EP3110929B1 - Schmiermittelzusammensetzung auf basis von metallnanopartikeln - Google Patents

Schmiermittelzusammensetzung auf basis von metallnanopartikeln Download PDF

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Publication number
EP3110929B1
EP3110929B1 EP15706812.3A EP15706812A EP3110929B1 EP 3110929 B1 EP3110929 B1 EP 3110929B1 EP 15706812 A EP15706812 A EP 15706812A EP 3110929 B1 EP3110929 B1 EP 3110929B1
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Prior art keywords
lubricant composition
group
composition according
compound
dithiophosphate
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EP15706812.3A
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English (en)
French (fr)
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EP3110929A1 (de
Inventor
Benoit Thiebaut
Fabrice DASSENOY
Paula USSA
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TotalEnergies Onetech SAS
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Total Marketing Services SA
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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
    • C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06—Particles of special shape or size
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants

Definitions

  • the present invention is applicable to the field of lubricants, and more particularly to the field of lubricants for motor vehicles.
  • the invention relates to a lubricating composition comprising metallic nanoparticles. More particularly, the invention relates to a lubricating composition comprising an anti-wear additive and metallic nanoparticles.
  • the lubricating composition according to the invention simultaneously exhibits good stability as well as good friction properties which last over time.
  • additive concentrate type composition comprising an anti-wear additive and metallic nanoparticles.
  • the level of friction can be adjusted by adding friction modifiers to these gear oils.
  • the improvement in the energy performance of the lubricating compositions can be obtained in particular by mixing friction modifiers in the base oils.
  • organometallic compounds comprising molybdenum are commonly used. In order to obtain good friction reduction properties, a sufficient quantity of molybdenum must be present within the lubricating composition.
  • these compounds have the drawback of inducing the formation of sediments when the lubricating composition has too high a content of molybdenum element.
  • the poor solubility of these compounds modifies or even deteriorates the properties of the lubricating composition, in particular its viscosity.
  • a composition that is too viscous or not viscous enough is detrimental to the movement of moving parts, to the correct starting of an engine, to the protection of an engine when it has reached its operating temperature, and therefore ultimately causes in particular an increase in fuel consumption.
  • these compounds contribute to an increase in the ash content, reducing their potential for use in a lubricating composition, in particular in Europe.
  • compositions comprising organomolybdenum-type friction modifier compounds with organophosphorus and/or organosulfur and/or organophosphorus anti-wear and extreme pressure compounds, in particular to improve the anti-wear properties of these oils. engines or transmissions.
  • the document CN 101691517 describes an engine oil comprising nanoparticles of tungsten disulphide, making it possible to improve engine life and reduce fuel consumption.
  • the content of tungsten disulphide nanoparticles ranges from 15 to 34%, which can lead to risks of instability of the oil over time.
  • FR 2 910 911 discloses a lubricant composition
  • a lubricant composition comprising a base oil and metal-containing nanoparticles, the particles having an average diameter of 1 to 10 nm.
  • a lubricating composition in particular for motor vehicles, which is not a grease while exhibiting good properties for reducing friction and retaining satisfactory anti-flaking properties.
  • One objective of the present invention is to provide a lubricating composition which overcomes all or part of the aforementioned drawbacks.
  • Another objective of the invention is to provide a lubricating composition which is stable and easy to implement.
  • Another object of the present invention is to provide a method of lubrication which makes it possible in particular to reduce friction on the surface of mechanical parts, and more particularly of an engine or a transmission member of motor vehicles.
  • the metallic nanoparticles have an average size, determined using images obtained by transmission electron micrography or by high-resolution transmission electron microscopy, of 50 to 200 nm and are concentric polyhedra with a multilayer or sheet structure.
  • an anti-wear compound comprising a dithiophosphate group in a lubricating composition comprising at least one base oil and metallic nanoparticles as defined above makes it possible to confer on said composition very good friction reducing properties.
  • an anti-wear compound comprising a dithiophosphate group and metallic nanoparticles as defined above in a lubricating composition makes it possible to maintain this reduction in friction over time.
