EP0719313B1 - Gemischte antioxydationsmittelzusammensetzung - Google Patents

Gemischte antioxydationsmittelzusammensetzung Download PDF

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Publication number
EP0719313B1
EP0719313B1 EP94928344A EP94928344A EP0719313B1 EP 0719313 B1 EP0719313 B1 EP 0719313B1 EP 94928344 A EP94928344 A EP 94928344A EP 94928344 A EP94928344 A EP 94928344A EP 0719313 B1 EP0719313 B1 EP 0719313B1
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EP
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Prior art keywords
lubricating oil
additive
oil
antioxidant
lubricating
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EP94928344A
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English (en)
French (fr)
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EP0719313A1 (de
Inventor
Harold Shaub
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/066—Arylene diamines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/067—Polyaryl amine alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • This invention relates to lubricating oil additives, and to lubricating oil compositions and concentrates prepared therefrom. More specifically it relates to an additive containing a combination of a molybdenum compound and an aromatic amine compound as an antioxidant.
  • Lubricating oils as used in, for example, the internal combustion engines of automobiles or trucks are subjected to a demanding environment during use.
  • This environment results in the oil suffering oxidation which is catalysed by the presence of impurity species in the oil such as iron compounds and is also promoted by the elevated temperatures experienced by the oil during use.
  • This catalysed oxidation of the oil contributes to the formation of corrosive oxidation products and sludge in the oil but can also cause the viscosity of the oil to increase or even cause the oil to solidify.
  • This oxidation of lubricating oils during use is usually controlled to some extent by the use of antioxidant additives which may extend the useful life of the oil particularly by reducing or preventing unacceptable viscosity increases.
  • antioxidants which do not contribute to the phosphorus content of motor vehicle exhausts as phosphorus is detrimental to the performance of catalyst based exhaust purification systems.
  • some antioxidants such as for example diphenylamines cannot be used at relatively high concentrations as this may result in sedimentation or deposits in hot engine areas such as the diesel ring areas in diesel engines.
  • the invention is concerned with the problem of providing an improved antioxidant for use in lubricating oils.
  • Both US 4 370 246 and US 4 394 279 describe the use of combinations of specific molybdenum compounds with aromatic amines wherein the molybdenum compounds are prepared from the reaction of an acidic molybdenum compound with a basic nitrogen compound selected from either Mannich bases phosphonamides, thiophosphonamide, phosphoramide, succinamide, carboxylic acid amide, dispersant viscosity index improvers or mixtures thereof and either carbon disulfide or other sulphur containing compounds.
  • a basic nitrogen compound selected from either Mannich bases phosphonamides, thiophosphonamide, phosphoramide, succinamide, carboxylic acid amide, dispersant viscosity index improvers or mixtures thereof and either carbon disulfide or other sulphur containing compounds.
  • US 4 479 883 is concerned with the provision of lubricant compositions with improved friction reducing properties containing a mixture of dithiocarbamates.
  • EP0 447 916 A1 is concerned with engine oil compositions which exhibit fuel saving effects.
  • the compositions are based on the combination of an overbasic oil-soluble metal salt in combination with a friction modifier and an antioxidant.
  • GB 1 097 372 describes a synthesis for molybdenum dialkyldithiocarbamates and there use in lubricants.
  • JP 51080825 describes the synthesis of molybdenum additives from molybdenum trisulphide secondary amine and carbon disulphide. The synthesis allows high purity product to be prepared in high yield and in one step.
  • a lubricating oil additive which comprises a combination of an oil-soluble molybdenum containing compound of general formula I: wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each independently represent a C 7 to C 24 hydrocarbyl radical, X and X 1 may be the same or different and independently represent S or O, and the Mo is in oxidation state five or less; and at least one oil-soluble aromatic amine.
  • hydrocarbyl radical an organic moiety which comprises hydrogen and carbon and which unless the context states otherwise may be aliphatic (including alicyclic), aromatic or a combination thereof. It may be substituted or unsubstituted, alkyl, aryl or alkaryl and may optionally contain unsaturation or heteroatoms such as O, N or S. It is preferred that the hydrocarbyl radical does not contain heteroatom substitution. It is preferred that the hydrocarbyl radical is a hydrocarbyl radical of C 10 to C 18 and most preferably is a C 12 or C 13 aliphatic hydrocarbyl radical.
  • Suitable aliphatic hydrocarbyl radicals include, 2-ethylhexyl, nonylphenyl, dodecyl, pentyl, cyclohexyl, phenylmethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, or t-butyl.
  • the choice of R 1 , R 2 , R 3 and R 4 must be such that the resulting molybdenum compound of general structure I is oil-soluble.
  • X and X 1 are the same. It is most preferred that X and X 1 are S.
  • aromatic amine any secondary amine with at least one aromatic group; such an amine gives a synergistic antioxidant effect when used in combination with a molybdenum compound of general formula I.
  • the oil-soluble secondary aromatic amines are diphenylamines of general formula II: wherein R 5 and R 6 may be the same or different and each independently represents a hydrocarbyl radical as hereinbefore defined. It is preferred that R 5 and R 6 are C 1 to C 28 aliphatic hydrocarbyl radicals. A and B may be the same or different and may equal 0, 1, 2 or 3. It is preferred that A and B are the same and that they equal 1. It is also preferred that the diphenylamines have a nitrogen content of between 2.5 and 5% by weight. It is preferred that R 5 and R 6 are located in the meta or para positions relative to the amino substitution in the aromatic rings of the diphenylamines.
  • diphenylamines examples include di-octyldiphenylamine, t-pentyldiphenylamine, diisobornyldiphenylamine, didecyldiphenylamine, didodecyldiphenylamine, dihexyldiphenylamine, di-t-butyldiphenylamine,di-t-octyldiphenylamine, dinonyldiphenylamine, dibutyldiphenylamine,
  • distyryldiphenylamine examples include di-substituted derivatives wherein the R 5 and R 6 are different and independently represent hydrocarbyl radicals such as for example t-butyl, t-octyl, styryl, n-butyl or n-octyl.
