EP2652099B1 - Grease composition - Google Patents

Grease composition Download PDF

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Publication number
EP2652099B1
EP2652099B1 EP11805228.1A EP11805228A EP2652099B1 EP 2652099 B1 EP2652099 B1 EP 2652099B1 EP 11805228 A EP11805228 A EP 11805228A EP 2652099 B1 EP2652099 B1 EP 2652099B1
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EP
European Patent Office
Prior art keywords
graphite
composition according
grease composition
ppm
grease
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP11805228.1A
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German (de)
French (fr)
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EP2652099A1 (en
Inventor
Franck Bardin
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TotalEnergies Marketing Services SA
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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
    • C10M141/02—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 oxygen-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
    • C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/06—Sulfur
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • 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
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0416—Carbon; Graphite; Carbon black used as thickening agents
    • 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
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • 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
    • C10M2205/026—Butene
    • 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/08—Groups 4 or 14
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives

Definitions

  • the present invention relates to grease compositions for use in the homokinetic joints of transmission lines of motor vehicles, or other gear mechanisms for which low friction greases are desired.
  • a transmission joint or mechanical coupling is a mechanical system consisting of several moving parts relative to each other, or deformable, which allows the mutual drive of two rotating parts whose axes of rotation occupy variable relative positions during operation. In other words, it is a link that transmits the rotation of an axis to another axis moving relative to the first.
  • a transmission joint is called homokinetic if, at any moment, the rotation speeds of the two shafts are equal.
  • the greases used in the constant velocity joints must have an anti-wear effect, and preferably a low coefficient of friction to reduce or prevent noise, vibration and jolts.
  • known constant velocity joint greases frequently contain anti-wear additives, which are for example phosphorus or phosphorus compounds, and friction modifiers, for example organic compounds containing molybdenum, which may have effects on one or the other of these properties, or both. It is also known to use, as friction modifiers, solid lubricants such as molybdenum disulfide (MoS2) or tungsten (WS2), or graphite.
  • anti-wear additives are for example phosphorus or phosphorus compounds
  • friction modifiers for example organic compounds containing molybdenum, which may have effects on one or the other of these properties, or both.
  • solid lubricants such as molybdenum disulfide (MoS2) or tungsten (WS2), or graphite.
  • Requirement FR 2,723,747 discloses high temperature greases for homokinetic joints comprising mineral and / or synthetic base oils, polyurea thickeners and MoS 2 as a solid lubricant, as well as graphite and at least one organic molybdenum compound, preferentially molybdenum dithiocarbamate.
  • Graphite solid lubricants, MoDTC, PTFE allow to lower the MoS 2 expensive solid lubricant content, but without substituting it completely.
  • MoS 2 solid lubricants have a high price and introduce a high metal content into the formulas, which is undesirable for environmental reasons. None in this application suggests lowering the metal (Mo) content of the fat by completely substituting other MoS 2 solid lubricants.
  • the molybdenum content of the compositions disclosed is at least of the order of 5000 ppm.
  • Polyurea thickened greases are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and have little storage stability. The precautions to be taken make the manufacturing processes more complex and more expensive. The availability of raw materials is also lower compared to those of greases thickened with metallic soaps, in particular Lithium and Lithium complex. The polyureas are superior in thermal behavior, but their thixiotropic character also poses problems of destructuring under mechanical stress and storage hardening. It will therefore be preferred, for formulating greases for homokinetic joint technically easier, and more economical to manufacture, from non-toxic and non-hazardous materials, use metal soaps of fatty acids as thickeners.
  • Some commercial greases for constant velocity joints are, for example, formulated from mineral and / or synthetic base oils, lithium or complex lithium thickeners, and MoS 2 molybdenum disulfide, at a level of about 3% by weight. which represents a content of about 18,000 ppm Mo. Below this MoS 2 content, the wear and friction performances are insufficient.