  • this maintenance over time of the effectiveness of friction reduction could be explained by the protection against the oxidation of the metallic nanoparticles by the anti-wear compound comprising a dithiophosphate group, thus extending the action of metallic nanoparticles on the surface of a mechanical part, and more particularly of a transmission member or motor vehicle engine.
  • the present invention makes it possible to formulate stable lubricating compositions comprising a reduced content of metallic nanoparticles and yet exhibiting remarkable friction reduction properties.
  • the lubricating compositions according to the invention have remarkable friction reduction properties which last over time.
  • the lubricating compositions according to the invention have good oil stability and a viscosity which does not vary or varies very little.
  • the lubricating compositions according to the invention have satisfactory anti-flaking properties.
  • the lubricating compositions according to the invention have a reduced risk of oxidation.
  • the lubricating compositions according to the invention have remarkable fuel saving properties
  • the lubricating composition consists essentially of at least one base oil, at least one anti-wear compound comprising a dithiophosphate group and at least metallic nanoparticles as defined above in a content by weight ranging from 0 0.01 to 2% relative to the total weight of the lubricating composition.
  • the application also describes an engine oil comprising a lubricating composition as defined above.
  • the application also describes a transmission oil comprising a lubricating composition as defined above.
  • the invention also relates to the use of a lubricating composition as defined above for lubricating a mechanical part, preferably a transmission member or a vehicle engine, advantageously motor vehicles.
  • the invention also relates to the use of a lubricating composition as defined above for reducing friction on the surface of a mechanical part, preferably a transmission member or a vehicle engine, advantageously motor vehicles.
  • the invention also relates to the use of a lubricating composition as defined above for reducing the fuel consumption of vehicles, in particular motor vehicles.
  • the application also describes a process for lubricating a mechanical part, preferably a transmission member or a vehicle engine, advantageously motor vehicles, said process comprising at least one step of bringing the mechanical part into contact with a lubricating composition as defined above.
  • the application also describes a method for reducing friction on the surface of a mechanical part, preferably of a transmission member or of a vehicle engine, advantageously of motor vehicles, comprising at least bringing the mechanical part into contact with a lubricating composition as defined above.
  • the application also describes a method for reducing the fuel consumption of a vehicle, in particular of a motor vehicle, comprising at least one step of bringing a mechanical part of the engine of the vehicle into contact with a lubricating composition as defined above.
  • the invention also relates to the use of an anti-wear compound comprising a dithiophosphate group to reduce the oxidation of a lubricating composition
  • composition of the concentrate type of additives comprising at least at least one compound comprising a dithiophosphate group and tungsten disulphide nanoparticles.
  • the lubricating composition according to the invention comprises metallic nanoparticles in a content by weight ranging from 0.01 to 2% relative to the total weight of the lubricating composition.
  • metallic nanoparticles in particular metallic particles, generally solid, whose average size is less than or equal to 600 nm.
  • the metallic nanoparticles consist of at least 80% by mass of at least one metal, or else of at least 80% by mass of at least one metal alloy or else of at least 80% by mass of at least one metal chalcogenide, in particular of transition metal, with respect to the total mass of the nanoparticle.
  • the metallic nanoparticles consist of at least 90% by mass of at least one metal, or else of at least 90% by mass of at least one metal alloy or else of at least 90% by mass of at least one metal chalcogenide, in particular of transition metal, with respect to the total mass of the nanoparticle.
  • the metallic nanoparticles consist of at least 99% by mass of at least one metal, or else of at least 99% by mass of at least one metal alloy or else of at least 99% by mass of at least one metal chalcogenide, in particular of transition metal, with respect to the total mass of the nanoparticle, the remaining 1% being constituted by impurities.
  • the metal of which the metallic nanoparticle is made can be chosen from the group formed by tungsten, molybdenum, zirconium, hafnium, platinum, rhenium, titanium, tantalum and niobium, preferably molybdenum or tungsten, advantageously tungsten.
