oxidants such as alkyl phenols, amino phenols, and amines; corrosion inhibitors such as dicarboxylic acids of at least 16 carbon atoms, alkali and alkaline earth salts of sulphonic and fatty acids, and compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group; extreme pressure agents such as esters of phosphorus acids, aromatic sulphur compounds, sulphurized oils, esters, and olefins, sulphurized phosphorized oils, acids, and esters, chlorinated hydrocarbons and esters; urea or thiourea derivatives; polymerized olefins and unsaturated esters.  The Specification as open to inspection under Sect. 91 comprises reaction products of organic compounds generally with hydrogen sulphide and ammonium hydrosulphide, compounds specified including aromatic hydrocarbons, alcohols, both saturated and unsaturated, monohydric and polyhydric, phenols and petroleum hydrocarbons. This subject-matter does not appear in the Specification as accepted.