  • R 5 and R 6 are different and independently represent hydrocarbyl radicals such as for example t-butyl, t-octyl, styryl, n-butyl or n-octyl.
  • Some of these diphenylamines are commercially available and are sold under the trademarks, Vanlube DND, Naugalube 438L, Pearsall OA502, Lubrizol 5150A, Vanlube SL, Naugalube 680, Inganox L-57 and Vanlube 848.
  • oil-soluble molybdenum compounds of Formula I are commercially available.
  • products where X and X 1 are O and where R 1 , R 2 , R 3 and R 4 are C 13 H 27 aliphatic hydrocarbyl groups and where the molybdenum is in oxidation state V are sold under the trademarks Molyvan 807 and Molyvan 822 as antioxidants and friction reducing additives by R.T. Vanderbilt Company Inc. Norwalk CT USA.
  • These molybdenum compounds may be prepared by the methods described in US 3 356 702 wherein MoO 3 is converted to soluble molybdate by dissolving in alkali metal hydroxide solution, neutralised by the addition of acid followed by the addition of a secondary amine and carbon disulfide.
  • the molybdenum compounds of general structure I wherein X and X 1 are S may be prepared by a number of methods.
  • JP 51080825 (Asahi Denka Kogyo K.K.) discloses a method wherein MoS 3 , secondary amine and CS 2 are reacted together in an inert organic solvent.
  • Bull. Jap. Petrol. Inst. 1971, 13(2), 243-9 discloses a method wherein sulfurized molybdenum dialkyl- dithiocarbamates prepared according to US 3 356 702 are treated in xylene solution with P 2 S 5 with heating followed by the dissolving in DMF of the resulting precipitate with further heating.
  • the molybdenum compounds of general structure I co-operate with the aromatic amines to produce a synergistic antioxidant effect it is believed that the mechanism may involve a regenerative process. It is believed that during oxidation of the oil, oxidation intermediates oxidise the molybdenum compound to a higher oxidation state. It is then believed that the aromatic amine is able to interact with the higher oxidation state molybdenum compound reducing it so that the original molybdenum compound of lower oxidation state is regenerated with the diphenylamine being converted to a quinone intermediate.
  • the molybdenum compound is in oxidation state five or less so that the molybdenum can be oxidised to a higher oxidation state. It is also necessary that the redox potential of the higher oxidation state molybdenum compound and the diphenylamine are such that the higher oxidation state molybdenum compound can be reduced to a lower oxidation state.
  • mixtures of molybdenum compounds of general formula I may be used and/or mixtures of oil-soluble aromatic amines may be used as the lubricating oil additive of the present invention.
  • Also provided by the invention is the use as a lubricating oil antioxidant of a combination of an oil-soluble molybdenum containing compound of general formula I and at least one oil-soluble aromatic amine.
  • the invention provides for a lubricating oil composition which comprises a lubricating oil and a lubricating oil additive comprising the combination of an oil-soluble molybdenum compound of general formula I and at least one oil-soluble aromatic amine.
  • concentration of the lubricating oil additive is typically in the range of 0.01 to about 15% by weight based on the total weight of the composition and is preferably from about 0.1 to about 7% by weight.
  • Suitable lubricating oils for use in preparing the lubricating composition include those oils which are conventionally employed as crankcase lubricating oils for internal combustion engines and those which may be employed as power transmitting fluids such as automatic transmission fluids, hydraulic fluids, or gear lubricants.
  • the lubricating oil may be a synthetic oil such as for example alkylesters of dicarboxylic acids, polyglycols and alcohols, polyalphaolefins, alkylbenzenes, organic esters of phosphoric acids, or polysilicone oils.
  • the lubricating oil may be a natural oil including mineral oils which may vary widely as to their crude source e.g. whether paraffinic, naphthenic or mixed paraffinic-naphthenic; as well as to their formation, e.g. distillation range, straight run or cracked, hydrorefined, or solvent extracted.
  • the invention further provides a lubricating oil concentrate.
  • a lubricating oil concentrate In the preparation of lubricating oil compositions it is a convenient practice to introduce additives in the form of a concentrate; which introduction may be made by methods known in the art.
  • the lubricating oil concentrate may contain between 2.5 to 90 weight percent more preferably 5 to 75 weight percent of the additive composition in a suitable solvent.
  • Suitable solvents may include hydrocarbon oils e.g. mineral lubricating oil or synthetic oil.
  • the ratio of Mo compound of general formula I to the oil-soluble aromatic amine may be selected so as to provide an antioxidant effect of sufficient magnitude to meet the end use requirements of the lubricating oil - for example, to achieve adequate performance in the Sequence III E engine test for crankcase lubricating oils (according to the procedure of ASTM STP315).
  • the Mo compound of general formula I and the oil-soluble aromatic amine are employed in a ratio of from 1:10 to 10:1 (by wt), more preferably from 3:1 to 1:3 (by wt).
  • the lubricating oil additive may be used as the sole additive for the composition or concentrate or may be used in combination with several different types of additive which may be required to fulfill other requirements of the composition or concentrate during use.
  • the composition may be used as a crankcase lubricating oil, a cylinder lubricant for applications such as marine diesel, industrial oil, functional fluid such as power transmission fluid, tractor oil, gear oil or hydraulic fluid. Accordingly the compositions or concentrates of the invention may in addition to the lubricating oil additive contain one or more of the following:
  • compositions are for use as crankcase lubricants they preferably contain at least; an ashless dispersant and/or a viscosity index improver dispersant, a detergent, and an antiwear additive in amounts effective to provide their respective functions.
  • the preferred ashless dispersant in the compositions and concentrates of this invention is a long chain hydrocarbyl substituted mono- or di- carboxylic acid material, i.e. acid, anhydride, or ester, and includes a long chain hydrocarbon, generally a polyolefin, substituted with an alpha or beta unsaturated C 4 to C 10 carboxylic acid material, such as itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, or cinnamic acid.