  • M is chosen from the group formed by tungsten, molybdenum, zirconium, hafnium, platinum, rhenium, titanium, tantalum and niobium.
  • M is selected from the group consisting of molybdenum and tungsten.
  • M is tungsten
  • X is chosen from the group formed by oxygen, sulfur, selenium and tellurium.
  • X is chosen from sulfur or tellurium.
  • X is sulfur
  • the metallic nanoparticles according to the invention are chosen from the group formed by MoS2, MoSe 2 , MoTe 2 , WS 2 , WSe 2 , ZrS 2 , ZrSe 2 , HfS 2 , HfSe 2 , PtS 2 , ReS 2 , ReSe 2 , TiS 3 , ZrS 3 , ZrSe 3 , HfS 3 , HfSe 3 , TiS 2 , TaS 2 , TaSe 2 , NbS 2 , NbSe 2 and NbTe 2 .
  • the metallic nanoparticles according to the invention are chosen from the group formed by WS 2 , WSe 2 , MoS 2 and MoSe 2 , preferentially WS 2 and MoS 2 , preferentially WS 2 .
  • the nanoparticles according to the invention have a fullerene-type structure.
  • fullerene designates a closed convex polyhedron nanostructure, composed of carbon atoms.
  • Fullerenes are similar to graphite, consisting of sheets of bonded hexagonal rings, but they contain pentagonal, and sometimes heptagonal, rings that prevent the structure from being flat.
  • fullerene-like structures are not limited to carbonaceous materials, but is likely to occur in all nanoparticles of materials in the form of sheets, especially for nanoparticles comprising chalcogens and metals of transition.
  • These structures are analogous to that of carbon fullerenes and are called inorganic fullerenes or fullerene-like structures (in English terms “Inorganic Fullerene like materials”, also referred to as “IF”).
  • Fullerene-like structures are described in particular by Tenne, R., Margulis, L., Genut M. Hodes, G. Nature 1992, 360, 444 .
  • the document EP 0580 019 describes in particular these structures and their method of synthesis.
  • the metallic nanoparticles are closed structures, of the spherical type, more or less perfect depending on the synthesis methods used.
  • the nanoparticles according to the invention are concentric polyhedrons with a multilayer or sheet structure. We speak of an "onion” or “nested polyhedron” structure.
  • the metallic nanoparticles are multilayer metallic nanoparticles comprising from 2 to 500 layers, preferably from 20 to 200 layers, advantageously from 20 to 100 layers.
  • the average size of the metallic nanoparticles according to the invention ranges from 50 to 200 nm.
  • the size of the metallic nanoparticles according to the invention can be determined using images obtained by transmission electron micrography or by electron microscopy. high resolution transmission.
  • the average particle size can be determined from the measurement of the size of at least 50 solid particles visualized on transmission electron micrographs.
  • the median value of the measured size distribution histogram of the solid particles is the average size of the solid particles used in the lubricating composition according to the invention.
  • the content by weight of metallic nanoparticles ranges from 0.05 to 2%, preferably from 0.1 to 1%, advantageously from 0.1 to 0.5% relative to the total weight of the lubricating composition.
  • NanoLub Gear Oil Concentrate marketed by the company Nanomaterials, which is in the form of a dispersion of multilayer nanoparticles of tungsten disulphide in a mineral or PAO type oil ( Poly Alfa Olefin).
  • the lubricating composition according to the invention comprises at least one anti-wear compound comprising a dithiophosphate group.
  • the anti-wear compound comprising a dithiophosphate group is called “dithiophosphate” in the rest of the present description.
  • the dithiophosphate can be chosen from ammonium dithiophosphates, amine dithiophosphates, ester dithiophosphates and metal dithiophosphates, taken alone or as a mixture.
  • the dithiophosphate is chosen from the ammonium dithiophosphates of formula (I): in which R1 and R2 represent, independently of each other, an optionally substituted hydrocarbon group comprising from 1 to 30 carbon atoms.
  • R1 and R2 independently of each other represent a hydrocarbon group, optionally substituted, comprising from 2 to 24 carbon atoms, more preferentially from 3 to 18 carbon atoms, advantageously from 5 to 12 carbon atoms.