  • the patent EP 0708 172 describes a low-friction grease for homokinetic joints comprising a base oil, a single or complex lithium soap thickener, one or more organic components containing molybdenum, of the MoDTC or MoDTP type, at least one zinc dithiophosphate, an agent extreme metal-free phospho-sulfur pressure, a calcium salt of oxidized wax, petroleum sulfonate or aromatic alkylsulfonates.
  • Examples of compositions disclosed have either a high molybdenum content (about 8500 ppm) and / or a high phosphorus content (about 2000 ppm phosphorus), which poses environmental problems.
  • WO 2007/085643 discloses polyurethane thickened homokinetic joint grease compositions comprising from 0.1 to 5% by weight of WS2, and from 0.1 to 5% by weight of zinc dithiophosphate and / or molybdenum dithiocarbamate. This application also discloses the possibility of using as an additive in greases graphite or MoS 2 . However, the use of graphite (or MoS 2 ) in combination with MoDTC is disadvised because this combination has, according to this application, an adverse effect on the anti-wear properties and the coefficient of friction of greases.
  • the documents WO 2010/114209 and JP 2009138055 disclose grease compositions for homokinetic joints.
  • These greases according to the invention have improved antiwear properties compared with greases for known constant velocity joints based on lithium soap.
  • the friction properties are equivalent to those of known greases.
  • These fats can moreover achieve these performances with a molybdenum content and possibly phosphorus lower than the fats of the prior art.
  • the grease compositions according to the invention comprise phosphorus at a content of less than 1500 ppm, preferably less than 1200 ppm.
  • the grease compositions according to the invention comprise zinc at a content of less than 1500 ppm.
  • the grease compositions according to the invention are free of MoS 2 solid lubricant.
  • the grease compositions according to the invention are free of polytetrafluoroethylene solid lubricant.
  • the grease compositions according to the invention comprise exclusively one or more simple metal or complex fatty acid soaps as a thickener.
  • the grease compositions according to the invention comprise at least one simple soap or complex of lithium, sodium, calcium, barium, or titanium, alone or as a mixture, as a thickener.
  • the grease compositions according to the invention comprise one or more single or complex lithium soaps as thickeners.
  • the grease compositions according to the invention comprise a mineral base oil (a), and a synthetic base oil (a), preferably chosen from polyalphaolefins.
  • the grease compositions according to the invention further comprise a polymer (e) preferably chosen from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
  • a polymer (e) preferably chosen from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
  • the grease compositions according to the invention may also comprise one or more phosphosulfur anti-wear and / or extreme pressure additives (f), preferably chosen from zinc dithiophosphates.
  • the grease compositions according to the invention have a phosphorus content of between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.
  • compositions according to the invention have a zinc content of between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 800 and 1000 ppm.
  • the present invention also relates to the use of grease compositions as described above as greases for homokinetic joints of motor vehicle transmissions.
  • the present invention also relates to one of the homokinetic joints filled with grease compositions as described above.
  • the other base oil (s) used in the 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 (American Petroleum Institute).
  • 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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
  • the base oils of the grease compositions according to the present invention may also be synthetic oils, such as certain esters, silicones, polyalkylene glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.
  • synthetic oils such as certain esters, silicones, polyalkylene glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.
  • the base oils may also be oils of natural origin, for example esters of alcohol and carboxylic acids, obtainable from natural resources such as sunflower oil, rapeseed oil, palm oil. ...
  • synthetic oils of the polyoaplphadefin (PAO) type are present in combination with mineral oils.
  • the polyalphaolefins are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene). Their weight average molecular weight is typically between 250 and 3000.
  • the base oil mixture is set so that its viscosity at 40 ° C according to ASTM D 445 is between 30 and 140 cSt, preferably between 50 and 100 cSt.
  • a wide range of light polyalphaolefins can be used, such as for example PAO 6 (31 cSt at 40 ° C), PAO 8 (48 cSt at 40 ° C), or heavy, such as PAO 40 ( 400 cSt at 40 ° C), or PAO 100 (1000 cSt at 40 ° C).
