Patent GB-590885-A (GB)
Title: Improvements relating to petroleum hydrocarbon products and the manufacture of addition agents therefor
IPC: C07F9/02
Filed: 1944-01-17
Abstract: Oxidation and deterioration of petroleum hydrocarbon products is inhibited by incorporating therein a small quantity of the reaction product of sulphur and phosphorus, or of a phosphorus sulphide with or without either or both of sulphur and phosphorus, with a compound having the formula ArXMT where Ar is an aromatic or substituted aromatic nucleus, X is a non-metal of Group 6 of the periodic table, M is a divalent metal of Group 2 of the periodic table and T is OH or (OM)n XAr where n is O, 1 or 2.  The aromatic nucleus may be benzene, biphenyl, naphthalene or anthracene and may contain substituents such as the alkyl, aryl, carboxyl, hydroxyl, alkoxy, sulphhydryl, nitro, esterified carboxyl, keto, amino, aldehydo, chlormethyl, aminomethyl, alkyl thiomethyl, alkyl xantho methyl, metal substituted carboxyl, metal substituted hydroxyl or sulphhydryl groups or the halogens. Thus, the compound to be phosphorized and sulphurized may have the formula RArXMT where R represents at least one alkyl group joined to the nucleus Ar, the sum total of carbon atoms in such groups being at least 5 and T being in this case OH or (OM)nXArR.  In reacting the aromatic compound with sulphur and phosphorus, it may be treated first with one element and then with the other.  The sulphurizing phosphorizing reaction may be effected by fusion. Other substances which may be present however during the reaction are solvents, particularly high boiling hydrocarbon solvents such as xylol or a petroleum fraction, higher alcohol anti-foaming agents such as stearyl, lauryl, cetyl or woolfat alcohol and olefinic materials such as tetraisobutylene, cracked gas or an unsaturated alcohol. Petroleum hydrocarbon products in which the sulphurized phosphorized compounds may be incorporated include crankcase lubricants, extreme pressure lubricants, engine flushing oils, industrial oils, general machinery oils, process oils, rust preventive compositions, greases, motor fuels, diesel fuels and kerosene.  In the case of motor fuels containing tetraethyl lead or other anti-knock agents, the sulphurized phosphorized compounds serve not only as anti-oxidants for the fuel but also as stabilizers for the anti-knock agent itself. In addition to the sulphurized phosphorized compounds, other agents may be added to the petroleum hydrocarbon products such as dyes, pour depressors, heat thickened fatty oils, sulphurized fatty oils, organometallic compounds, metallic or other soaps, sludge dispersers, anti-oxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, voltolized waxes, colloidal solids such as graphite or zinc oxide, and solvents and assisting agents such as esters, ketones, alcohols, aldehydes, and halogenated or nitrated compounds. Assisting agents which are particularly desirable are the higher alcohols such as octyl, lauryl, cetyl, stearyl, heptadecyl, oleyl, phenyloctyl or octadecyl benzyl alcohol, naphthenic alcohols, synthetic alcohols obtained by the oxidation of such petroleum hydrocarbons as paraffin wax of petrolatum, and alcohols isolated from natural products such as woolfat or sperm oil.  The woolfat or sperm oil may also itself be used as an assisting agent.  Where the sulphurized phosphorized compounds are incorporated in mineral lubricating oils, detergents such as metal soaps, metal phenates, metal alcoholates, metal phenol sulphides, metal organo phosphates, thiophosphates, phosphites or thiophosphites, metal sulphonates, metal thiocarbamates, and metal xanthates or thioxanthates may also be added.  Specific detergents mentioned are barium tert.-octylphenol sulphide, cobalt tert.-amylphenol sulphide, calcium mahogany sulphonates, tin salt of wax alkylated phenol sulphide, strontium mahogany sulphonates, magnesium cetylphenate, 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 p  amyl xanthate, barium dioctyl dithiophosphate, zinc methyl cyclohexyl dithiophosphate, calcium dihexadecyl monothiophosphite, calcium cetyl phosphate, barium mahogany sulphonates, zinc diisopropyl salicylate, tin naphthenate, aluminium naphthenate, magnesium mahogany sulphonates, 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.  In examples, mineral lubricating oil compositions are described which contain (i) the reaction product obtained by treating, with P2S5 and also if desired with sulphur, a barium salt of p-tert.-octyl phenol prepared if desired in the presence of stearyl alcohol, (ii) the reaction product obtained by treating with P2S5 or P4S7 a barium salt of 2, 4-di-tert.