  • the dispersant contains at least about 1 mole (e.g. 1.05 to 1.2 moles, or higher) of the acid material per mole of polyolefin.
  • the proportion of the dispersant is preferably from 1 to 10 and especially 3 to 7 weight percent of the lubricating oil.
  • Preferred olefin polymers for the reaction with carboxylic acids are polymers derived from a C 2 to C 5 monoolefin.
  • Such olefins include ethylene, propylene, butylene, isobutylene, pentene, oct-1-ene or styrene.
  • the polymers may be homopolymers such as polyisobutylene or copolymers of two or more of such olefins. These include copolymers of: ethylene and propylene; butylene and isobutylene; propylene and isobutylene; etc.
  • Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g.
  • 1 to 10 mole percent is a C 4 to C 18 diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.
  • the olefin polymer may be completely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight.
  • the olefin polymers usually have number average molecular weights above about 700, including number average molecular weights within the range of from 1,500 to 5,000 with approximately one double bond per polymer chain.
  • An especially suitable starting material for a dispersant additive is polyisobutylene.
  • the number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W.W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography,” John Wiley and Sons, New York, 1979.
  • the olefin polymer and the carboxylic acid material may be simply heated together as disclosed in US-A-3 361 673 and 3 401 118 to cause a thermal "ene" reaction to take place.
  • the olefin polymer can be first halogenated, for example chlorinated or brominated, to about 1 to 8, preferably 3 to 7, weight percent chlorine or bromine, based on the weight of polymer, by passing chlorine or bromine through the polyolefin at a temperature of 100° to 250°C, e.g.
  • halogenated polymer may then be reacted with sufficient unsaturated acid or anhydride at 100° to 250°C, usually 180° to 220°C, for from 0.5 to 10, e.g. 3 to 8 hours. Processes of this general type are taught in US-A-3 087 436; 3 172 892; 3 272 746 and others.
  • halogen When a halogen is used, from 65 to 95 weight percent of the polyolefin normally reacts with the carboxylic acid or anhydride. Thermal reactions, carried out without the use of halogen or a catalyst, cause only from 50 to 75 weight percent of the polyisobutylene to react. Chlorination increases reactivity.
  • the carboxylic acid or anhydride can then be further reacted with amines, alcohols, including polyols, amino-alcohols, etc., to form other useful dispersant additives.
  • amines e.g., benzyl alcohols
  • polyols e.g., benzyl alcohols
  • amino-alcohols e.g., benzyl alcohols
  • the acid or anhydride is to be further reacted, e.g. neutralized, then generally a major proportion of at least 50 percent of the acid units up to all the acid units will be reacted.
  • Useful amine compounds for reaction with the hydrocarbyl substituted carboxylic acid or anhydride include mono- and polyamines of from 2 to 60, e.g. 3 to 20, total carbon atoms and from 1 to 12, e.g. 2 to 8, nitrogen atoms in a molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g. hydroxy groups, alkoxy groups, amide groups, nitriles, or imidazoline groups. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups, are particularly useful.
  • Preferred amines are aliphatic saturated amines, including those of the general formulae: wherein R 7 , R 8 and R 9 are each hydrogen; C 1 to C 25 straight or branched chain alkyl radicals; C 1 to C 12 alkoxy-(C 6 alkylene) radicals; C 2 to C 12 alkylamino-(C 2 to C 6 alkylene) radicals; each s can be the same or a different number of from 2 to 6, preferably 2 to 4; and t is a number from 0 to 10, preferably 2 to 7. At least one of R 7 , R 8 and R 9 must be hydrogen.
  • Suitable amines include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetramine; tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine; di(1,3-propylene)triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM); diisopropanol amine; diethanol amine; triethanol
  • amine compounds include: alicyclic diamines such as 1,4-di-(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula: wherein p 1 and p 2 are the same or different and each is an integer from 1 to 4, and n 1 , n 2 and n 3 are the same or different and each is an integer from 1 to 3. Examples of such amines include 2-pentadecyl imidazoline and N-(2-aminoethyl) piperazine.
  • alkylene amines can also be employed.
  • Commercial mixtures of amine compounds may advantageously be used.
  • one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylene tetramine, tetraethylene pentamine and corresponding piperazines.
  • alkylene dihalide such as ethylene dichloride or propylene dichloride
  • ammonia which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylene tetramine, tetraethylene pentamine and corresponding piperazines.
  • Low cost poly(ethyleneamine) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Pol
  • Useful amines also include polyoxyalkylene polyamines such as those of the formulae:
  • the polyoxyalkylene polyamines above may have average molecular weights ranging from 200 to 4,000 and preferably from 400 to 2,000.
  • the preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from 200 to 2,000.
  • the polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403," etc.
  • the amine is readily reacted with the carboxylic acid material, e.g. alkenyl succinic anhydride, by heating an oil solution containing 5 to 95 weight percent of carboxylic acid material to from 100 to 250°C, preferably 125 to 175°C, generally for 1 to 10, e.g. 2 to 6 hours, until the desired amount of water has been removed.
  • the heating is preferably carried out to favour formation of imides, or mixtures of imides and amides, rather than amides and salts.
  • Reaction ratios can vary considerably, depending upon the reactants, amounts of excess amine, type of bonds formed, etc. Generally from 0.3 to 2, preferably from 0.3 to 1.0 e.g. 0.4 to 0.8, mole of amine, e.g.
  • bis-primary amine is used, per mole of the carboxylic acid moiety content, e.g. grafted maleic anhydride content.
  • carboxylic acid moiety content e.g. grafted maleic anhydride content.
  • one mole of olefin reacted with sufficient maleic anhydride to add 1.10 mole of maleic anhydride groups per mole of olefin when converted to a mixture of amides and imides about 0.55 moles of amine with two primary groups would preferably be used, i.e. 0.50 mole of amine per mole of dicarboxylic acid moiety.
  • the nitrogen-containing dispersant can be further treated by boration as generally taught in US-A-3 087 936 and 3 254 025.
