Patent GB-585803-A (GB)
Title: Improvements in or relating to addition agents for mineral lubricating oils
IPC: F02B77/04
Filed: 1943-10-12
Abstract: Internal combustion engines are maintained in a clean condition during operation by employing as the lubricant a mineral lubricating oil which contains a small proportion of a compound containing the structural group:- <FORM:0585803/III/1> where M is a polyvalent metal selected from Groups II, III, VIII and the right hand column of Group IV of the Periodic Table, X is a non-metallic element of Group VI of the Periodic Table, R is a branched-chain alkyl radicle, n is an integer not greater than 4 and m is the valency of the metal M, the total number of carbon atoms in the radicles R being at least 8.  The benzene nucleus of the structural group may contain additional substituents such as -NO2, -NH2, -COOH, -OCH3 and -SH or alternatively two structural groups may be linked together with sulphur or oxygen as in the case of metal salts of alkyl phenol sulphide sulphonic acids and metal salts of the sulphonic acids produced by sulphonating the condensation products of aldehydes with alkylated phenols or with alkylated phenol sulphides. Specific compounds mentioned which contain the structural group are calcium "triisobutyl phenol" sulphonate, zinc "triisobutyl phenol" sulphonate, tin "triisobutyl cresol" sulphonate, calcium barium or zinc "tetraisobutyl phenol" sulphonate, calcium "pentaisobutyl phenol" sulphonate and the barium sulphonate salt of "triisobutyl phenol" sulphide sulphonic acid, the "triisobutyl phenol," "tetraisobutyl phenol" and "pentaisobutyl phenol" being the products obtained by alkylating phenol with triisobutylene, tetraisobutylene and pentaisobutylene respectively.  The mineral lubricating oil may also contain dyes, pour point depressors, sludge dispersers, antioxidants, thickeners, viscosity index improvers, oiliness agents, solvents, plasticizers, defoaming agents, heat thickened or sulphurized fatty oils, organo metallic compounds, metallic or other soaps, resins, rubber, olefin polymers, voltolized fats mineral oils or waxes, colloidal solids such as graphite or zinc oxide, esters, ketones, alcohols, aldehydes, and halogenated or nitrated compounds. Among the alcohols mentioned are octyl, lauryl, cetyl, stearyl, oleyl, naphthenic, phenyl octyl or octadecyl benzyl alcohols and the alcohols obtained from wool fat, sperm oil or oxidized petroleum hydrocarbons.  Materials rich in alcohols such as woolfat or sperm oil may also be added.  In addition to their use as crankcase lubricants, the mineral lubricating oil compositions of the present invention may be employed in extreme pressure lubricants, spindle oils, textile oils, metal cutting oils, engine flushing oils, turbine oils, insulating and transformer oils, steam cylinder oils, slushing compositions and greases.  In examples, mineral lubricating oil compositions are described which contain (a) calcium or zinc "triisobutyl phenol" sulphonate, (b) calcium or zinc "tetraisobutyl phenol" sulphonate or (c) calcium "tetraisobutyl phenol" sulphonate, barium "diisobutyl phenol" sulphide, barium "diisobutyl phenol" disulphide and stearyl alcohol.  For comparison purposes, mineral lubricating oil compositions are described which contain (i) nickel oleate, (ii) barium mahogany sulphonate, (iii) barium "diisobutyl phenol" sulphide, barium "diisobutyl phenol" disulphide and stearyl alcohol or (iv) calcium "wax phenol" sulphonate, the "wax phenol" being prepared by alkylating phenol with chlorinated paraffin wax.ALSO:Compounds containing the structural group: <FORM:0585803/IV/1> where M is a polyvalent metal selected from Groups II, III, VIII and the right hand column of Group IV of the Periodic Table, X is a non-metallic element of Group VI of the Periodic Table, R is a branched-chain alkyl radicle, n is an integer not greater than 4, m is the valency of the metal M and the total number of carbon atoms in the radicles R is at least 8, are employed as lubricating oil additives.  The benzene nucleus of the structural group may contain additional substituents such as -NO2, -NH2, -COOH, -OCH3 and -SH or alternatively two structural groups may be linked together with sulphur or oxygen as in the case of metal salts of alkyl phenol sulphide sulphonic acids and metal salts of the sulphonic acids produced by sulphonating the condensation products of aldehydes with alkylated phenols or with alkylated phenol sulphides. Specific compounds mentioned which contain the structural group are calcium "triisobutyl phenol" sulphonate, zinc "triisobutyl phenol" sulphonate, tin "triisobutyl cresol" sulphonate, calcium, barium or zinc "tetraisobutyl phenol" sulphonate, calcium "pentaisobutyl phenol" sulphonate and the barium sulphonate salt of "triisobutyl phenol" sulphide sulphonic acid, the "triisobutyl phenol," "tetraisobutyl phenol" and "pentaisobutyl phenol" being the products obtained by alkylating phenol with triisobutylene, tetraisobutylene and pentaisobutylene respectively.  Compounds which contain the structural group may be prepared by reacting a phenol with an olefin or olefin polymer in the presence of sulphuric acid to form the alkylated phenol sulphonic acid and then neutralising the acid with a metallic oxide or hydroxide.  In this method of preparing the alkylated phenol sulphonic acids the sulphuric acid serves both as an alkylation catalyst and as a sulphonating agent.  An alternative procedure is first to alkylate the phenol in the presence of an alkylating catalyst other than sulphuric acid and then sulphonate the alkylated phenol with sulphuric acid.  Thus phenol can be alkylated with diisobutylene in the presence of stannic chloride and hydrogen chloride or with a mixed butene polymer of 16 to 20 carbon atoms using an Alcl3-HC1 catalyst and the alkyl phenol thus obtained then sulphonated.  Other alkylating agents which may be employed are low molecular weight polymers of olefins such as ethylene, propene, pentene and isopentene or of mixtures of these, or terpenes.  Phenols which may be alkylated include phenol itself, cresol, tert.-butyl phenol, petroleum phenols and the corresponding thio-phenols.  In preparing the metal salts of the alkylated phenol sulphonic acids it is sometimes more convenient first to prepare an alkali metal salt of the sulphonic acid and then to convert this to a polyvalent metal salt by reaction with an inorganic salt of the polyvalent metal.  In examples: (a) phenol is alkylated with triisobutylene in presence of sulphuric acid, the latter acting also as sulphonating agent; the "triisobutyl phenol" sulphonic acid thus obtained is converted first to its sodium salt by neutralisation with sodium hydroxide and then to its calcium or zinc salt by double decomposition with calcium or zinc chloride; (b) the calcium and zinc salts of "tetraisobutyl phenol" sulphonic acid are prepared by a similar procedure employing tetraiosbutylene instead of triisobutylene; the barium salt of "tetraisobutyl phenol" sulphonic acid is prepared by neutralisation of the sulphonic acid with barium carbonate.  For comparison purposes the preparation of calcium "wax phenol" sulphonate is described, phenol being alkylated with chlorinated paraffin wax in presence of aluminium chloride and the "wax phenol" thus produced being first sulphonated with sulphuric acid and then neutralised with calcium hydroxide.