Patent GB-691365-A (GB)
Title: Salts of substituted isothioureas and compositions containing the same
IPC: C07C335/32
Filed: 1950-02-09
Abstract: A salt formed from an acid of phosphorus and an S-substituted isothiourea of formula RSC(NH)NH2, where R is an aliphatic or cyclo aliphatic hydrocarbon radical or an aralkyl radical, the total number of carbon atoms in the salt being not less than 12, is used as an additive for oils of mineral origin.  To form the salt, any acid of phosphorous may be used such as orthophosphoric acid, phosphorus acid and their organo-substituted derivatives, thiophosphoric and thiophosphorous acids, phosphonic and thiophosphonic acids and the acids obtained by the action of sulphides of phosphorus on alcohols, phenols and hydrocarbon materials.  The substituent group in the organo-substituted phospho-acids may be aliphatic such as C1-C30 alkyl straight or branched chain, saturated or unsaturated and may contain other substituents such as halogen atoms or hydroxyl, amino or nitro groups.  The branched chain alkyl groups derived from Oxo alcohols are especially useful.  The organic group may also be aromatic (phenyl, alkylated phenyl, including wax-alkylated phenyl, and benzyl or residues of alkylated phenol sulphides).  Specified acids include di-isopropyl dithiophosphoric acid, di-2-ethylhexyl dithiophosphoric acid, di-n-decyl dithiophosphoric acid, dioleyl dithio-phosphoric acid, di-wax-alkylated phenyl dithiophosphoric acid, diethyl phosphoric acid di-2-ethylhexyl phosphoric acid, di-n-decyl phosphoric acid, di-wax alkylated-phenyl phosphoric acid, C8 Oxo thiophosphorous acid and heptadecyl-phenyl-hydroxymethyl phosphonic acid.  Other suitable acids may be obtained by the reaction of P2S5 or other phosphorus sulphide on hydrocarbons such as paraffins, aromatic hydrocarbons, olefins, diolefins, olefin polymers of molecular weight from 100 to 50,000, acetylenes, alkyl aromatics, cycloaliphatics and petroleum fractions.  The organic substituent in the S-substituted isothiourea may be saturated or unsaturated and of straight or branched chain.  Specified groups include methyl, ethyl, isopropyl, n-butyl, tert.-butyl, n-octyl, tert.-octyl, n-decyl, n-dodecyl, tert.-dodecyl, C7 to C20 Oxo, oleyl, paraffin wax chain groups, cyclohexyl, benzyl and substituted benzyl.  In an example the preparation of S-dodecyl isothiourea heptadecyl-phenyl-hydroxymethyl phosphonate is described. Dodecyl bromide and thiourea are refluxed and the product converted to the hydrochloride by addition of hydrochloric acid. The phosphonic acid is made by reacting heptadecyl-phenyl-ketone and phosphorus trichloride.  The two products thus obtained are reacted together in the presence of sodium methylate with ethyl alcohol and benzene as solvents.  The precipitated sodium chloride is filtered off giving, after evaporation of solvents, a viscous oil.  Other examples describe the preparation of the S-dodecyl isothiourea salts of P2S5-isobutylene, wax-phenyl phosphate and wax-phenyl dithiophosphate.ALSO:The salts formed by reacting an acid of phosphorus and an S-substituted isothiourea of formula RSC(NH)NH2, where R is an aliphatic or cycloaliphatic hydrocarbon radical or an aralkyl radical, the total number of carbon atoms in the salt being not less than 12, have surface-active properties.  They may be used as detergent additives in lubricating oils, motor fuels, hydraulic fluids, torque convertor fluids, cutting oils, turbine oils, transformer oils and lubricating greases.  To form the salt, any acid of phosphorus may be used such as orthophosphoric acid, phosphorous acid and their organo-substituted derivatives, thiophosphoric and thiophosphorous acids, phosphonic and thiophosphonic acids and the acids obtained by the action of sulphides of phosphorus on alcohols, phenols and hydrocarbon materials.  The substituent group in the organo-substituted phospho-acids may be aliphatic such as C1-C30 alkyl straight or branched chain, saturated or unsaturated and may contain other substituents such as halogen atoms or hydroxyl, amino or nitro groups.  The branched chain alkyl groups derived from "Oxo" alcohols are especially useful.  The organic group may also be aromatic (phenyl, alkylated phenyl including wax-alkylated phenyl, and benzyl or residues of alkylated phenol sulphides).  Specified acids include di-isopropyl dithiophosphoric acid, di-2-ethylhexyl dithiophosphoric acid, di-n-decyl dithiophosphoric acid, dioleyl dithio-phosphoric acid, di-wax-alkylated phenyl dithiophosphoric acid, diethyl phosphoric acid, di-2-ethylhexyl phosphoric acid, di-n-decyl phosphoric acid, di-wax alkylated-phenyl phosphoric acid, C8 "Oxo" thiophosphorous acid and heptadecylphenyl-hydroxymethyl phosphonic acid.  Other suitable acids may be obtained by the reaction of P2S5 or other phosphorus sulphide on hydrocarbons such as paraffins, aromatic hydrocarbons, olefins, diolefins, olefin polymers of molecular weight from 100 to 50,000, acetylenes, alkyl aromatics, cycloaliphatics, and petroleum fractions.  