  • the greases according to the present invention are thickened with metal fatty acid soaps.
  • Metallic fatty acid soaps can be prepared separately, or in situ during the manufacture of the fat (in the latter case, the fatty acid (s) are dissolved in the base oil, and then the metal hydroxide is added. appropriate).
  • These thickeners are commonly used products in the field of fats, readily available and inexpensive. They present the best technical compromise, by combining both good mechanical properties, good thermal resistance, and good water resistance.
  • Long-chain fatty acids typically comprising from 10 to 28 carbon atoms, saturated or unsaturated, optionally hydroxylated, are preferably used.
  • Long-chain fatty acids are, for example, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, oleic, linoleic and erucic acids, and their hydroxylated derivatives.
  • Hydroxystearic acid 12 is the best known derivative of this class, and preferred.
  • These long-chain fatty acids generally come from vegetable oils, for example palm oil, castor oil, rapeseed oil, sunflower oil, ... or animal fats (tallow, whale oil, etc.).
  • So-called simple soaps can be formed using one or more long-chain fatty acids.
  • So-called complex soaps can also be formed by using one or more long-chain fatty acids in combination with one or more short-chain hydrocarbon carboxylic acids having at most 8 carbon atoms.
  • the saponification agent used to make the soap may be a metal compound of Lithium, Sodium, Calcium, Barium, Titanium, Aluminum, preferably Lithium and Calcium, and preferably a hydroxide, oxide or carbonate of these metals.
  • Metal soaps in particular Lithium, Sodium, Calcium, Barium, Titanium, form a fibrous structure, with the exception of simple or complex aluminum soaps, which have a spherical gel structure.
  • One or more metal compounds may be used in the greases according to the invention. It is thus possible to associate lithium soaps, combined with calcium soaps to a lesser extent. This has the advantage of improving the water resistance of greases.
  • the metal soaps are employed at levels of the order of 5 to 20% by weight, preferably 8 to 15% by weight, preferably 10 to 12%, typically 11% by weight in the greases according to the invention.
  • the amount of metallic soap (s) is generally adjusted to obtain Grade 00, Grade 0, Grade 1 or Grade 2 fats according to the NLGI classification.
  • the greases according to the invention mainly contain metal fatty acid soaps as thickeners.
  • metal fatty acid soaps simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
  • the greases according to the invention mainly contain simple or complex lithium soaps as thickeners.
  • lithium soaps, simple or complex together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
  • the quantity of the metal soap or fatty acids, simple or complex constitutes at least 50%, more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention. invention.
  • the amount of lithium soap, simple or complex constitutes at least 50%, even more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention.
  • the greases according to the invention may contain, as the major thickener, metal soap of simple or complex fatty acids, and smaller amounts of other thickeners, such as polyureas, or inorganic thickeners, such as bentonite or alumino silicates.
  • the greases according to the invention are free of polyurea thickeners, which are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and unstable. in storage.
  • the greases according to the invention exclusively contain simple or complex fatty acid metal soaps as thickeners.
  • the greases according to the invention exclusively contain metal soaps of simple or complex fatty acids of lithium as thickeners.
  • the grease compositions according to the invention contain graphite and molybdenum dithiocarbamate, which gives them anti-wear properties. improved compared to known commercial fats. These properties can be achieved with a lower molybdenum content than known fats.
  • the molybdenum content of the greases according to the invention is between 1000 and 2800 ppm.
  • the ratio Mo / [graphite], between the content of molybdenum, in ppm, and the mass percentage of graphite in said composition, is between 1250 and 1550. Indeed, it is found that, when these compounds are present in the proportions mentioned above. above, the grease compositions also have very good anti-wear and friction properties, equivalent to those of known commercial greases. These good properties are also achieved with a molybdenum content, and possibly a level of other metallic elements such as zinc or a phosphorus element level, lower than those of known fats.
