Patent GB-679465-A (GB)
Title: Improvement in lubricant improving agent and lubricant containing same
IPC: C10M163/00
Filed: 1947-05-07
Abstract: Phosphor-sulphurized, phosphorized or sulphurized organic materials are employed as ingredients in lubricating oil compositions (see Group III).  Materials mentioned are (i) those obtained by heating one of the following first with sulphur and then with P4S3: methyl oleate, ethyl oleate, propyl oleate, butyl oleate, capryl oleate, lauryl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate chlorbenzyl oleate, methyl ricinoleate, ethyl ricinoleate, butyl ricinoleate, lauryl ricinoleate, benzyl ricinoleate, methyl palmitoleate, butyl palmitoleate, methyl linoleate, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax; (ii) those obtained by heating one of the following first with sulphur and then with P4S7: methyl oleate, phenyl oleate, benzyl-oleate, propyl ricinoleate; (iii) those obtained by heating one of the following with sulphur: methyl oleate, ethyl oleate, butyl oleate, capryl oleate, phenyl oleate, benzyl oleate, methyl cyclohexyl oleate, naphthenyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, ethyl ricinoleate, lard oil, cottonseed oil, linseed oil, rapeseed oil, sperm oil, castor oil, mustard oil, neats-foot oil, olive oil, peanut oil, soyabean oil, partially hydrogenated linseed oil, partially hydrogenated tung oil, oleyl alcohol, cetene, isobutylene, diisobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (iv) those obtained by heating one of the following with PCl3: n-butyl alcohol, capryl alcohol, oleyl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol, mixture of methyl cyclohexanol and propyl cyclohexanol, thiocapryl phenol, thiophenol, amyl mercaptan, decyl mercaptan, lauryl mercaptan, cyclohexyl mercaptan, methyl cyclohexyl mercaptan, benzyl mercaptan, methyl lactate, sulphurized methyl ricinoleate; (v) those obtained by heating one of the following with P4S3: oleic acid, palmitoleic acid, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax, propyl oleate, lard oil; and (vi) 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, methyl oleate, glycol dioleate, rapeseed oil, sperm oil, partially hydrogenated linseed oil, octene, turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax.  Specifications 679,462, 679,464 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 lubricating composition especially suitable for use as a gear lubricant in automotive vehicles comprises a lubricating oil together with (a) an oil-soluble phosphosulphurized material produced by treating, with a phosphorus- and sulphur-containing reagent, a sulphurized ester derived from an unsaturated aliphatic acid and an organic hydroxy or mercapto compound containing one or two -OH or -SH groups, (b) a separate oil-soluble organic phosphorus compound wherein the phosphorus present has a valance of less than 5 and (c) a separate organic sulphur compound having an active sulphur content which satisfies the requirements of a table in the Specification.  The lubricating oil may be a mineral, animal, vegetable or synthetic oil.  The composition may additionally have chemically-combined halogen present therein and may also contain pour point depressors, solubilizing agents, viscosity improvers, detergents, soaps, thickeners or foam inhibitors.  Specific examples of ingredient (a) mentioned are (i) the products obtained by heating one of the following first with sulphur and then with P4S3:-methyl oleate, ethyl oleate, propyl oleate, butyl oleate, capryl oleate, lauryl oleate, oleyl oleate, benzyl oleate, naphthenyl oleate, methyl cyclohexyl oleate, phenyl oleate, glycol dioleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, chlorbenzyl oleate, methyl ricinoleate ethyl ricinoleate, butyl ricinoleate, lauryl ricinoleate, benzyl ricinoleate, methyl palmitoleate, butyl palmitoleate, methyl linoleate; and (ii) those obtained by heating one of the following first with sulphur and then with P4S7:- methyl oleate, phenyl oleate, benzyl oleate, propyl ricinoleate.  The various types of compounds which may be employed as ingredient (b) are discussed and the specific examples of ingredient (b) mentioned are (1) the products obtained by heating one of the following with PCl3: n-butyl alcohol, capryl alcohol, oleyl alcohol, sulphurized oleyl alcohol, cyclohexanol, methyl cyclohexanol, mixture of methyl cyclohexanol and propyl cyclohexanol, capryl phenol, thiocapryl phenol, thiophenol, amyl mercaptan, decyl mercaptan, lauryl mercaptan, cyclohexyl 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, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax, sulphurized wax unsaturate, propyl oleate, lard oil; or (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, methyl oleate, glycol dioleate, rapeseed oil, sperm oil, partially hydrogenated linseed oil, octene, turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax. Examples of ingredient (c) mentioned are (i) the products obtained by heating one of the following with sulphur:-methyl oleate, ethyl oleate, butyl oleate, capryl oleate, phenyl oleate, benzyl oleate, methyl cyclohexyl oleate, naphthenyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, ethyl ricinoleate, lard oil, cottonseed oil, linseed oil, rapeseed oil, sperm oil, castor oil, mustard oil, neatsfoot oil, olive oil, peanut oil, soyabean oil, partially hydrogenated linseed oil, partially hydrogenated tung oil, oleylalcohol, cetene, isobutylene, di-isobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (ii) one of the following:-diamylsulphide, dilauryl sulphide, chlorbenzyl trisulphide, thioanthrene; (iii) one of the following disulphides: - diamyl, dihexyl, dioctyl, dilauryl, dicyclohexyl, diphenyl, dibenzyl, di (chlorbenzyl), ditolyl, dixylyl, chlorphenyl ethyl; (iv) one of the following tri-or tetra-sulphides:-butyl, amyl, lauryl, benzyl, xylyl; or (v) one of the following tetrathiophosphates: - triamyl, trilauryl, trikeryl, tribenzyl.  The various types of halogen compounds which may be employed in order to introduce chemically-combined halogen into the composition are discussed and specific examples of such compounds mentioned are (1) chlorination products of one of the following:-diphenyl, diphenyl ether, naphthalene, methyl cyclohexane, cyclohexanone, paraffin wax, kerosene, foots oil, stearic acid, phenyl stearic acid; or (2) one of the following:-hexachlorethane, unsym di-(p-chlorphenyl) dichlorethylene, dichlorstearic acid, methyl dichlorstearate, o-dichlorbenzene, trichlor diphenyl ether, hexachlor diphenylether.  Detergents mentioned are the calcium salts of mahogany acids, and foam inhibitors mentioned are the silicone polymer known commercially as Dow Corning 200 and the chlorination product of this silicone polymer.  The Specification contains 40 examples of suitable compositions.  Specifications 679,462, 679,464 and 679,466 and U.S.A.  Specification 2,042,880 are referred to.