  • R1 and R2 independently represent an unsubstituted hydrocarbon group, said hydrocarbon group possibly being an alkyl, alkenyl, alkynyl, phenyl or benzyl group.
  • R1 and R2 independently represent a linear or branched alkyl hydrocarbon group, more preferably a linear alkyl hydrocarbon group.
  • R1 and R2 independently represent a hydrocarbon group optionally substituted by at least one oxygen, nitrogen, sulfur and/or phosphorus atom, preferably by at least one oxygen atom.
  • ammonium dithiophosphate mention may be made of ammonium dimethyl dithiophosphates, ammonium diethyl dithiophosphates and ammonium dibutyl dithiophosphates.
  • R3 and R4 independently of each other represent a hydrocarbon group, optionally substituted, comprising from 2 to 24 carbon atoms, more preferentially from 3 to 18 carbon atoms, advantageously from 5 to 12 carbon atoms.
  • R3 and R4 independently represent an unsubstituted hydrocarbon group, said hydrocarbon group possibly being an alkyl, alkenyl, alkynyl, phenyl or benzyl group.
  • R3 and R4 independently represent a linear or branched alkyl hydrocarbon group, more preferably a linear alkyl hydrocarbon group.
  • R3 and R4 independently represent a hydrocarbon group optionally substituted by at least one oxygen, nitrogen, sulfur and/or phosphorus atom, preferably by at least one oxygen atom.
  • R5, R6 and R7 independently represent a hydrocarbon group comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, advantageously from 5 to 12 carbon atoms.
  • R8 and R9 independently represent an optionally substituted hydrocarbon group comprising from 2 to 24 carbon atoms, more preferentially from 3 to 18 carbon atoms, advantageously from 5 to 12 carbon atoms.
  • R8 and R9 independently represent an unsubstituted hydrocarbon group, said hydrocarbon group possibly being an alkyl, alkenyl, alkynyl, phenyl or benzyl group.
  • R8 and R9 independently represent a linear or branched alkyl hydrocarbon group, more preferably a linear alkyl hydrocarbon group.
  • R8 and R9 independently represent a hydrocarbon group optionally substituted by at least one oxygen, nitrogen, sulfur and/or phosphorus atom, preferably by at least one oxygen atom.
  • R8 and R9 represent, independently of each other, a hydrocarbon group comprising from 2 to 6 carbon atoms.
  • R10 and R11 independently represent a hydrocarbon group comprising from 2 to 6 carbon atoms.
  • the metal is selected from the group consisting of zinc, aluminum, copper, iron, mercury, silver, cadmium, tin, lead, antimony, bismuth, thallium, chromium, molybdenum, cobalt, nickel, tungsten, sodium, calcium, magnesium, manganese and arsenic.
  • Preferred metals are zinc, molybdenum, antimony, preferably zinc and molybdenum.
  • the metal is zinc.
  • Metal dithiophosphates are neutral as exemplified in formula (IV) or basic when a stoichiometric excess of metal is present.
  • R12 and R13 independently represent an optionally substituted hydrocarbon group comprising from 2 to 24 carbon atoms, more preferentially from 3 to 18 carbon atoms, advantageously from 5 to 12 carbon atoms.
  • R12 and R13 independently represent an unsubstituted hydrocarbon group, said hydrocarbon group possibly being an alkyl, alkenyl, alkynyl, phenyl or benzyl group.
  • R12 and R13 independently represent a linear or branched alkyl hydrocarbon group, more preferably a linear alkyl hydrocarbon group.
  • R12 and R13 independently represent a hydrocarbon group optionally substituted by at least one oxygen, nitrogen, sulfur and/or phosphorus atom, preferably by at least one oxygen atom.
  • the dithiophosphate according to the invention is a zinc dithiophosphate of formula (IV-a) or of formula (IV-b): wherein R12 and R13 are as defined above.