  • Tris (hydroxymethyl) amino methane can be reacted with the aforesaid acid material to form amides, imides or ester type additives as taught by GB-A-984 409, or to form oxazoline compounds and borated oxazoline compounds as described, for example, in US-A-4 102 798, 4 116 876 and 4 113 639.
  • the ashless dispersants may also be esters derived from the long chain hydrocarbyl substituted carboxylic acid material and from hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc.
  • the polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to 8 carbon atoms.
  • polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, etc.
  • the ester dispersant may also be derived from unsaturayd alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, and oleyl alcohol.
  • unsaturayd alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, and oleyl alcohol.
  • Still other classes of alcohols capable of yielding the esters comprise the ether-alcohols and amino-alcohols including, for example the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene or amino-arylene oxy-arylene radicals.
  • the ester dispersant may be a di-ester of succinic acid or an acidic ester, i.e. a partially esterified succinic acid; or a partially esterified polyhydric alcohol or phenol, i.e. an ester having free alcoholic or phenolic hydroxyl radicals. Mixtures of the above illustrated esters are likewise contemplated.
  • the ester dispersant may be prepared by one of several known methods as illustrated for example in US-A-3 381 022.
  • Mannich base type dispersants such as those described in US-A-3 649 229 and 3 798 165 may also be used in these compositions.
  • Such Mannich base dispersants can be formed by reacting a high molecular weight, hydrocarbyl- substituted mono- or polyhydroxyl benzene (e.g. having a number average molecular weight of 1,000 or greater) with amines (e.g. polyalkyl polyamines, polyalkenyl polyamines, aromatic amines, carboxylic acid-substituted polyamines and the succinimide formed from any one of these with an olefinic succinic acid or anhydride) and carbonyl compounds (e.g. formaldehyde or para formaldehyde).
  • amines e.g. polyalkyl polyamines, polyalkenyl polyamines, aromatic amines, carboxylic acid-substituted polyamines and the succinimide formed from any one of these with an olefinic succ
  • a particularly suitable dispersant is one derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g. tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof.
  • polyethylene amines e.g. tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof.
  • Metal-containing rust inhibitors and/or detergents are frequently used with ashless dispersants.
  • Such detergents and rust inhibitors include oil-soluble mono- and di-carboxylic acids, the metal salts of sulfonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates and naphthenates in neutral or basic form.
  • Highly basic (or "over-based") metal salts which are frequently used as detergents, appear particularly prone to promote oxidation of hydrocarbon oils containing them.
  • these metal-containing rust inhibitors and detergents are used in lubricating oil in amounts of from 0.01 to 10, e.g. 0.1 to 5, weight percent, based on the weight of the total lubricating composition.
  • Highly basic alkali metal and alkaline earth metal sulfonates are frequently used as detergents. They are usually produced by heating a mixture comprising an oil-soluble sulfonate or alkaryl sulfonic acid, with an excess of alkali metal or alkaline earth metal compound above that required for complete neutralization of any sulfonic acid present and thereafter forming a dispersed carbonate complex by reacting the excess metal with carbon dioxide to provide the desired overbasing.
  • the sulfonic acids are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum by distillation and/or extraction or by the alkylation of aromatic hydrocarbons as for example those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl and the halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 30 carbon atoms.
  • alkaryl sulfonates usually contain from 9 to 70 or more carbon atoms, preferably from 16 to 50 carbon atoms per alkyl substituted aromatic moiety.
  • the alkali metal or alkaline earth metal compounds which may be used in neutralizing these alkaryl sulfonic acids to provide the sulfonates include the oxides and hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates and ethers of sodium, magnesium, calcium, strontium and barium. Examples are calcium oxide, calcium hydroxide, magnesium oxide, magnesium acetate and magnesium borate.
  • the alkaline earth metal compound is used in excess of that required to complete neutralization of the alkaryl sulfonic acids. Generally, the amount ranges from 100 to 220 percent, although it is preferred to use at least 125 percent of the stoichiometric amount of metal required for complete neutralization.
  • Preferred alkaline earth sulfonate additives are magnesium alkyl aromatic sulfonate additives having a high total base number (TBN) as measured by ASTM 02896 of at least 250, more preferably ranging from 300 to 400, and calcium alkyl aromatic sulfonates having a TBN of at least 250, preferably 300-400.
  • TBN total base number
  • Neutral metal sulfonates are frequently used as rust inhibitors.
  • Polyvalent metal alkyl salicylate and naphthenate materials are known additives for lubricating oil compositions to improve their high temperature performance and to counteract deposition of carbonaceous matter on pistons (US-A-2 744 069).
  • An increase in reserve basicity of the polyvalent metal alkyl salicylates and naphthenates can be realized by utilizing alkaline earth metal, e.g.
  • Such materials include alkaline earth metal, particularly magnesium, calcium, strontium and barium, salts of aromatic acids having the general formula: HOOC-ArR 10 OH-Z w (ArR 10 OH) r
  • Ar is an aryl radical of 1 to 6 rings
  • R 10 is an alkyl group having from 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms (optimally about 12)
  • Z is a sulfur (-S-) or methylene (-CH 2 -) bridge
  • w is a number from 0 to 4
  • r is a number from 0 to 4.
  • overbased methylene bridged salicylate-phenate salt is readily carried out by conventional techniques such as by alkylation of a phenol followed by phenation, carboxylation, hydrolysis, methylene bridging a coupling agent such as an alkylene dihalide followed by salt formation concurrent with carbonation.
  • An overbased calcium salt of a methylene bridged phenol-salicylic acid of the general formula: with a TBN of 60 to 150 is also useful.
  • Another type of basic metal detergent the sulfurized metal phenates
  • the individual R 11 groups may each contain from 5 to 40, preferably 8 to 20, carbon atoms.
  • the metal salt is prepared by reacting an alkyl phenol sulfide with a sufficient quantity of metal containing material to impart the desired alkalinity to the sulfurized metal phenate.