The organic substitutent in the S-substituted isothiourea may be saturated or unsaturated and of straight or branched chain.  Specified groups include methyl, ethyl, isopropyl, n-butyl, tert.-butyl, n-octyl, tert.-octyl, n-decyl, n-dodecyl, tert.-dodecyl, C7 to C20 "Oxo," oleyl, paraffin wax chain groups, cyclohexyl, benzyl and substituted benzyl.  In examples, S-dodecyl isothiourea heptadecylphenyl-hydroxymethyl phosphonate and S-dodecyl isothiourea salts of P2S5-isobutylene, wax-phenyl phosphate and wax-phenyl dithiophosphate are described.ALSO:To an oil of mineral origin there is added a salt formed from an acid of phosphorus and an S-substituted isothiourea of formula RSC(NH)NH2, where R is an aliphatic or cycloaliphatic hydrocarbon radical or an aralkyl radical, the total number of carbon atoms in the salt being not less than 12.  The S-substituted isothiourea salt may be used as a detergent additive in lubricating oils, motor fuels, hydraulic fluids, torque converter fluids, cutting oils, turbine oils, transformer oils and lubricating greases.  To form the salt, any acid of phosphorus may be used, such as orthophosphoric acid, phosphorus acid and their organosubstituted derivatives, thiophosphoric and thiophosphorous acids, phosphonic and thiophosphonic acids and the acids obtained by the action of sulphides of phosphorus on alcohols, phenols and hydrocarbon materials.  The substituent group in the organo-substituted phospho-acids may be aliphatic such as C1-C30 alkyl straight or branched chain, saturated or unsaturated, and may contain other substituents such as halogen atoms or hydroxyl, amino or nitro groups.  The branched chain alkyl groups derived from "Oxo" alcohols are especially useful. The organic group may also be aromatic (phenyl, alkylated phenyl including wax-alkylated phenyl, and benzyl or residues of alkylated phenol sulphides).  Specified acids include di-isopropyl dithiophosphoric acid, di-2-ethylhexyl dithiophosphoric acid, di-n-decyl dithiophosphoric acid, dioleyl dithiophosphoric acid, di-wax-alkylated phenyl dithiophosphoric acid, diethyl phosphoric acid, di-2-ethylhexyl phosphoric acid, di-n-decylphosphoric acid, di-wax-alkylated-phenyl phosphoric acid, C8 "Oxo" thiophosphorous acid and heptadecyl-phenyl-hydroxy-methyl phosphonic acid.  Other suitable acids may be obtained by the reaction of P2S5 or other phosphorus sulphide or hydrocarbons such as paraffins, aromatic hydrocarbons, olefins, diolefins, olefin polymers of molecular weight from 100 to 50,000, acetylenes, alkyl aromatics, cycloaliphatics and petroleum fractions.  The organic substituent in the S-substituted isothiourea may be saturated or unsaturated and of straight or branched chain.  Specified groups include methyl, ethyl, isopropyl, n-butyl, tert.-butyl, n-octyl, tert.-octyl, n-decyl, n-dodecyl, tert.-dodecyl, C7 to C20 "Oxo," oleyl, paraffin wax chain groups, cyclohexyl, benzyl and substituted benzyl.  The additives may be used in mineral lubricating oils in amounts of about 0.001 to about 10.0 per cent, depending on the amount of detergency required, and are preferably used in amounts of from 1.0 to 6.0 per cent. Conveniently a concentrated solution (25 to 50 per cent) in oil is prepared and diluted or blended with the base oil as required.  To improve the oxidation resisting properties of the composition, organic sulphur compounds such as sulphurized mineral oils, sulphurized terpenes, sulphurized olefins and diolefins, sulphurized animal and vegetable oils and sulphurized isobutylene polymers may be added. There may also be present in the compositions other detergent additives such as metal soaps, metal petroleum sulphonates, metal phenates, metal alcoholates, metal alkyl phenol sulphides, metal organo phosphates, thiophosphates, phosphites and thiophosphites, metal salicylates, metal anthates and thioxanthates, metal thiocarbamates, amines and amine derivatives, reaction products of metal phenates and sulphur, reaction products of metal phenates and phosphorus sulphides and metal phenol sulphonates. Specified additional additives include barium tert.-octylphenol sulphide, calcium tert.-amylphenol sulphide, nickel oleate, barium octadecylate, calcium phenyl stearate, zinc di-isopropyl salicylate, aluminium naphthenate, calcium cetyl phosphate, barium di-tert-amylphenol sulphide, calcium petroleum sulphonate, zinc methyl cyclohexyl thiophosphate, and calcium dichlorostearate. Any mineral oil fraction or extract may be used as the base oil. Hydrogenated oils, white oils, shale oil and the oils prepared by the polymerization of olefins, or by the hydrogenation of coal and its products may also be used.  For certain purposes the mineral oils may be mixed with animal, vegetable or fish oils or their hydrogenated or voltolized products.  Suitable mineral lubricating oils possess a viscosity of 40-150 S.U.S. at 210 DEG F and a viscosity index of 0-100 or even higher.  Other agents which may be added include dyes, pour depressors, h