Patent GB-785133-A (GB)
Title: Improved extreme pressure lubricants
Inventor: DAVID VERNON WARNER
IPC: C10M135/20
Filed: 1955-05-25
Abstract: A lubricating composition, suitable for use at extreme pressures, high speeds and high temperatures, comprises a lubricating oil and a minor proportion of a reaction product of a compound of formula RSX, wherein R is a hydrocarbon radicle and X is a halogen atom, with a compound containing an olefinic double bond.  The lubricating oil may be a mineral and/or a synthetic oil, and may be blended with a fatty oil such as castor oil or lard oil.  Synthetic oils mentioned are polymerized olefins, copolymers of alkylene glycols and alkylene oxides, organic esters, for example di-(2-ethylhexyl) sebacate, dioctyl phthalate and trioctyl phosphate, polymeric tetrahydrofuran and polyalkyl silicone polymers.  Typical sulphenyl halides RSX which may be employed are alkyl sulphenyl chlorides, phenyl sulphenyl chloride, p-methyl phenyl sulphenyl chloride, phenylmethyl sulphenyl chloride, beta-phenylethyl sulphenyl chloride, cyclohexyl sulphenyl chloride and the corresponding fluorides, bromides and iodides.  The preferred compounds containing an olefinic double bond are the alkenes, cycloalkenes, alkyl-substituted cycloalkenes and aryl-substituted alkenes (e.g. styrene).  Compounds containing more than one olefinic double bond (e.g. butadiene, isoprene, terpenes and cyclopentadiene) and olefinic compounds containing non-hydrocarbon substituents (e.g. oleic acid, cinnamic acid, maleic acid, phenyl isocrotonic acid, allyl ether, allyl chloride, trichloroethylene and geraniol) may also be employed. The reaction product of the compound RSX with the olefinic compound is a beta-halothioether.  The lubricating composition may contain additional ingredients such as thickeners (e.g. soaps or inorganic gelling agents), antioxidants, corrosion inhibitors or anti-rusting compounds, wear-reducing agents, blooming agents, pour-point depressants, viscosity improvers and anti-foaming agents (e.g. dimethyl silicone polymer).  Suitable antioxidants are alkylphenols, benzyl aminophenols, dibutyl phenylene diamine, diphenylamine, dinaphthylamine and N-phenyl-alpha- or betanaphthylamine.  The corrosion inhibitors may be dicarboxylic acids or organic compounds containing acidic radicles and also nitrile, nitro or nitroso groups (e.g. alpha-cyanostearic acid). Examples of wear-reducing agents are organic phosphates, thiophosphates and phosphites and aromatic mono- and poly-sulphides (including phenol sulphides.  Additional ingredients, which may be present in the lubricating composition, are oil-soluble urea or thiourea derivatives (e.g. urethanes, allophanates, carbazides and carbazones), polyisobutylene and polymerized unsaturated esters of fatty acids and monohydric alcohols.  In the examples, lubricating compositions are described consiting of mineral lubricating oil and the reaction product of cyclohexene and methyl sulphenyl chloride (i.e. 2-chlorocyclohexyl methyl sulphide) or the reaction product of 4-octyl cyclohexene and methyl sulphenyl chloride.ALSO:Sulphenyl halides of formula RXS, wherein R is a hydrocarbon radicle and X is a halogen atom, are prepared by the low temperature halogenation of the corresponding disulphide.  Thus, low temperature chlorination of dimethyl disulphide yields methyl sulphenyl chloride.  Lubricant additives (see Group III) may be obtained by reacting the sulphenyl halides with compounds containing an olefinic double bond.  Sulphenyl halides mentioned are C1-C5 alkyl sulphenyl chlorides, cyclohexyl sulphenic chloride, phenyl sulphenyl chloride, p-methylphenyl sulphenyl chloride, phenylmethyl sulphenyl chloride and beta-phenylethyl sulphenyl chloride, and also the corresponding fluorides, bromides and iodides.  Suitable compounds containing an olefinic double bond are C2-C6 alkenes, C6 and C5 cycloalkenes, alkylated cyclohexenes, butadiene, isoprene, styrene, terpenes, cyclopentadiene, oleic acid, cinnamic acid, maleic acid, phenyl isocrotonic acid, allyl ether, allyl chloride, trichloroethylene and geraniol.  The sulphenyl halides react with the compounds containing an olefinic double bond to form beta-halothioethers.  Thus, cyclohexene and methyl sulphenyl chloride yield 2-chlorocyclohexyl methyl sulphide, while styrene and ethyl sulphenyl chloride yield alpha-chloro-betaethylmercapto-ethyl benzene.