  • the sulfurized alkyl phenols which are useful generally contain from 2 to 14 percent by weight, preferably 4 to 12 weight percent sulfur based on the weight of sulfurized alkyl phenol.
  • the sulfurized alkyl phenol may be converted by reaction with a metal-containing material including oxides, hydroxides and complexes in an amount sufficient to neutralize said phenol and, if desired, to overbase the product to a desired alkalinity by procedures well known in the art.
  • a metal-containing material including oxides, hydroxides and complexes in an amount sufficient to neutralize said phenol and, if desired, to overbase the product to a desired alkalinity by procedures well known in the art.
  • Preferred is a process of neutralization utilizing a solution of metal in a glycol ether.
  • the neutral or normal sulfurized metal phenates are those in which the ratio of metal to phenol nucleus is about 1:2.
  • the "overbased” or “basic” sulfurized metal phenates are sulfurized metal phenates wherein the ratio of metal to phenol is greater than the stoichiometric ratio, e.g. basic sulfurized metal dodecyl phenate has a metal content up to (or greater) than 100 percent in excess of the metal present in the corresponding normal sulfurized metal phenate. The excess metal is produced in oil-soluble or dispersible form (as by reaction with CO 2 ).
  • the detergents which may be included in the compositions of the present invention may optionally be borated in a known manner. Such boration provides the detergent with a measure of anti-wear activity.
  • metal-containing detergents comprising calcium and magnesium salts or calcium, magnesium and sodium salts, as described above.
  • Antiwear Additives including extreme pressure agents
  • anti-wear additives may be included in the compositions or concentrates of the invention.
  • organic sulphides and polysulphides including especially dialkyl sulphides and polysulphides, e.g. dibutyl polysulphides, and dibenzyl sulphides and polysulphides, which may be substituted, e.g. with halogen, may be incorporated in the compositions or concentrates.
  • Sulphurized esters e.g. sulphurized methyl or isopropyl oleate and other sulphurized compounds, e.g.
  • sulphurized olefins such as sulphurized diisobutylene, sulphurized tripropylene or sulphurized dipentene may also be added to the compositions.
  • More complex sulphurized compounds such as sulphurized alkyl phenols and sulphurized terpenes and Diels-Alder adducts and sulphurized polymers, e.g. butadiene/butyl acrylate copolymers, may also be used as may sulphurized tall oil fatty acid esters.
  • Esters of beta-thiodipropionic acid, e.g. butyl, nonyl, tridecyl or eicosyl esters may also be used.
  • Anti-wear additives in the form of phosphorous esters may also be used.
  • phosphites include dibutyl phosphite, dihexyl phosphite, dicyclohexyl phosphite, alkyl phenyl phosphites such as dimethylphenyl phosphite and mixed higher alkyl, e.g. oleyl, and alkyl phenyl, e.g. 4-pentyl phenyl phosphite.
  • Phosphites based on polymers such as low molecular weight, polyethylenes and polypropylenes may also be used.
  • Preferred anti-wear additives for addition to the compositions and concentrates of the present invention are the dihydrocarbyl dithiophosphate metal salts. They also provide some antioxidant activity.
  • the zinc salts are most commonly used in lubricating oils in amounts of 0.1 to 10, preferably 0.2 to 2, weight percent, based upon the total weight of the lubricating oil composition. Salts of other metals, e.g. barium and cadmium, can also be used. They may be prepared in accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol or a phenol with P 2 S 5 and then neutralizing the dithiophosphoric acid with a suitable zinc compound.
  • Mixtures of alcohols may be used including mixtures of primary and secondary alcohols, secondary generally for importing improved antiwear properties, with primary giving improved thermal stability properties. Mixtures of the two are particularly useful.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • the zinc dihydrocarbyl dithiophosphates useful in the present invention are oil-soluble salts of dihydrocarbyl esters of dithiphosphoric acids and may be represented by the following formula: wherein R 12 and R 13 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R 12 and R 13 groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, s-hexyl, i-hexyl, i-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, nonyl-phenyl, dodecyl-cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc.
  • the total number of carbon atoms (i.e. R 12 and R 13 ) in the dithiophosphoric acid generally should be about 5 or greater and preferably 8 or greater.
  • Borated derivatives of the aforesaid antiwear agents may also be included in the compositions or concentrates of the invention.
  • antioxidants which are especially useful in lubricating oil compositions or concentrates are based on oil-soluble copper compounds, e.g. in the form of a synthetic or natural carboxylic acid salt.
  • oil-soluble is meant that the compound is oil-soluble or solubilized under normal blending conditions in the oil or concentrate.
  • oil-soluble copper compounds include salts of C 10 to C 18 fatty acids such as stearic or palmitic acid; but unsaturated acids (such as oleic acid), branched carboxylic acids (such as naphthenic acids) of molecular weight from 200 to 500, dicarboxylic acids such as polyisobutenyl succinic acids, and synthetic carboxylic acids can all be used because of the acceptable handling and solubility properties of the resulting copper carboxylates.
  • unsaturated acids such as oleic acid
  • branched carboxylic acids such as naphthenic acids
  • dicarboxylic acids such as polyisobutenyl succinic acids
  • synthetic carboxylic acids can all be used because of the acceptable handling and solubility properties of the resulting copper carboxylates.
  • Suitable oil-soluble copper dithiocarbamates have the general formula (R 14 R 15 N.CS.S) p Cu; where p is 1 or 2 and R 14 and R 15 may be the same or different hydrocarbyl radicals containing from 1 to 18 carbon atoms each and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R 14 and R 15 groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may be, for example, ethyl, n-propyl, n-butyl, i-butyl, sec-butyl, amyl, sec-hexyl, i-hexyl, i-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, nonyl-phenyl, dodecyl-phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc.
  • the total number of carbon atoms i.e. R 14 and R 15
  • R 14 and R 15 generally should be about 5 or greater.
  • Copper salts of dithiophosphonic acids (the acid as described hereinbefore in relation to antiwear additives specifically as zinc salts), copper sulfonates, phenates and acetyl acetonates can also be used.