  • metal dithiophosphate As metal dithiophosphate according to the invention, one can quote for example Additin ® RC 3038, Additin ® RC 3045, Additin ® RC 3048, Additin ® RC 3058, Additin° RC 3080, Additin° RC 3180, Additin° RC 3212, Additin° RC 3580, Kikulube° Z112, Lubrizol ® 1371, Lubrizol ® 1375, Lubrizol ® 1395, Lubrizol ® 5179, Oloa ® 260, Oloa® 267.
  • the content by weight of anti-wear compound comprising a dithiophosphate group ranges from 0.1 to 5%, relative to the total weight of the lubricating composition.
  • the content by weight of compound comprising a dithiophosphate group ranges from 0.2 to 4%, more preferably from 0.5 to 2%, advantageously from 0.5 to 1.5% per relative to the total weight of the lubricating composition.
  • the lubricating compositions according to the invention can contain any type of mineral, synthetic or natural, animal or vegetable lubricating base oil suitable for their use.
  • the base oil(s) used in the lubricating compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized below, singly or in combination.
  • Table I Content Saturates content Sulfur content Viscosity index (VI) Group I Mineral Oils ⁇ 90% > 0.03% 80 ⁇ IV ⁇ 120 Group II Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ IV ⁇ 120 Group III Hydrocracked or hydroisomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group IV Polyalphaolefins (PAO) Group V Esters and other bases not included in bases groups I to IV
  • the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking and hydroisomerization, hydrofinishing.
  • the base oils of the lubricating compositions according to the invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
  • the polyalphaolefins used as base oils are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100° C. of between 1.5 and 15 cSt measured according to the ASTM D445 standard. Their weight-average molecular weight is typically between 250 and 3000 measured according to standard ASTM D5296. Blends of synthetic and mineral oils can also be used.
  • a lubricating base for producing the lubricating compositions according to the invention there is no limitation as to the use of such and such a lubricating base for producing the lubricating compositions according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulphur, resistance to oxidation, suitable for use in a gearbox, in particular in a motor vehicle gearbox, in particular in a manual gearbox.
  • the lubricating bases represent at least 70% by mass, relative to the total mass of the lubricating composition, Typically, they represent between 75 and 99.9% by mass, relative to the total mass of the lubricating compositions according to the invention.
  • the lubricating composition according to the invention has a kinematic viscosity at 100° C. measured according to the ASTM D445 standard ranging from 4 to 50 cSt.
  • the kinematic viscosity at 100° C. measured according to the ASTM D445 standard of the composition according to the invention ranges from 4 to 45 cSt, preferably from 4 to 30 cSt.
  • the lubricating compositions comprise at least one Group IV base.
  • the lubricating compositions have a viscosity index (VI) greater than 95 (ASTM 2270 standard).
  • the lubricating compositions according to the invention may also contain any type of additive suitable for their use in the formulations of oils for transmissions, for example one or more additives chosen from polymers, antioxidants, anti-corrosion additives, modifiers different frictions of the metallic nanoparticles according to the invention and the dispersants, present at the usual levels required for the application.
  • the additive is chosen from dispersants having a weight-average molecular mass greater than or equal to 2000 Daltons.
  • the weight-average molecular mass of the dispersant is evaluated according to the ASTM D5296 standard.
  • dispersant within the meaning of the present invention, is meant more particularly any compound which improves the maintenance in suspension of the metallic nanoparticles.
  • the dispersant can be chosen from compounds comprising at least one succinimide group, polyolefins, olefin copolymers (OCP), copolymers comprising at least one styrene unit, polyacrylates or their derivatives. .
  • derivatives any compound comprising at least one group or one polymeric chain as defined above.
  • the dispersant according to the invention is chosen from compounds comprising at least one succinimide group.
  • the dispersant is chosen from compounds comprising at least one substituted succinimide group or compounds comprising at least two substituted succinimide groups, the succinimide groups being linked at their top bearing a d atom. nitrogen by a polyamine group.
  • substituted succinimide group within the meaning of the present invention, is meant a succinimide group of which at least one of the carbon vertices is substituted by a hydrocarbon group comprising from 8 to 400 carbon atoms.
