Patent GB-742267-A (GB)
Title: Improvements in or relating to lubricating oils and processes for preparing the same
IPC: C10M107/00
Filed: 1953-02-25
Abstract: A normally solid hydrocarbon wax of 15-100 C atoms is converted into a lubricant by heating with one or more olefins of from 2-10 C atoms, at 400-700 DEG  F. and superatmospheric pressure in the presence of a hydrocarbon halide catalyst, separating lighter constituents, preferably those boiling below 250 DEG  F. at 1 mm., by distillation, and de-waxing the heavy residue to give a resulting composition having a viscosity index of at least 100 and a pour point not greater than about 10 DEG  F.  The preferred waxes are crystalline and micro-crystalline waxes recovered from petroleum oils and consisting of paraffins of 20-40 C atoms. Other waxes include paraffins from pentadecane up to heptacontane; hydrocarbons containing a ring and a long chain substituent, e.g. dodecylcyclohexane, octadecylbenzene, 2-octadecyldecalin, and tetradecylcyclopentane; ceresin, ozokerite; polyethylenes and synthetic waxes from the Fischer-Tropsch process; waxes from destructive or non-destructive hydrogenation; and fractions or mixtures of these.  Normally gaseous olefins are preferably employed, especially ethylene.  Others include pentenes up to decenes, cyclopentene and cyclohexene.  The catalyst is preferably an aliphatic halide, e.g. chloroform, methylene chloride, methyl chloride, carbon tetrachloride, tetrachlorethane, dichlorpropane, butyl chloride, chlorinated naphthas, methylene fluoride, propyl bromide, octyl iodide, and dichlor-monofluormethane.  1-25, preferably 2-10 mols. olefin per mol. of wax, are used and, generally 0.1-10, preferably 1-5 per cent of catalyst, based on the weight of wax.  The wax is melted or dissolved in a solvent which may be a petroleum oil.  Thus, crude oils containing wax may be used.  The olefin is reacted in presence of the catalyst at pressures of 100-15,000, preferably 1000-4000 p.s.i.g., supplied by addition of inert gas if required.  Olefin, and preferably catalyst, may be added progressively during reaction to avoid polymerization.  Reaction times are suitably 1-20 hours.  On completion, distillation to remove catalyst and a light oil containing olefin polymers, and dewaxing to remove unreacted wax is effected.  The product normally contains 60-95 per cent of alkylate, the remainder mainly polymer.  Recovered olefins, catalyst, and wax may be further reacted.  The products may be blended to give lubricants and power transmitting fluids [Group III].  In examples, ethylene, propylene, 2-butene and 2-methyl-1-butene are reacted with petroleum waxes, eicosane, cetane and crude wax-containing oil using chloroform as catalyst. Comparative results using CH2Cl2 and CHCl2 as catalysts, and HCl, ZnCl2 and BF3, all of which have no catalytic effect, are given. Hydrogenation of the product to remove unsaturation by subjecting to a maximum hydrogen pressure of 2300 p.s.i.g. at 392 DEG  F. for 6 hours in the presence of Raney nickel is also exemplified.ALSO:A normally solid hydrocarbon wax of 15-100 C atoms is converted into a lubricant by heating with one or more olefins of from 2-10 C atoms, at 400-700 DEG F and superatmospheric presure in the presence of a hydrocarbon halide catalyst, separating lighter constituents, preferably those boiling below 250 DEG F at 1 mm., by distillation, and de-waxing the heavy residue to give a resulting composition having a viscosity index of at least 100 and a pour point not greater than about 10 DEG F.  The preferred waxes are crystalline and microcrystalline waxes recovered from petroleum oils and consisting of paraffins of 20-40 C atoms.  Other waxes include paraffins from pentadecane up to heptacontane, hydrocarbons containing a ring and a long chain substituent, e.g. dodecylcyclohexane, octadecylbenzene, 2-octadecyldecalin, and tetradecylcyclopentane; ceresin, ozokerite; polyethylenes and synthetic waxes from the Fischer-Tropsch process; waxes from destructive or non-destructive hydrogenation; and fractions or mixtures of these.  Normally gaseous olefins are preferably employed, especially ethylene.  Others include pentenes up to decenes, cyclopentene, and cyclohexene.  The catalyst is preferably an aliphatic halide, e.g. chloroform, methylene chloride, methyl chloride, carbon tetrachloride, tetrachlorethane, dichlorpropane, butylchloride, chlorinated naphthas, methylene fluoride, propyl bromide, octyl iodine, and dichlor-monofluormethane. 1-25, preferably 2-10 moles olefin per mole of wax are used and, generally 0.1-10, preferably 1-5 per cent of catalyst, based on the weight of wax.  The wax is melted or dissolved in a solvent which may be a petroleum oil.  Thus, crude oils containing wax may be used. The olefin is reacted in presence of the catalyst at pressures of 100-15,000, preferably 1,000-4,000 p.s.i.g., supplied by addition of inert gas if required.  Olefin, and preferably catalyst, may be added progressively during reaction to avoid polymerization.  Reaction times are suitably 1-20 hrs.  On completion, distillation to remove catalyst and a light oil containing olefin polymers, and dewaxing to remove unreacted wax is effected.  The product normally contains 60-95 per cent of alkylate, the remainder mainly polymer.  Recovered olefins, catalyst, and wax may be further reacted.  The products may be blended with up to 50 per cent of mineral oils or synthetic hydrocarbon oils, additives such as detergents, e.g. metal phenates and sulphurized derivatives, salts of alkyl phenol sulphides, sulphonates, phosphates, phosphonates, mercaptides, carboxylates, and non-ashing detergents such as sorbitan or pentaerythritol mono-oleate and methacrylate/methacrylamide polymers; inhibitors such as organic sulphides and selenides, metal dithiocarbamates, salts and esters of organic thiophosphoric acids and aromatic amines; V.I. improvers such as methacrylate polymers; defoaming agents; metal deactivators; and extreme pressure agents.  They may be thickened to greases with metal soaps, ethylene polymers, inorganic aerogels, and polyamides. They are used as lubricants and power transmitting fluids.  In examples, ethylene, propylene, 2-butene, and 2-methyl -1- butene are reacted with petroleum waxes, eicosane, cetane, and crude wax-containing oil using chloroform as catalyst. Comparative results using CH2Cl2, and CHCl2F as catalysts, and HC1, ZnCl2, and BF3, all of which have no catalytic effect, are given.  The miscibility of the products with a solvent refined mineral oil, and with a calcium petroleum sulphonate and sulphurized calcium phenate is illustrated. Hydrogenation of the product to remove unsaturation by subjecting to a maximum hydrogen pressure of 2,300 p.s.i.g. at 392 DEG F. for 6 hrs. in the presence of Raney nickel is also exemplified.