  • antioxidants can be used in amounts such that, in the final lubricating composition, a copper concentration of from 5 to 500 ppm is present.
  • antioxidants may also be used in the compositions of the invention.
  • antioxidants include hindered phenols, which may contain sulphur, e.g. 4,4'-methylene bis (2,6-di(t-butyl)phenol), 4,4'-thio bis (2,6-di(t-butyl)phenol) and p-alkylated hindered phenols; unhindered phenols which again may contain sulphur such as 2,2'-thio bis-(4-nonyl phenol) and 2,2'-methylene bis (4-nonylphenol); phenothiazine derivatives, e.g.
  • alkyl substituents such as dioctyl and dinonyl phenothiazines; substituted alpha and betanaphthyl amines such as phenyl beta-naphthylamine and its alkylated derivatives; other amino aryl compounds such as for example 4,4'-bis(secbutylamino) diphenylmethane; dithiocarbamates such as zinc, nickel, copper, or molybdenum dithiocarbamates; and phosphosulphurized olefins, e.g. phosphosulphurized pinene or styrene.
  • dioctyl and dinonyl phenothiazines substituted alpha and betanaphthyl amines such as phenyl beta-naphthylamine and its alkylated derivatives
  • other amino aryl compounds such as for example 4,4'-bis(secbutylamino) diphenylmethane
  • Corrosion inhibitors which act by deactivating metal parts with which they come in contact and/or as sulphur scavengers can also be used in the compositions or concentrates of the invention.
  • examples of such agents include benzotriazole derivatives; thiadiazole compounds, e.g. 2,5-dimercapto 1,3,4-thiadiazole; mercaptobenzothiazole compounds in the form of amine salts, sulphonamides, thiosulphonamides, and condensates of mercaptobenzothiazole with amines and formaldehyde; salicylaldehyde/diamine condensation products; dialkylphosphites, e.g.
  • dioleyl or di-2-ethylhexyl phosphite trialkyl and triarylphosphites, e.g. tris-(2-ethyl-hexyl), triphenyl or tri(4-nonylphenol) phosphites
  • thiophosphonates such as triphenyl or trilauryl thiophosphonate or trilauryl tetrathiophosphonate.
  • Friction modifiers and fuel economy agents which are compatible with the other ingredients of the new compositions or concentrates may also be included.
  • examples of such materials are glyceryl monoesters and/or diesters of higher fatty acids, e.g. glyceryl mono-oleate and esters of long-chain polycarboxylic acids with diols, e.g. the butane diol ester of a dimerized unsaturated fatty acid, and oxazoline compounds.
  • Viscosity index improvers are typically polymers of number average molecular weight 10 3 to 10 6 - for example ethylene copolymers or polybutenes. Viscosity index improvers may be modified to have dispersant properties and suitable viscosity index improver dispersants for use in compositions of the invention are described in, for example, European Specification No 24 146 A.
  • Preferred viscosity index improvers with dispersant properties for use in the compositions of the present invention comprise a poly-olefin moiety to which is grafted an unsaturated carboxylic acid moiety, the carboxylic acid groups being reacted with an amine, hydroxyamine or alcohol.
  • Antioxidants may be evaluated using the sequence III E test (ASTM STP 315) which is a standard test used for assessing the oxidation resistance of lubricants and which is a more stringent version of the sequence III D test (ASTM STP 315M and ASTM STP 315).
  • the sequence III method produces a result after 64 hrs of testing with an acceptable performance being a 375% or less increase in kinematic viscosity as measured at 40°C after this period.
  • the principle of this method is to observe oil thickening as a result of oxidation.
  • One such method which is commonly used is a thin film high temperature catalytic oxidation test performed using a DSC.
  • Table 1 lists details of the diphenylamines nominally of general structure II which were used in the following examples.
  • Table 1 No. Diphenylamine Trade Name % N R 5 and R 6 in general formula II 1 Pearsall OA 502 3.9
  • Mixture of C 4 , C 8 and styryl 4 Naugalube 680 4.3 Mixture of C 4 , C 8 and styryl 5 Irganox L-57 4.7 Mixture of t-butyl and t-octyl 6 Vanlube 848 4.7 Mixture of t-butyl and t-octyl 7 Vanlube DND 3.3
  • the Differential Screening Calorimetry (DSC) test method used in the examples below is a thin film high temperature catalytic oxidation test.
  • the compounds to be tested for antioxidancy performance are added at the required treat rate to a sample of lubricant oil containing 500 ppm Fe and 2000 ppm Pb.
  • This test sample (6-9mg) is placed in the center of an aluminum DSC pan and inserted into a DuPont 990 High Pressure DSC.
  • the cell of the DSC is then purged three times with 100 psi O 2 and then filled with O 2 at 250 psi.
  • the cell is then heated at a programmed ramped rate of 100°C/min to the isothermal temperature of 190°C.
  • the oxidation induction time (OIT; time to auto-oxidation) is the time at which the baseline intersects with a line tangent to the curve of the exothermal heat flow versus time scan.
  • OIT is reported in minutes.
  • the magnitude of the OIT is an indication of the effectiveness of the compounds or compound mixtures under test as antioxidants; the larger the OIT the greater the antioxidant effect.
  • the control formulation in which the amines and the molybdenum compounds were tested comprised an Amoco Whiting base oil and an additive package which contained: a polyisobutene substituted succinimide dispersant, a low base number calcium sulphonate, a 400 total base number magnesium sulphonate, ZDDP and a demulsifier.
  • a polyisobutene substituted succinimide dispersant a polyisobutene substituted succinimide dispersant
  • a low base number calcium sulphonate a 400 total base number magnesium sulphonate
  • ZDDP total base number magnesium sulphonate
  • demulsifier a demulsifier
  • a molybdenum compound which is a commercially available material sold under the trade mark Molyvan 822 and is believed to have the nominal structure below, was evaluated with diphenylamines as listed in table 3 by means of the same DSC method.
  • Examples 8 to 23 were carried out using the same base oil and additive package as in Examples 1-7.
  • Examples 24 and 25 were carried out using a different base oil namely Petroscan Hydrocracked, with the same additive package. Again the results, which are shown in Table 3, show the synergistic effect observed with the combination of molybdenum compound of general formula I and diphenylamine of general formula II.
  • a molybdenum compound of formula MoS 2 DTC 3 wherein the DTC represents a dithiocarbamate group and the molybdenum is in oxidation state six was found to exhibit no synergistic antioxidant effect when used with diphenylamines of general formula II.