  • compositions according to the invention contain molybdenum dithiocarbamates, friction modifying additives well known to those skilled in the art.
  • molybdenum dithiocarbamate organometallic friction modifiers may for example be dialkyldithiocarbamates of molybdenum corresponding to formula (I): Where X 1 , X 2 , X 3 , X 4 are alkyl chains, preferably containing 2 to 13 carbon atoms, preferably 2 to 6 carbon atoms.
  • the amount of MoDTC of the compositions according to the invention is adjusted so that their molybdenum content is between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm.
  • This content can be measured according to the usual techniques, plasma, atomic absorption, flurescence X.
  • MoDTC as the only additive (antiwear) in a fat composition. Indeed, it is known that the MoDTC requires a minimum activation temperature and the presence of other additives (antiwear, extreme pressure) to be effective.
  • Greases comprising MoDTC without other antiwear and / or extreme pressure additives would not be effective, especially at low temperatures.
  • MoDTC is thus associated with phosphorus additives, for example dithiophosphates.
  • the MoDTC is combined with graphite, which makes it possible to produce fats having very good properties in wear and friction, with a low molybdenum and phosphorus content.
  • the grease compositions according to the invention contain graphite.
  • graphite known for its properties as a solid lubricant, makes it possible to reduce the content of friction modifying and anti-wear additives containing molybdenum (and possibly phosphorus), without adding a metallic element, and by maintaining the wear properties. and friction suitable for applying homokinetic joints.
  • the graphite employed in the compositions according to the invention is a powder of micrometric size, with particle sizes included approximately between 1 and 15 microns, and for example a size distribution characterized by a diameter D50 of between 3 and 8 microns, preferably between 5 and 7 microns.
  • the fat composition according to the invention comprises between 0.5 and 3.0% by weight of graphite, preferably between 0.7 and 2.0%, preferentially between 0.75 and 1.7%, preferably between 1.0 and 1.0%. and 1.5% by weight of graphite.
  • the greases according to the invention optionally contain sulfur-phosphorus anti wear and extreme pressure additives commonly used in the formulation of greases and lubricants.
  • thiophosphoric acid thiophosphorous acid
  • esters of these acids their salts
  • dithiophosphates particularly zinc dithiophosphates.
  • Zinc dithiophosphates of formula (II) are particularly preferred:
  • R 1 , R 2 , R 3 and R 4 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 14 carbon atoms, or optionally substituted aryl groups containing from 6 to 30, preferably 8 to 18 carbon atoms.
  • compositions according to the invention can be used alone or as a mixture in the grease compositions according to the invention.
  • Their mass percentage in the compositions according to the invention is preferably between 0.5 and 5% by weight, preferably between 0.7 and 2% by weight, or between 0.8 and 1.5% by weight relative to the total weight of the composition.
  • Their quantity will be adjusted so as to respect the limiting levels in molybdenum and phosphorus elements of the compositions according to the invention.
  • the molybdenum (Mo) content of the compositions according to the invention is between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm.
  • the phosphorus content (P) of the compositions according to the invention is preferably less than 1500 ppm, preferentially less than 1200 ppm, preferably between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.
  • This content can be measured according to the usual techniques, plasma, atomic absorption.
  • the zinc content of the compositions according to the invention is less than 1500 ppm, preferably between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 700 and 1200 ppm, preferentially between 800 and 1000 ppm.
  • the lubricating compositions according to the present invention may also contain phosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts
  • phosphorus anti-wear and extreme pressure additives such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts
  • the lubricating compositions according to the present invention may also contain sulfur-containing wear and extreme pressure additives, such as dithiocarbamates, thiadiazoles and benzothiazoles, sulfur-containing olefins.
  • the greases according to the invention may also contain any type of additive suitable for their use, for example antioxidants, such as amines or phenolics, antirust which may be oxygenated compounds such as esters, copper passivates.
  • antioxidants such as amines or phenolics
  • antirust which may be oxygenated compounds such as esters, copper passivates.
