Patent GB-679464-A (GB)
Title: Improvement in lubricant improving agent and lubricant containing same
IPC: C10M159/12
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, propyl 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, butyl ricinoleate, lauryl ricinoleate, benzyl ricinoleate, methyl palmitoleate, butyl palmitoleate, methyl linoleate, palmitoleic acid, wax unsaturate prepared 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, methyl palmitoleate, propyl ricinoleate; (iii) those obtained by heating one of the following with sulphur: methyl oleate, n-butyl oleate, benzyl oleate, methyl cyclohexyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lard oil, cottonseed oil, linseed oil, oleyl alcohol, cetene, isobutylene, di-isobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (iv) those obtained by heating one of the following with PCl3: -n-butyl alcohol, capryl 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; (v) those obtained by heating one of the following with P4S3: oleic acid, hexadecene, methyl cyclohexanol, methyl 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, propyl oleate, glycol dioleate, rapeseed oil, sperm oil, partially hydrogenated linseed oil, octene turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax Specifications 679,461, 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) the product obtained by treating, with a phosphorus-and sulphur-containing reagent, a sulphurized ester derived from an unsaturated monocarboxylic acid and an organic compound containing one or two -OH or -SH groups, and (b) a separate organic phosphorus compound in which a substantial portion of the phosphorus present has a valence of less than 5.  The composition may additionally have chemically-combined halogen present therein and may also contain separate organic sulphur compounds, pour point depressors, solubilizing agents, viscosity improvers, 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.  The esters to be employed in preparing ingredient (a) may be those mentioned in the parent Specification. These esters are sulphurized by treatment with sulphur or other sulphur-imparting reagent and then treated with phosphorus sulphide or other reagent containing phosphorus and sulphur. Suitable sulphur-imparting and phosphorus- and sulphur-containing reagents are listed.  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, propyl 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, 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, methyl palmitoleate, 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, 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, sulphurized palmitoleic acid, hexadecene, methyl cyclohexanol, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax, sulphurized wax unsaturate, methyl 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, propyl oleate, glycol dioleate, rapeseed oil, sperm oil, partially hydrogenated linseed oil, octene, turpentine, wax unsaturate produced by dehydrochlorinating chlorinated paraffin wax.  Separate organic sulphur compounds which may be present in the composition are (i) those obtained by heating one of the following with sulphur:- methyl oleate, n-butyl oleate, benzyl oleate, methyl cyclohexyl oleate, thiomethyl oleate, thioamyl oleate, thiophenyl oleate, methyl ricinoleate, lard oil, cottonseed oil, linseed oil, oleyl alcohol, cetene, isobutylene, diisobutylene, wax unsaturate prepared by dehydrochlorinating chlorinated paraffin wax; (ii) one of the following disulphides:- di-t-butyl, diamyl, dihexyl, dialuryl, dicyclohexyl, diphenyl, dibenzyl, di (chlorbenzyl), ditolyl, dixylyl, chlorphenyl ethyl; (iii) one of the following tri-or tetra-sulphides:-butyl, lauryl; (iv) one of the following:-keryl tetrathiophosphate, thianthrene.  Halogen compounds which may be present in the composition in order to introduce chemically-combined halogen are (1) chlorination p  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 diphenyl ether.  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 679,461, 679,462, 679,465 and 679,466 and U.S.A.  Specification 2,042,880 also are referred to.