  • the dispersant is chosen from polyisobutylene succinimide-polyamine
  • the dispersant according to the invention has a weight-average molecular mass ranging from 2000 to 15000 Daltons, preferably ranging from 2500 to 10000 Daltons, advantageously from 3000 to 7000 Daltons.
  • the dispersant has a number molecular mass greater than or equal to 1000 Daltons, preferably ranging from 1000 to 5000 Daltons, more preferably from 1800 to 3500 Daltons, advantageously from 1800 to 3000 Daltons.
  • the number molecular weight of the dispersant is evaluated according to the ASTM D5296 standard.
  • the content by weight of dispersant having a weight average molecular mass greater than or equal to 2000 Daltons ranges from 0.1 to 10%, preferably from 0.1 to 5%, advantageously from 0.1 to 3% relative to the total weight of the lubricating composition.
  • the polymers can be chosen from the group of shear-stable polymers, preferably from the group consisting of copolymers of ethylene and alpha-olefin, polyacrylates such as polymethacrylates, olefin copolymers (OCP), Ethylene Propylene Diene Monomers (EPDM), polybutenes, copolymers of styrene and olefin, hydrogenated or not, or copolymers of styrene and acrylate.
  • polyacrylates such as polymethacrylates, olefin copolymers (OCP), Ethylene Propylene Diene Monomers (EPDM), polybutenes, copolymers of styrene and olefin, hydrogenated or not, or copolymers of styrene and acrylate.
  • the antioxidants can be chosen from amino antioxidants, preferably diphenylamines, in particular dialkylphenylamines, such as octadiphenylamines, phenyl-alpha-naphthyl amines, phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur antioxidants (sulphurized phenates) .
  • amino antioxidants preferably diphenylamines, in particular dialkylphenylamines, such as octadiphenylamines, phenyl-alpha-naphthyl amines, phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur antioxidants (sulphurized phenates) .
  • the friction modifiers can be compounds providing metallic elements different from the metallic nanoparticles according to the invention or else an ashless compound.
  • compounds providing metallic elements mention may be made of complexes of transition metals such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon compounds containing oxygen, nitrogen, sulfur or phosphorus, such as dithiocarbamates or molybdenum dithiophosphates.
  • the ashless friction modifiers are of organic origin and can be chosen from monoesters of fatty acids and polyols, alkoxylated amines, fatty alkoxylated amines, amine phosphates, fatty alcohols, fatty epoxides, borate fatty epoxides, fatty amines or fatty acid glycerol esters.
  • fat or “fat(s)” is meant within the meaning of the present invention a hydrocarbon group comprising from 8 to 24 carbon atoms.
  • the anti-corrosion additives can be chosen from phenolic derivatives, in particular ethoxylated phenolic derivatives substituted by alkyl groups in the ortho position.
  • the corrosion inhibitors may be derivatives of dimercaptothiadiazole.
  • the lubricating composition is not an emulsion.
  • the lubricating composition is anhydrous.
  • the application also describes an engine oil comprising a lubricating composition according to the invention.
  • the application also describes a transmission oil comprising a lubricating composition according to the invention.
  • the lubricating composition according to the invention can lubricate at least one mechanical part or one mechanical component, in particular bearings, gears, universal joints, transmissions, the piston/segment/liner system, the camshafts, the clutch , manual or automatic gearboxes, axles, rocker arms, crankcases, etc.
  • the lubricating composition according to the invention can lubricate a mechanical part or a metal component of the transmissions, of the clutch, of the axles, of manual or automatic, preferably manual, gearboxes.
  • the invention also relates to the use of a lubricating composition as defined above for lubricating a mechanical part, preferably a transmission member or a vehicle engine, advantageously vehicles automobiles.
  • the invention also relates to the use of a lubricating composition as defined above for reducing friction on the surface of a mechanical part, preferably a transmission member or a vehicle engine, advantageously of motor vehicles.
