Patent GB-598767-A (GB)
Title: Improvements in or relating to the prevention or inhibition of oxdiation in petroleum hydrocarbon products
IPC: C10M159/12
Filed: 1945-06-11
Abstract: Deterioration of petroleum hydrocarbon products due to oxidation is prevented or inhibited by incorporating therein a small quantity of the reaction product of the elements phosphorus and sulphur or of a phosphorus sulphide with a metal salt of a compound having the general formula:-R-Ar (XH)-Yx -R1 where R is hydrogen or one or more organic groups, Ar is an aromatic nucleus, X is oxygen, sulphur, selenium or tellurium, Y is sulphur, selenium or tellurium, x is 1, 2, 3 or 4 and R1 is an organic group.  The metal salt may be reacted with a mixture of phosphorus and sulphur, or first with one element and then with the other, or with a phosphorus sulphide such as P2S5, P4S3, or P4S7, or with sulphur and/or phosphorus and a phosphorus sulphide, or with any other substance or substances containing essentially only the elements phosphorus and sulphur.  The group R1 may be alkyl, aryl, alkaryl or aralkyl with or without substituent atoms or groups such as halogen, nitro, amino, hydroxy, alkoxy, aroxy or mercapto. Various substituent atoms or groups may be attached to the aromatic nucleus Ar, for instance alkyl, cycloalkyl, aralkyl, aryl, carboxyl, hydroxyl, alkoxy, aroxy, sulphhydryl, nitro, esterified carboxyl, keto, amino, aldehydo, chlormethyl, aminomethyl, alkyl thiomethyl, alkyl xanthomethyl, metal substituted carboxyl, metal substituted sulpho, metal substituted hydroxyl or sulphhydryl, halogen.  Different types of atoms or groups may be attached to the same aromatic nucleus.  When the metal salts employed are those of polyvalent metals, it is not essential that all of the metal valences be satisfied by replacing the hydrogen of the XH group; some of them may be satisfied by other acidic organic groups such as carboxyl, aroxy, alkoxy, organo-substituted inorganic acid groups such as phosphoric, phosphorous, thiophosphoric, thiophosphorous, phosphonic, phosphinic, sulphonic and sulphinic.  The substances to be reacted with phosphorus and sulphur may be the metal salts of hydroxy and mercapto substituted aromatic sulphides especially metal salts of the sulphides of phenols and thiophenols such as alkyl phenol thioethers, alkyl phenol disulphides and polymers of alkyl phenol sulphides. Instead of the normal metal salts, basic metal salts may be employed, that is, those salts formed for example by reacting phenol sulphides with more than the amount of metallic oxide or hydroxide necessary to form the normal salts. Metal salts specified as suitable for reaction with phosphorus and sulphur include barium or calcium or mixed calcium-barium tert. octyl phenol sulphide, barium di-tert. amyl phenol sulphide, calcium isohexadecyl phenol sulphide, tin paraffin wax alkylated salicylic acid sulphide, magnesium or cobalt tert. amyl phenol sulphide, barium salt of 2-hydroxy-3, 5-di-tert.-amyl-4-diethylamino diphenyl sulphide, zinc salt of salicylic acid sulphide octyl ester, barium-2-stearyl-4-amyl phenol sulphide, tin salt of C16-C20 branched chain alkyl phenol sulphide, barium salt of bis (2, 4-diamyl phenol)-4-amyl phenol dithioether, calcium mixed salt of tert. amyl phenol sulphide and iso-octyl salicylate, aluminium mixed salt of tert. octyl phenol sulphide and stearic acid, tin mixed salt of di-tert. amyl phenol sulphide and naphthenic acids, barium mixed salt of tert. octyl phenol sulphide and petroleum mahogany sulphonic acids, nickel mixed salt of tert.-amyl phenol sulphide and amyl xanthic acid, zinc mixed salt of isododecyl phenol sulphide and methyl cyclohexyl thiophosphoric acid, nickel mixed salt of tert.-amyl phenol sulphide and oleic acid, and magnesium mixed salt of tert. octyl phenol sulphide and cetyl phenol. Petroleum hydrocarbon products in which the additives may be incorporated include motor fuels, particularly those containing tetraethyl lead or other anti-knock agents, Diesel fuels, kerosene and mineral lubricating oil compositions such as crankcase lubricants, extreme pressure lubricants, engine flushing oils, p industrial oils, general machinery oils, process oils, rust preventative compositions and greases.  Where the additive is to be incorporated in a mineral lubricating oil, the reaction between phosphorus and sulphur and the metal salt may be carried out in a lubricating oil medium, thus obtaining a concentrate of the additive which can be blended with further lubricating oil.  The reaction in lubricating oil may be carried out in the presence of foam reducing agents or solubilisers particularly higher aliphatic alcohols such as stearyl, lauryl or cetyl alcohol or wool fat alcohol, high molecular weight amines or nitriles such as stearonitrile or lauronitrile, the products obtained by condensing phenol with the reaction products of sulphur halides and diisobutylene, and olefinic materials such as tetraisobutylene, cracked paraffin wax or an unsaturated alcohol.  