Patent GB-679466-A (GB)
Title: Improvement in lubricants and additional compositions therefor
IPC: C10M163/00
Filed: 1947-05-07
Abstract: Phospho-sulphurized, phosphorized or sulphurized organic materials are employed as ingredients in compositions for adding to lubricating oil (see Group III).  Materials mentioned are (i) those obtained by heating one of the following first with sulphur and then with P4S3: methyl oleate, lauryl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, glycerol trioleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lauryl ricinoleate, benzyl ricinoleate, methyl linoleate, oleyl acetate, lard oil, rapeseed oil, sperm oil, peanut oil, partially hydrogenated soyabean oil, partially hydrogenated linseed oil, partially hydrogenated tung oil, oleyl alcohol, turpentine, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax, fuel oil unsaturate prepared by dehydrochlorinating chlorinated fuel oil, white oil unsaturate prepared by dehydrochlorinating chlorinated white oil, cetene, oleic acid; (ii) those obtained by heating one of the following first with sulphur and then with P4S7: methyl oleate, phenyl oleate, benzyl oleate, castor oil; (iii) the phospho-sulphurized lard oil of (i) heated with P4S7; (iv) those obtained by heating one of the following with sulphur: methyl oleate, n-butyl oleate, benzyl oleate, thioamyl oleate, methyl ricinoleate, soyabean oil, linseed oil, tung oil, oleyl alcohol, cetene, di-isobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (v) those obtained by heating one of the following with PCl3: n-butyl alcohol, capryl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol, propyl cyclohexanol, mixture of methyl cyclohexanol and propyl cyclohexanol, capryl phenol, thiocapryl phenol, thiophenol, amyl mercaptan, decyl mercaptan, lauryl mercaptan, methyl cyclohexyl mercaptan, benzyl mercaptan, methyl lactate, sulphurized methyl ricinoleate; (vi) those obtained by heating one of the following with P4S3: oleic acid, palmitoleic acid, lard oil, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax; and (vii) those obtained by heating one of the following with P4S7: n-butyl alcohol, capryl alcohol, lauryl alcohol, oleyl alcohol, capryl phenol, oleic acid, linoleic acid, rapeseed oil, sperm oil, methyl oleate, glycol dioleate, hexadecene, caprylene, turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax.  Specifications 679,461, 679,462 and 679,465 are referred to.  The Specification as open to inspection under Sect. 91, gives lists of other organic compounds, including unsaturated hydrocarbons, alcohols, aldehydes, acids and their salts and esters, which may be phosphorized and/or sulphurized.  This subject-matter does not appear in the Specification as accepted.ALSO:A composition for adding to lubricating oil to improve its lubricating properties (especially to improve the oil in its use as a gear lubricant), comprises (a) an oil-soluble phospho-sulphurized organic material, (b) a separate oil-soluble organic phosphorus compound and (c) a separate oil-soluble organic halogen compound.  The composition may additionally include a separate organic sulphur compound and may also contain pour point depressors, solubilizing agents, viscosity improvers, detergents, soaps, thickeners or foam inhibitors.  The lubricating oil may be a mineral, animal, vegetable or synthetic oil.  Ingredient (a) is an organic material which has been treated with one or more reagents whereby both phosphorus and sulphur are imparted thereto. A list of such reagents is given.  Organic materials which may be phospho-sulphurized are fatty acids and esters thereof, and preferably the organic materials are unsaturated compounds. Phospho-sulphurized materials mentioned are (i) those obtained by heating one of the following first with sulphur and then with P4S3:-methyl oleate, lauryl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, glycerol trioleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lauryl ricinoleate, benzyltricinoleate, methyl linoleate, oleyl acetate, lard oil, rapeseed oil, sperm oil, peanut oil, partially hydrogenated soyabean oil, partially hydrogenated linseed oil, partially hydrogenated tung oil, oleyl alcohol, turpentine, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax, fuel oil unsaturate prepared by dehydrochlorinating chlorinated fuel oil, white oil unsaturate prepared by dehydrochlorinating chlorinated white oil, cetene, oleic acid; (ii) those obtained by heating one of the following first with sulphur and then with P4S7:-methyl oleate, phenyl oleate, benzyl oleate, castor oil; (iii) the phospho-sulphurized lard oil of (i) heated with P4S7.  Organic phosphorus compounds which may be employed as ingredient (b) are (1) those obtained by heating one of the following with Pcl3:-n-butyl alcohol, capryl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol, propyl cyclohexanol, mixture of methyl cyclohexanol and propyl cyclohexanol, capryl phenol, thiocapryl phenol, thiophenol, amyl mercaptan, decylmercaptan, lauryl mercaptan, methyl cyclohexyl mercaptan, benzyl mercaptan, methyl lactate, sulphurized methyl ricinoleate; (2) those obtained by heating one of the following with P4S3:-oleic acid, palmitoleic acid, lard oil, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax; (3) those obtained by heating one of the following with P4S7:-n-butyl alcohol, capryl alcohol, lauryl alcohol, oleyl alcohol, capryl phenol, oleic acid, linoleic acid, rapeseed oil, sperm oil, methyl oleate, glycol dioleate, hexadecene, caprylene, turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax.  Organic halogen compounds which may be employed as ingredient (c) are (i) shlorination products of one of the following:-diphenyl, diphenyl ether, naphthalene, methyl cyclohexane, cyclohexanone, paraffin wax, kerosene, foots oil, stearic acid, phenyl stearic acid; or (ii) one of the following:-hexachlorethane, unsym di-(p-chlorphenyl) dichlorethylene, dichlorstearic acid, methyl dichlorstearate, o-dichlorbenzene, hexachlor diphenyl ether, trichlor diphenyl ether, dehydrochlorinated D.D.T., dibutyl chlorphthalate, methyl chlorsalicylate.  Organic sulphur compounds which may be present in the composition are (1) those obtained by heating one of the following with sulphur:-methyl oleate, n-butyl oleate, benzyl oleate, thioamyl oleate, methyl ricinoleate, soyabean oil, linseed oil, tung oil, oleyl alcohol, cetene, diisobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (2) one of the following disulphides:- di-t-butyl, dihexyl, dioctyl, diphenyl, dibenzyl, di (chlorbenzyl), di (chlorphenyl), dixylyl, phenyl amyl; (3) one of the following tri- or tetra-sulphides:-butyl, lauryl, cetyl, benzyl, xylyl; (4) one of the following tetrathiophosphates:-lauryl, keryl, benzyl; or (5) thanthrene. Detergents mentioned are calcium salts of chlorinated mahogny acids. Foam inhibitors mentioned are the silicone polymer known commercially as Dow Corning 200 and the chlorination product of this silicone polymer.  The Specification contains 33 examples of suitable compositions.  Specifications 679,461, 679,462 and 679,465 and U.S.A. Specification 2,042,880 are referred to.