Patent GB-700804-A (GB)
Title: Lubricating oil compositions
Filed: 1950-05-15
Abstract: A lubricant (see Group III) comprises an oxidizable synthetic hydrocarbon lubricating oil which may be polymeric and a minor proportion, sufficient to inhibit oxidative deterioration of the oil, of a substance of the general formula R - (X)n - (Y) m - R1 wherein R and R1 are like or unlike organic radicles of which at least one contains not less than 8 carbon atoms, X is selenium or tellurium, Y is oxygen, sulphur selenium or tellurium, m is zero or an integer, n is an integer, and a non-benzenoid carbon atom in each of radicles R and R1 is connected directly to the appropriate X or Y atom of the formula. The lubricating oils mentioned include (a) polyesters such as the linear condensation products of dimers of unsaturated vegetable oil fatty acids with organic dihydroxy compounds, (b) polyamides obtained by condensing dimers of unsaturated vegetable oil fatty acids with diamines or hydroxyamines and (c) polyoxyalkylene glycols or their ester, ether or ester-ether derivatives.  The lubricants may contain additional ingredients such as metal salts of organo substituted phosphates, metal salts of phenols, metal salts of organo substituted acids of boron, sulphur and arsenic, metal salts of carboxylic acids and rust inhibitors, especially the higher alkyl acid esters of polybasic aliphatic acids.  In the examples, lubricants consist of (i) polymerized propylene oxide lubricating oil and dilauryl selenide, with or without zinc dibutyl dithiocarbonate or zinc dithiocarbonates of reduced cyclic petroleum nitrogen bases, (ii) propylene oxide - isobutylene oxide -1- butylene oxide copolymer lubricating oil and dilauryl selenide and (iii) acetylated polymer of propylene oxide, mineral oil and dilauryl selenide.  For comparison purposes, lubricants are described consisting of (iv) propylene oxide polymer and dicetyl sulphide, with or without calcium cetyl phosphate and (v) the copolymer of (ii) and hexadecyl trisulphide. Specification 649,976, [Group III], is referred to.ALSO:Substances of the general formula R-(X)n-(Y)m-R1, wherein R and R1 are like or unlike organic radicles of which at least one contains not less than 8 carbon atoms, X is selenium or tellurium, Y is oxygen, sulphur, selenium or tellurium, m is zero or an integer, n is an integer, and a non-benzenoid carbon atom in each of radicles R and R1 is connected directly to the appropriate X or Y atom of the formula, are employed as lubricant additives (see Group III). Radicles R and R1 may be straight or branched chain alkyl groups, straight or branched chain unsaturated aliphatic groups, or cycloalkyl or other cycloaliphatic groups.  Radicles R and R1 may contain aromatic groups, such as phenyl, hydroxyphenyl or aminophenyl groups, and non-hydrocarbon groups or atoms, such as chlorine and bromine atoms, hydroxyl, ether, keto, amino, free carboxyl, metal substituted carboxyl, esterified carboxyl, mercapto, mercaptide and monodi- or poly-sulphide groups. Substances specified may be classified as normal or branched chain alkyl monoselenides, alkyl monoselenides bearing non-hydrocarbon substituents in the alkyl groups (e.g. bis (b -chlorocetyl) selenide and bis (b -hydroxy cetyl) selenide), alkyl diselenides, alkyl mono- and di-tellurides, the various mono- and polyselenides and mono- and poly-tellurides prepared by reacting sodium or other alkali metal mono- or poly-selenides or mono- or poly-tellurides with halogenated hydrocarbons such as alkyl chlorides, chlorinated hydrocarbon lubricating oil and chlorinated hydrocarbon wax, diparaffin sulphoselenide prepared by condensing chlorinated paraffin wax with the product of dissolving selenium in aqueous or alcoholic sodium sulphide or polysulphide, dilauryl selenoxide.  Suitable methods of preparing these selenides and tellurides are as follows:-(1) by condensation of aliphatic halides with metal selenides, tellurides, polyselenides or polytellurides, (2) by condensation of metal selenomercaptides or telluromercaptides with halogenated hydrocarbons, (3) by oxidation of selenomercaptans, (4) by action of caustic alkali on aliphatic selenocyanates and (5) by heating aliphatic or aryl-substituted aliphatic monoselenides with selenium. In examples, (a) dicetyl selenide is prepared by condensing normal cetyl chloride with sodium selenide in ethyl alcohol solution, (b) dicetyl telluride is prepared by condensing normal cetyl chloride with sodium telluride in ethyl alcohol solution, (c) dilauryl diselenide is prepared by the action of caustic soda on lauryl selenocyanate and (d) dioctadecyl diselenide is prepared by condensing sodium diselenide with octadecyl chloride. Specification 649,976 is referred to.ALSO:A lubricant comprises an oxidizable synthetic non-hydrocarbon lubricating oil and a minor proportion, sufficient to inhibit oxidative deterioration of the oil, of a substance of the general formula R-(X)n-(Y)m-R4, wherein R and R1 are like or unlike organic radicles of which at least one contains not less than 8 carbon atoms, X is selenium or tellurium, Y is oxygen, sulphur, selenium or tellurium, m is zero of an integer, n is an integer, and a non-benzenoid carbon atom in each of radicles R and R1 is connected directly to the appropriate X or Y atom of the formula. The preparation of such substances is described (see Group IV(b)). The lubricating oils may be polymeric (see Group IV(a)) and oils mentioned are (a) polyesters such as the linear condensation products of dimers of unsaturated vegetable oil fatty acids with organic dihydroxy compounds and the polymers of esterfied unsaturated dicarboxylic acids, (b) polyamides obtained by condensing dimers of unsaturated vegetable oil fatty acids with diamines or hydroxyamines, (c) polyoxyalkylene glycols or their ester, ether or ester-ether derivatives, (d) alkyl diesters of dicarboxylic acids and (e) thioethers such as bis (gamma-2-ethyl-hexyl-oxypropyl) sulphide.  The lubricants may contain additional ingredients such as metal salts of organo substituted phosphates, metal salts of phenols (especially polyvalent metal salts of higher alkyl phenols), metal salts of organo substituted acids of boron, sulphur and arsenic (particularly calcium, magnesium, zinc, cadmium or aluminium salts of aryl sulphonic acids or petroleum sulphonic acids), metal salts of carboxylic acids (such as salts of aryl carboxylic acids, fatty acids and substituted aliphatic mono- and polycarboxylic acids containing nonhydrocarbon substituents; specific salts mentioned are calcium cetyl oxalate, calcium cetyl citrate, magnesium alpha hydroxy stearate and magnesium tartrate), rust inhibitors (especially the higher alkyl acid esters of polybasic aliphatic acids such as lauryl acid maleate and mono-or dicetyl citrate).  The lubricants may be crankcase oils, especially for use under heavy load, turbine oils or cutting oils.  In the examples, lubricants consist of (i) polymerized propylene oxide lubricating oil and dilauryl selenide, with or without zinc dibutyl dithiocarbamate or zinc dithiocarbamates of reduced cyclic petroleum nitrogen bases, (ii) propylene oxide-isobutylene oxide- 1-butylene oxide copolymer lubricating oil and dilauryl selenide and (iii) acetylated polymer of propylene oxide, mineral oil and dilauryl selenide.  For comparison purposes, lubricants are described consisting of (iv) propylene oxide polymer and dicetyl sulphide, with or without calcium cetyl phosphate and (v) the copolymer of (ii) and hexadecyl trisulphide.  Specification 649,976 is referred to.