Patent GB-679461-A (GB)
Title: Improvement in lubricants and additive 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, butyl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, thio-methyl oleate, chlorbenzyl oleate, methyl ricinoleate, methyl palmitoleate, methyl linoleate, oleyl acetate, lard oil, wax unsaturate prepared by dehydrochlorinating chlor wax, fuel oil unsaturate prepared by dehydrochlorinating chlorinated fuel oil, white oil unsaturate prepared by dehydrochlorinating chlorinated white oil, cetene, oleic acid, linoleic acid, abietic acid; (ii) those obtained by heating one of the following first with sulphur and then with P4S7; methyl oleate, phenyl oleate, benzyl oleate, methyl palmitoleate; (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, phenyl oleate, benzyl oleate, naphthenyl oleate, tethyl cyclohexyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lard oil, castor oil, rapeseed oil, soyabean oil, sperm oil, cottonseed oil, linseed oil, tung oil, oleyl alcohol, cetene, isobutylene, di-isobutylene, wax unsaturate prepared by dehydrochlorinating chlor wax; (v) those obtained by heating one of the following with PCl3: n-butyl alcohol, capryl alcohol, oleyl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol {the product in this case being predominantly tri-(methyl cyclohexyl) phosphite}, capryl phenol, thiocapryl phenol, thiophenol, amyl mercaptan, lauryl mercaptan, cyclohexyl mercaptan, methyl cyclohexyl mercaptan, benzyl mercaptan, sulphurized methyl ricinoleate; (vi) those obtained by heating one of the following with P4S3: oleic acid, palmitoleic acid, hexadecene, methyl cyclohexanol, wax unsaturate prepared by dehydrochlorinating chlor wax; (vii) those obtained by heating one of the following with P4S7: capryl alcohol, oleyl alcohol, capryl phenol, oleic acid, linoleic acid, rapeseed oil, sperm oil, partially hydrogenated linseed oil, hexadecene, caprylene, turpentine, wax unsaturate produced by dehydrochlorinating chlor wax, or (viii) (dicapryl phenyl) (diethyl) phosphite prepared by heating dicapryl phenol with PCl3 and reacting the product with ethyl alcohol. Specifications 679,462, 679,465 and 679,466 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 sulphur compound and (c) a separate oil-soluble phosphorus compound.  The composition may additionally have chemically-combined halogen present therein and may also contain detergents, soaps, thickeners or foam inhibitors.  The lubricating oil to which the composition may be added may be of mineral, animal, vegetable or synthetic origin.  Ingredient (a) is an organic material which has been treated with one or more reagents whereby both phosphorus and sulphur are imparted thereto.  Organic materials which may be phosho-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, butyl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, thiomethyl oleate, chlorbenzyl oleate, methyl ricinoleate, methyl palmitoleate, methyl linoleate, oleyl acetate, lard oil, wax unsaturate prepared by dehydrochlorinating chlor wax, fuel oil unsaturate prepared by dehydrochlorinating chlorinated oil, white oil unsaturate prepared by dehydrochlorinating chlorinated white oil, cetene, oleic acid, linoleic acid, abietic acid; (ii) those obtained by heating one of the following first with sulphur and then with P4S7:-methyl oleate, phenyl oleate, benzyl oleate, methyl palmitoleate; (iii) the phospho-sulphurized lard oil of (i) heated with P4S7.  Organic sulphur compounds which may be employed as ingredient (b) are (1) those obtained by heating one of the following with sulphur: - methyl oleate, n-butyl oleate, phenyl oleate, benzyl oleate, naphthenyl oleate, methylcyclohexyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lard oil, castor oil, rapeseed oil, soya-bean oil, sperm oil, cottonseed oil, linseed oil, tung oil, oleyl alcohol, cetene, isobutyl-lene, di-isobutylene, wax unsaturate prepared by dehydrochlorinating chlor wax; (2) one of the following disulphides:-dibutyl, di-t-butyl, diamyl, dihexyl, dioctyl, dilauryl, dicyclohexyl, diphenyl, dibenzyl di (chlorbenzyl), ditolyl, dixylyl, phenylamyl, chlorphenyl ethyl; (3) one of the following tri- or tetra-sulphides butyl, lauryl, cetyl, benzyl, xylyl; (4) one of the following tetrathiophosphates:-amyl, lauryl, keryl, benzyl; or (5) thianthrene. Organic phosphorus compounds which may be employed as ingredients (c) are (i) those obtained by heating one of the following with PCl3:-n-butyl alcohol, capryl alcohol, oleyl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol, (the product in this case being predominantly tri-(methyl cyclohexyl) phosphite), capryl phenol, thiocapryl phenol, thiophenol, amyl mercaptan, lauryl mercaptan, cyclohexyl mercaptan, methyl cyclohexyl mercaptan, benzyl mercaptan, sulphurized methyl ricinoleate; (ii) those obtained by heating one of the following with P4S3:-oleic acid, palmitoleic acid, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlor wax; (iii) those obtained by heating one of the following with P4S7:-capryl alcohol, oleyl alcohol, capryl phenol, oleic acid, linoleic acid, rapeseed oil, sperm oil, partially hydrogenated linseed oil, hexadecene, caprylene, turpentine, wax unsaturate produced by dehydrochlorinating chlor wax; or (iv) (dicapryl phenyl) (diethyl) phosphite.  Halogen compounds which may be present as an ingredient of the composition in order to introduce chemically-combined halogen are (1) halogenated diphenyl ether, particularly a chlorinated diphenyl ether, e.g. hexachlor diphenyl ether; (2) chlorination products of one of the following:-diphenyl) dichlorethylene dichlorstearic cyclohexanone, paraffin wax, kerosene, foots oil; or (3) one of the following:-hexachlorethane, unsym. di-(p-chlorphenyl, naphthalene, methyl cyclohexane, acid, methyl dichlorstearate, o-dichlorbenzene.  Detergents mentioned are the calcium salts of mahogany acids or of chlorinated mahogany 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 70 examples of suitable compositions.  Specifications 679,462, 679,465 and 679,466, and U.S.A. Specification 2,042,880 are referred to.