-amyl phenol prepared in the presence of stearyl alcohol, (iii) the reaction product obtained by treating with P2S5 the barium salt of phenol prepared by alkylating ordinary phenol with refinery butene polymers and (iv) calcium, barium or zinc mahogany sulphonates in addition to the sulphurized phosphorized compounds.  Details of tests are given in which mineral lubricating oil compositions containing the sulphurized phosphorized compounds are compared with mineral lubricating oil compositions containing the corresponding unsulphurized unphosphorized metal phenates.ALSO:Additives for petroleum hydrocarbon products are prepared by reacting sulphur and phosphorus, or a phosphorus sulphide with or without either or both of sulphur and phosphorus, with a compound having the formula ArXMT where Ar is an aromatic or substituted aromatic nucleus, X is a non-metal of Group 6 of the periodic table, M is a divalent metal of Group 2 of the periodic table and T is OH or (OM)nXAr where n is 0, 1 or 2.  The aromatic nucleus may be benzene, biphenyl, naphthalene or anthracene and may contain substituents such as alkyl, aryl, carboxyl, hydroxyl, alkoxy, sulpphydryl, nitro, esterified carboxyl, keto, amino, aldehydo, chlormethyl, aminomethyl, alkyl thiomethyl, alkyl xanthomethyl, metal substituted carboxyl, metal substituted hydroxyl or sulphhydryl groups or the halogens.  Thus the compound to be phosphorized and sulphurized may have the formula R Ar XMT where R represents at least one alkyl group joined to the nucleus Ar, the sum total of carbon atoms in such groups being at least 5 and T being in this case OH or (OM)nX Ar R.  In reacting the aromatic compound with sulphur and phosphorus, it may be treated first with one element and then with the other.  The sulphurizing phosphorizing reaction may be effected by fusion.  Other substances which may be present however during the reaction are solvents, particularly high boiling hydrocarbon solvents such as xylol or a petroleum fraction, higher alcohol anti-foaming agents such as stearyl, lauryl, cetyl or woolfat alcohol and olefinic materials such as tetraisobutylene, cracked gas or an unsaturated alcohol.  Preferred compounds for sulphurisation and phosphorization are the metal phenates of alkylated phenols. Suitable alkylated phenols may be prepared by alkylating phenol, cresol, naphthol or other phenolic compounds with such alkylating agents as alcohols, alkyl halides, alkyl phosphates and olefins with the aid of alkylation catalysts such as metal halides, hydrochloric acid, hydrofluoric acid, sulphuric acid, phosphoric acid or activated clay.  Conveniently, olefinic material such as petroleum refinery gases, containing mixtures of olefins, may be used as the alkylating agent, or individual olefins may be employed, such as butene, amylene or an olefin polymer such as diisobutylene or triisobutylene.  Other suitable alkylated phenols are those prepared by condensing phenols with chlorinated petrolatum or chlorinated paraffin wax or with a chlorinated kerosene or gas oil.  Halogenated or nitrated phenols are also suitable as are naturally occurring phenols such as those obtained by alkaline extraction of certain petroleum stocks or those obtained from cashew nut shell liquid or from other vegetable sources.  For converting the phenolic materials to metal phenates, the sodium or potassium salts may first be formed by reaction of the phenolic materials with sodium or potassium hydroxide and those salts then converted to the desired divalent metal salts by double decomposition.  Alternatively, the alkylated phenol may be reacted directly with the alcoholate, oxide or hydroxide of the desired metal.  Specific substances suitable for sulphurization and phosphorization are barium or calcium tertiary octyl phenate, barium diamyl phenate, barium cetyl phenate, zinc isohexadecyl phenate, calcium salt of petroleum phenols, barium salt of wax-alkylated phenol, magnesium salt of octadecyl cresol and the barium phenate-zinc carboxylate of lauryl salicylic acid. In examples: (i) diisobutylene is prepared by polymerising isobutylene in presence of sulphuric acid and the diisobutylene is used to alkylate phenol in the presence of tin chloride and hydrogen chloride; the p-tert.-octyl phenol thus obtained is then reacted with barium hydroxide in presence of mineral lubricating oil and, if desired, stearyl alcohol; the barium phenate solution thus obtained is treated with P2S5 and also, if desired, with sulphur; (ii) 2,4-di-tert.-amyl phenol is reacted with barium hydroxide in presence of mineral lubricating oil and stearyl alcohol and the barium phenate solution thus obtained is treated with P2S5 or P4S7, and (iii) phenol is akylated with refinery butene polymers in the presence of aluminium chloride and hydrogen chloride; the alkylated phenol thus obtained is converted to the corresponding barium phenate by reaction with barium hydroxide in presence of mi