Patent GB-687512-A (GB)
Title: Lubricating oil additives
IPC: C10M159/12
Filed: 1950-08-04
Abstract: Oil additives comprise products obtained by heating a sulphide of phosphorus or a mixture thereof with sulphur and/or phosphorus or a mixture of sulphur and phosphorus with an ester of an alcohol of the formula: <FORM:0687512/IV (b)/1> where R is a methylol radical or alkyl radical of 1-3 C atoms, R1 is a methyl or methylol radical, and m and n are numbers from 0-2, or an alcohol of the above formula with at least 1 hydroxy group substituted by a group: <FORM:0687512/IV (b)/2> where R1 and R2 are hydrogen or methyl, at least one being hydrogen, and p is a number from 1-10, said ester being derived from the alcohol by substituting all the free hydroxy groups with radicals of aliphatic monocarboxylic acids of 8-30 C atoms, or salts of said products and metals of Groups 1 or 2. Suitable alcohols are pentaerythritol, di- and tripentaerythritol, and ether-alcohols obtained by reacting ethylene or propylene oxide therewith. Pentaglycerol, pentaglycol, tetra-(hydroxy ethyl ether) of pentaerythritol, and 3 - methyl - 2,2 - dimethylol - 1 - butanol are also specified.  The esterifying acids may contain open or closed hydrocarbon chains, and are preferably unsaturated open chain acids with one double bond.  Examples are lauric, myristic, palmitic, stearic, arachidic, behenic oleic, erucic, linoleic, and undecylenic acids, material fatty acids or mixtures from coconut, palm, corn, soybean, fish, cottonseed, and rapeseed oils, tallow, and lard, oxidized petroleum fractions and waxes, hydrogenated acids, and unsaturated acids produced by hydrogenation and dehydrogenation of waxes, stearic, naphthenic, and other acids.  The amounts of sulphur and phosphorus used may be 0.1-3 and 0.1-1 atoms respectively for each double bond.  For saturated esters, the higher proportions are generally used.  The reaction is effected at 200-500 DEG  F., generally for 1-10 hours in presence of a solvent such as benzene, o-dichlorbenzene or a mineral oil.  The products may be reacted with oxides or hydroxides of Group 1 or 2 metals, especially calcium, at 50-400 DEG  F.  The additives are added to hydrocarbon lubricating oils in proportions of 0.01-15 per cent or concentrates containing 25-50 per cent may be prepared.  Examples describe the preparation of esters of pentaerythritol with oleic or stearic acid or both, of dipentaerythritol with oleic acid, reaction of these esters or of commercial pentaerythritol tetralinoleate and tetraoleate of pentaerythritol hydroxyethyl ether with P2S5 or S and P2S5, and preparation of calcium or potassium salts with calcium hydroxide or potassium sulphide.ALSO:Additives for lubricating oils comprise products obtained by heating a sulphide of phosphorus or a mixture thereof with sulphur and/or phosphorus or a mixture of sulphur and phosphorus with an ester of an alcohol of the formula: <FORM:0687512/III/1> where R is a methylol radical or alkyl radical of 1-3 C atoms, R1 is a methyl or methylol radical, and m and n are numbers from 0-2, or an alcohol of the above formula with at least 1 hydroxy group substituted by a group: <FORM:0687512/III/2> where R1 and R2 are hydrogen or methyl, at least 1 being hydrogen, and p is a number from 1-10, said ester being derived from the alcohol by substituting all the free hydroxy groups with radicals of aliphatic monocarboxylic acids of 8-30 C atoms, or salts of said products and metals of Groups 1 or 2. Suitable alcohols are pentaerythritol, di- and tri-pentaerythritol, and etheralcohols obtained by reacting ethylene or propylene oxide therewith.  Pentaglycerol, pentaglycol, tetra (hydroxy ethyl ether) of pentaerythritol, and 3-methyl-2, 2-dimethylol-1-butanol are also specified.  The esterifying acids may contain open or closed hydrocarbon chains, and are preferably unsaturated open chain acids with one double bond.  Examples are lauric, myristic, palmitic, stearic, arachidic, behenic, oleic, erucic, linoleic, and undecylenic acids, natural fatty acids, or mixtures from coconut, palm, corn, soybean, fish, cottonseed, and rapeseed oils, tallow, and lard, oxidized petroleum fractions and waxes, hydrogenated acids, and unsaturated acids, produced by hydrogenation and dehydrogenation of waxes, stearic naphthenic, and other acids.  The amounts of sulphur and phosphorus used may be 0.1-3 and 0.1-1 atoms respectively for each double bond.  For saturated esters, the higher proportions are generally used.  The reaction is effected at 200-500 DEG F, generally for 1-10 hours in presence of a solvent such as benzene, o-dichlorbenzene or a mineral oil.  The products may be reacted with oxides or hydroxides of Group 1 or 2 metals, especially calcium, at 50-400 DEG F.  The additives are added to hydrocarbon lubricating oils in proportions of .01-15 per cent or concentrates containing 25-50 per cent may be prepared.  The base stocks may be straight or refined, hydrogenated or synthetic hydrocarbon oils with which animal or vegetable oils may be blended. Auxiliary solvents, plasticizers and defoamers, especially higher alcohols, detergents such as metal soaps, sulphonates, phenates including sulphides thereof, phosphates, phosphites and their thio derivatives, guanidine salts, xanthates, thiocarbamates, anti-oxidants, V.I improvers, resins, rubber, and the like may be present.  Examples describe the preparation of esters of pentaerythritol with oleic or stearic acid or both, of dipentaerythritol with oleic acid, reaction of these esters or of commercial pentaerythritol tetralinoleate and tetraoleate of pentaerythritol hydroxyethyl ether with P2S5 or S and P2S5, and preparation of calcium or potassium salts with calcium hydroxide or potassium sulphide.