  • a subject of the invention is also the use of a lubricating composition as defined above for reducing the fuel consumption of vehicles, in particular motor vehicles.
  • a subject of the invention is also the use of a lubricating composition as defined above for reducing the spalling of a mechanical part, preferably of a transmission member or of a vehicle engine, advantageously of vehicles automobiles.
  • the application also describes a process for lubricating a mechanical part, preferably a transmission member or a vehicle engine, advantageously motor vehicles, said process comprising at least one step of bringing the mechanical part into contact with a lubricating composition as defined above.
  • the application also describes a method for reducing friction on the surface of a mechanical part, preferably of a transmission member or of a vehicle engine, advantageously of motor vehicles, comprising at least bringing the mechanical part into contact with a lubricating composition as defined above.
  • the application also describes a method for reducing the fuel consumption of a vehicle, in particular of a motor vehicle comprising at least one step of in contact with a mechanical part of the vehicle engine with a lubricating composition as defined above.
  • the application also describes a method for reducing the spalling of a mechanical part, preferably of a transmission member or of a vehicle engine, advantageously of motor vehicles, comprising at least bringing the mechanical part into contact with a lubricating composition as defined above.
  • the application also describes a composition of the concentrate type of additives comprising at least one anti-wear compound comprising a dithiophosphate group and tungsten disulphide nanoparticles.
  • composition of the concentrate type of additives can be added at least one base oil to obtain a lubricating composition according to the invention.
  • the invention also relates to the use of an anti-wear compound comprising a dithiophosphate group to reduce the oxidation of a lubricating composition
  • Lubricating compositions No. 1 to No. 4 are described in Table II; the percentages indicated are percentages by mass.
  • Table II Lubricant composition #1 #2 #3 #4 base oil 100 99 99 98 Compound comprising a dithiophosphate group 1 1 Tungsten Disulfide Nanoparticles (NanoLub Gear Oil Concentrate) 1 1
  • Test 1 evaluation of the friction properties of lubricating compositions
  • Table III shows the average coefficient of friction of lubricating compositions No. 1 to No. 4; the average coefficient of friction representing the average of the values of the coefficient of friction obtained after 4 tests.
  • Table III Composition #1 #2 #3 #4 Coefficient of friction 0.100 0.110 0.075 0.060
  • the lubricating composition according to the invention No. 4 has improved friction properties, compared to a lubricating composition comprising a compound comprising a dithiophosphate group according to the invention but does not not comprising metallic nanoparticles (composition No. 2) and relative to a composition comprising metallic nanoparticles according to the invention but not comprising a compound comprising a dithiophosphate group (composition No. 3).
  • lubricating composition No. 4 exhibits satisfactory stability.

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Claims (13)

  1. Schmiermittelzusammensetzung mit einer kinematischen Viskosität bei 100 °C, gemessen nach der Norm ASTM D445, von 4 bis 50 cSt und umfassend, bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung, mindestens 70 Gewichtsprozent mindestens eines Basisöls, 0,1 bis 5 Gewichtsprozent mindestens einer Antiverschleißverbindung, umfassend eine Dithiophosphatgruppe, und 0,01 bis 2 Gewichtsprozent feste metallische Nanopartikel, die eine Fullerenstruktur aufweisen, dargestellt durch die Formel MXn, wobei M ein Übergangsmetall, X ein Chalkogen darstellt, wobei n=2 oder n=3 abhängig von dem Oxidationszustand des Übergangsmetalls ist, wobei die metallischen Nanopartikel eine durchschnittliche Größe von 50 bis 200 nm aufweisen, bestimmt mittels Bilder, die durch Transmissionselektronenmikrographie oder hochauflösende Transmissionselektronenmikroskopie erlangt wurden, und konzentrische Polyeder mit einer Mehrschicht- oder Schichtstruktur sind.
  2. Schmiermittelzusammensetzung nach Anspruch 1, wobei M ausgewählt ist aus der Gruppe, bestehend aus Wolfram, Molybdän, Zirkonium, Hafnium, Platin, Rhenium, Titan, Tantal und Niobium.