In addition to the reaction products of phosphorus and sulphur with the metal salts other substances may be incorporated with the petroleum hydrocarbon products such as dyes, pour depressors, heat thickened fatty oils, sulphurised fatty oils, organo metallic compounds, metallic or other soaps, sludge dispersers, antioxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fatty oils or fats, voltolized mineral oils or waxes, colloidal solids such as graphite or zinc oxide, phenyl alpha naphthylamine voltolized sperm oil, 2, 6-di-tert.-butyl-4-methyl phenol, sulphurized sperm oil, p-tert.-amyl phenol sulphide, dibenzyl disulphide, polyisobutylene, sulphurised paraffin wax olefins, tricresyl phosphate, diamyl trisulphide, the condensation product of phenol with a sulphur chloride diisobutylene reaction product, solvents, assisting agents and detergents.  Specific solvents or assisting agents mentioned are esters, ketones, alcohols, aldehydes and halogenated or nitrated compounds.  In particular octyl, lauryl, cetyl, stearyl, heptadecyl, oleyl, naphthenic, phenyl octyl, or octadecyl benzyl alcohol or alcohols prepared by the oxidation of petroleum hydrocarbons such as paraffin wax or petrolatum, or alcohols obtained from wool fat or sperm oil, or the wool fat or sperm oil themselves may be employed.  Specific detergents mentioned are metal soaps, metal phenates, metal alcoholates, metal phenol sulphides, metal organophosphates, thiophosphates, phosphites and thiophosphites, metal sulphonates, metal thiocarbamates, metal xanthates and thioxanthates.  In particular barium tert.-octyl phenol sulphide, cobalt tert. amyl phenol sulphide, tin salt of paraffin wax alkylated phenol sulphide, calcium, barium, strontium, magnesium or zinc mahogany sulphonates, magnesium cetyl phenate, calcium ortho stearyl phenate, calcium salt of condensation product of amyl phenol and formaldehyde, nickel oleate, calcium dichlorostearate, aluminium-calcium mixed soap of fatty acids from oxidation of petroleum fractions, calcium isohexadecyl phenol sulphonate, barium octadecylate, calcium phenyl stearate, nickel dibutyl dithiocarbamate, nickel amyl xanthate, barium dioctyl dithiophosphate, zinc methyl cyclohexyl dithiophosphate, calcium dihexadecyl monothiophosphite, zinc tert.-octyl phenol sulphide thiophosphate, calcium cetyl phosphate, magnesium lauryl salicylate, zinc diisopropyl salicylate, tin or aluminium naphthenate, calcium double salt of octadecyl phenol sulphonic acid, barium phenate-zinc sulphonate of isohexadecyl phenol sulphonic acid, barium di-tert. amyl phenol sulphide and calcium phenate-barium carboxylate of octadecyl salicylic acid may be employed.  In the examples (i) tert. octyl phenol sulphide is reacted with barium hydroxide, with or without calcium hydroxide, if desired in the presence of stearyl alcohol and mineral lubricating oil and the product is treated with P2 S5 or P4 S7 and (ii) a mixture of diamyl phenol sulphide and diamyl phenol disulphide is reacted with barium hydroxide in the presence of stearyl alcohol and mineral lubricating oil and the product is treated with P2S5.  Lubricants are prepared by blending the compositions obtained in (i) with mineral lubricating oil and, if desired, adding calcium mahogany sulphonate.  Such lubricants are compared with similar lubricants containing the metal salt of tert. octyl phenol sulphide not treated with phosphorus sulphide. Specification 590,885 and U.S.A.  Specification 2,332,555 are referred to.ALSO:Additions for petroleum hydrocarbons are prepared by reacting the elements phosphorus and sulphur or a phosphorus sulphide with a metal salt of a compound having the general formula:-R-Ar(XH)-Yx-R1 where R is hydrogen or one or more organic groups, Ar is an aromatic nucleus, X is oxygen, sulphur, selenium or tellurium, Y is sulphur, selenium or tellurium, x is 1, 2, 3 or 4 and R1 is an organic group. The metal salt may be reacted with a mixture of phosphorus and sulphur, or first with one element and then with the other, or p  with a phosphorus sulphide such as P2S5, P4S3 or P4S7, or with sulphur and/or phosphorus and a phosphorus sulphide, or with any other substance or substances containing essentially only the elements phosphorus and sulphur.  The group R1 may be alkyl, aryl, aralkyl or alkaryl with or without substituent atoms or groups such as halogen, nitro, amino, hydroxy, alkoxy, aroxy, or mercapto. Various substituent atoms or groups may be attached to the aromatic nucleus Ar, for instance alkyl, cycloalkyl, aralkyl, aryl, carboxyl, hydroxy, alkoxy, aroxy, sulphhydryl, nitro, esterified carboxyl, keto, amino, aldehydo, chlormethyl, aminomethyl, alkyl thiomethyl, alkyl xanthomethyl, metal substituted carboxyl, metal substituted sulpho, metal substituted hydroxyl, or sulphhydryl, halogen. Different types of atoms or groups may be attached to the same aromatic nucleus.  When the metal salts employed are those of polyvalent metals, it is not essential that all of the