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Claims (16)

  1. Schmieröladditiv, das eine Kombination aus einer öllöslichen molybdänhaltigen Verbindung mit der allgemeinen Formel I:
    Figure imgb0012
     in der R1, R2, R3 und R4 gleich oder unterschiedlich sein können und jeweils unabhängig einen C7- bis C24-Kohlenwasserstoffrest wiedergeben, X und X1 gleich oder unterschiedlich sein können und unabhängig S oder O wiedergeben, und das Mo im Oxidationszustand von V oder weniger vorliegt, und mindestens einem öllöslichen Diphenylamin umfaßt.
  2. Schmieröladditiv nach Anspruch 1, bei dem R1, R2, R3 und R4 jeweils unabhängig einen C10- bis C18-Kohlenwasserstoffrest wiedergeben.
  3. Schmieröladditiv nach Anspruch 2, bei dem R1, R2, R3 und R4 jeweils unabhängig C12- oder C13-Kohlenwasserstoffreste wiedergeben.
  4. Schmieröladditiv nach einem der vorhergehenden Ansprüche, bei dem X=X1=S.
  5. Schmieröladditiv nach Anspruch 1, bei dem das Diphenylamin ein dialkyliertes Diphenylamin ist.
  6. Schmierölzusammensetzung, die ein Schmieröl und als Antioxidans das Schmieröladditiv nach einem der Ansprüche 1 bis 5 umfaßt.
  7. Schmierölzusammensetzung nach Anspruch 6, bei der das Schmieröladditiv in einer Konzentration von 0,01 bis 15 Gew.%, bezogen auf das Gesamtgewicht der Zusammensetzung, vorhanden ist.
  8. Schmierölzusammensetzung nach Anspruch 7, bei der das Schmieröladditiv in einer Konzentration von 0,1 bis 7 Gew.% vorhanden ist.
  9. Schmierölzusammensetzung nach Anspruch 6, bei der außerdem ein oder mehrere der folgenden Additive vorhanden sind: ein Dispergiermittel, ein Detergens, ein Antiverschleißadditiv, ein Korrosionsschutzmittel, ein Metalldesaktivator, ein Reibungsmodifizierungsmittel, ein Kraftstofferspamismittel, ein Viskositätsindexverbesserer und ein Antioxidans.
  10. Schmierölkonzentrat, das ein Lösungsmittel und das Schmieröladditiv nach einem der Ansprüche 1 bis 5 umfaßt.
  11. Schmierölkonzentrat nach Anspruch 10, das zwischen 2,5 und 90 Gew.% des Additivs umfaßt.
  12. Schmierölkonzentrat nach Anspruch 11, das zwischen 5 und 75 Gew.% des Schmieröladditivs umfaßt.
  13. Schmierölkonzentrat nach Anspruch 12, bei dem das Lösungsmittel ein Mineralöl oder synthetisches Öl ist.
  14. Schmierölkonzentrat nach Anspruch 9, bei dem außerdem ein oder mehrere der folgenden Additive vorhanden sind: ein Dispergiermittel, ein Detergens, ein Antiverschleißadditiv, ein Korrosionsschutzmittel, ein Metalldesaktivator, ein Reibungsmodifizierungsmittel, ein Kraftstoffersparnismittel, ein Viskositätsindexverbesserer und ein Antioxidans.
  15. Verwendung eines Schmieröladditivs nach einem der Ansprüche 1 bis 5 als Antioxidans in Schmierölen.
  16. Schmieröladditiv, das eine Kombination aus MOLYVAN 822 (eingetragene Marke) als Antioxidans; und mindestens einem öllöslichen Diphenylamin umfaßt.
EP94928344A 1993-09-13 1994-09-13 Gemischte antioxydationsmittelzusammensetzung Revoked EP0719313B1 (de)