  3. Schmiermittelzusammensetzung nach Anspruch 1 oder 2, wobei die Metallnanopartikel ausgewählt sind aus der Gruppe, die durch MoS2, MoSe2, MoTe2, WS2, WSe2, ZrS2, ZrSe2, HfS2, HfSe2, PtS2, ReS2, ReSe2, TiS3, ZrS3, ZrSe3, HfS3, HfSe3, TiS2, TaS2, TaSe2, NbS2, NbSe2 und NbTe2 gebildet ist.
  4. Schmiermittelzusammensetzung nach einem der vorherigen Ansprüche, wobei der Gewichtsgehalt an metallischen Nanopartikeln von 0,05 bis 2 % reicht, bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung.
  5. Schmiermittelzusammensetzung nach einem der vorherigen Ansprüche, wobei die Verbindung, die eine Dithiophosphatgruppierung umfasst, ausgewählt ist aus der Gruppe, bestehend aus Ammoniumdithiophosphaten, Amindithiophosphaten, Esterdithiophosphaten und Metalldithiophosphaten, einzeln oder in Gemisch.
  6. Zusammensetzung nach einem der vorherigen Ansprüche, wobei die Verbindung, die eine Dithiophosphatgruppierung umfasst, eine Verbindung von Formel (IV) ist
    Figure imgb0010
     wobei :
    • R12 eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe umfassend 1 bis 30 Kohlenstoffatome darstellt;
    • R13 eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe umfassend 1 bis 30 Kohlenstoffatome darstellt;
    • n die Wertigkeit des Metallkations darstellt.
  7. Schmiermittelzusammensetzung nach einem der vorherigen Ansprüche, wobei die Verbindung, die eine Dithiophosphatgruppierung umfasst, eine Verbindung von Formel (IVa) oder von Formel (IV-b) ist:
    Figure imgb0011
    Figure imgb0012
     wobei :
    • R12 eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe umfassend 1 bis 30 Kohlenstoffatome darstellt;
    • R13 eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe umfassend 1 bis 30 Kohlenstoffatome darstellt.
  8. Schmiermittelzusammensetzung nach einem der vorherigen Ansprüche, wobei der Gewichtsgehalt der Verbindung, die eine Dithiophosphatgruppierung umfasst, von 0,2 bis 4 % reicht, bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung.
  9. Schmiermittelzusammensetzung nach einem der vorherigen Ansprüche, ferner umfassend ein Additiv, ausgewählt aus scherstabilen Polymeren, Antioxidantien, Korrosionsschutzadditiven, von metallischen Nanopartikeln verschiedenen Reibungsmodifizierern und Dispergiermitteln.
  10. Verwendung einer Schmierstoffzusammensetzung nach einem der Ansprüche 1 bis 9 für die Schmierung eines Metallteils.
  11. Verwendung einer Schmiermittelzusammensetzung nach dem vorherigen Anspruch für die Schmierung eines mechanischen Teils von Kraftfahrzeugen.
  12. Verwendung einer Schmierstoffzusammensetzung nach einem der Ansprüche 1 bis 9, um den Kraftstoffverbrauch von Kraftfahrzeugen zu verringern.
  13. Verwendung einer Antiverschleißverbindung, umfassend eine Dithiophosphatgruppierung zum Verringern der Oxidation einer Schmiermittelzusammensetzung, umfassend mindestens ein Basisöl und feste metallische Nanopartikel, die eine Fullerenstruktur aufweisen, die durch die Formel MXn dargestellt ist, wobei M ein Übergangsmetall, X ein Chalkogen darstellt, mit n=2 oder n=3 in Abhängigkeit von dem Oxidationszustand des Übergangsmetalls, wobei die metallischen Nanopartikel eine durchschnittliche Größe, bestimmt mittels Bilder, die durch Transmissionselektronenmikrographie oder hochauflösende Transmissionselektronenmikroskopie erlangt werden, von 50 bis 200 nm aufweisen und konzentrische Polyeder mit einer Mehrschicht- oder Schichtstruktur sind.
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