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Application Number Priority Date Filing Date Title
US12071293A 1993-09-13 1993-09-13
US120712 1993-09-13
PCT/EP1994/003064 WO1995007963A1 (en) 1993-09-13 1994-09-13 Mixed antioxidant composition

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EP0719313A1 EP0719313A1 (de) 1996-07-03
EP0719313B1 true EP0719313B1 (de) 1997-08-06

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EP (1) EP0719313B1 (de)
JP (1) JPH09506118A (de)
AU (1) AU680553B2 (de)
CA (1) CA2171537A1 (de)
DE (1) DE69404849T2 (de)
ES (1) ES2105758T3 (de)
WO (1) WO1995007963A1 (de)

Cited By (2)

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US6103674A (en) * 1999-03-15 2000-08-15 Uniroyal Chemical Company, Inc. Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions
US9222054B2 (en) 2009-12-24 2015-12-29 Jx Nippon Oil & Energy Corporation Cylinder lubricating oil composition for crosshead-type diesel engine

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JP3284821B2 (ja) * 1995-04-21 2002-05-20 株式会社日立製作所 電動回転機
USRE38929E1 (en) * 1995-11-20 2006-01-03 Afton Chemical Intangibles Llc Lubricant containing molybdenum compound and secondary diarylamine
US5650381A (en) * 1995-11-20 1997-07-22 Ethyl Corporation Lubricant containing molybdenum compound and secondary diarylamine
US5824627A (en) * 1996-12-13 1998-10-20 Exxon Research And Engineering Company Heterometallic lube oil additives
US6358894B1 (en) 1996-12-13 2002-03-19 Infineum Usa L.P. Molybdenum-antioxidant lube oil compositions
US5840672A (en) * 1997-07-17 1998-11-24 Ethyl Corporation Antioxidant system for lubrication base oils
US5939364A (en) * 1997-12-12 1999-08-17 Exxon Research & Engineering Co. Lubricating oil containing additive comprising reaction product of molybdenum dithiocarbamate and dihydrocarbyl dithiophosphoric acid
JP4201902B2 (ja) * 1998-12-24 2008-12-24 株式会社Ａｄｅｋａ 潤滑性組成物
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
JP5756342B2 (ja) * 2011-05-26 2015-07-29 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
US10487043B2 (en) 2015-07-15 2019-11-26 Lanxess Solutions Us Inc. Diaryl amine antioxidants prepared from branched olefins
US10711219B2 (en) * 2017-12-11 2020-07-14 Infineum International Limited Automotive transmission fluid compositions for improved energy efficiency
EP4247922B1 (de) 2020-11-17 2025-08-20 Songwon Industrial Co., Ltd. Zusammensetzungen mit alkylierten diphenylaminen mit verbesserten eigenschaften
JP7499712B2 (ja) * 2021-02-02 2024-06-14 株式会社日立製作所 潤滑油の診断方法およびシステム
TW202311225A (zh) 2021-06-25 2023-03-16 韓商松原產業股份有限公司 O-烷基化位阻抗氧化劑

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JPS5180825A (ja) * 1975-01-14 1976-07-15 Asahi Denka Kogyo Kk Ganmoribudenkagobutsunoseizohoho
US4394279A (en) * 1981-08-07 1983-07-19 Chevron Research Company Antioxidant combinations of sulfur containing molybdenum complexes and aromatic amine compounds for lubricating oils
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US4846983A (en) * 1986-02-21 1989-07-11 The Lubrizol Corp. Novel carbamate additives for functional fluids
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JP2617807B2 (ja) * 1990-03-16 1997-06-04 日本石油株式会社 エンジン油組成物

Cited By (2)

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Publication number Priority date Publication date Assignee Title
US6103674A (en) * 1999-03-15 2000-08-15 Uniroyal Chemical Company, Inc. Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions
US9222054B2 (en) 2009-12-24 2015-12-29 Jx Nippon Oil & Energy Corporation Cylinder lubricating oil composition for crosshead-type diesel engine

Also Published As

Publication number Publication date
JPH09506118A (ja) 1997-06-17
WO1995007963A1 (en) 1995-03-23
ES2105758T3 (es) 1997-10-16
AU7781894A (en) 1995-04-03
DE69404849D1 (de) 1997-09-11
DE69404849T2 (de) 1998-01-29
EP0719313A1 (de) 1996-07-03
AU680553B2 (en) 1997-07-31
CA2171537A1 (en) 1995-03-23

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