  • the greases according to the invention may also contain polymers (e), for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example hydrogenated diene styrene, polymethacrylates (PMA) at levels generally between 1 and 35%.
  • polymers e
  • PIB polyisobutene
  • OCP copolymer olefins
  • PMA polymethacrylates
  • molar mass PIBs between 15,000 and 25,000 daltons at levels generally between 2 and 15% by weight, or between 5 and 10% by weight.
  • the greases according to the invention are preferably manufactured by forming the metal soap in situ.
  • One or more fatty acids are dissolved in a fraction of the base oil or base oil mixture at room temperature. This fraction is generally of the order of 50% of the total amount of oil contained in the final fat.
  • the fatty acids can be long acids, comprising from 14 to 28 carbon atoms, to form a simple soap, optionally combined with short fatty acids, comprising from 6 to 12 carbon atoms, to form complex soaps.
  • metal compounds preferably metal hydroxide type.
  • the preferred metal of the compositions according to the invention is lithium, possibly combined, to a lesser extent, with calcium.
  • the saponification reaction of the fatty acids is allowed to proceed with the metal compound (s) at a temperature of about 100 to 110 ° C.
  • the water formed is then evaporated by cooking the mixture at a temperature of about 200 ° C.
  • the grease is then cooled by the remaining fraction of base oil.
  • the additives are then incorporated at about 80 ° C.
  • Kneading is then carried out for a time sufficient to obtain a homogeneous fat composition.
  • the consistency of a grease measures its hardness or fluidity at rest. It is quantified by the depth of penetration of a cone of given dimensions and mass. The fat is previously subjected to mixing. The conditions for measuring the consistency of a grease are defined by ASTM D 217.
  • the fats are divided into 9 classes or 9 NLGI grades (National Lubricating Grease Institute) commonly used in the field of fats. These grades are shown in the table below.
  • the greases according to the invention are preferably greases with a consistency of between 265 and 430, preferably between 265 and 385, preferably between 265 and 340 tenths of a millimeter according to ASTM D217.
  • they are NLGI grade 00, 0, 1 or 2, that is to say that their consistency is respectively between 400 and 430, or 335 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
  • Grease compositions containing various additives are prepared from the same grease base comprising mineral and synthetic base oils, thickened with a single lithium soap prepared from lithium hydroxide (LiOH). H2O), and 12-hydroxystearic acid.
  • the composition of the fat foot is shown in Table 1 below.
  • the term "grease foot” commonly refers to a person skilled in the art as a grease composition containing only base oils and thickeners, and no additive.
  • All prepared fats are grade 2 according to the NLGI classification.
  • Grease A is a commercial grease for constant velocity joints
  • greases E, I and J are according to the invention.
  • the mass compositions of greases are given in Table 2, as well as their properties in wear and friction.
  • the wear properties were evaluated by measuring the wear diameter (in mm) after the 4-ball wear test according to ASTM D2266 (1 hour, load 40 kg, 75 ° C). According to STL Specification S71 3100, CV greases must lead to a wear diameter of less than 50 mm.

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Description

La présente invention est relative à des compositions de graisse utilisables dans les joints homocinétiques des lignes de transmission des véhicules à moteur, ou d'autres mécanismes d'engrenage pour lesquels des graisses à bas coefficient de friction sont recherchées.The present invention relates to grease compositions for use in the homokinetic joints of transmission lines of motor vehicles, or other gear mechanisms for which low friction greases are desired.

Un joint de transmission ou accouplement mécanique est un système mécanique composé de plusieurs pièces mobiles les unes par rapport aux autres, ou déformables, qui permet l'entraînement mutuel de deux pièces tournantes dont les axes de rotation occupent des positions relatives variables pendant le fonctionnement. En d'autres termes, c'est une liaison qui permet de transmettre la rotation d'un axe à un autre axe mobile par rapport au premier. Un joint de transmission est dit homocinétique si, à tout instant, les vitesses de rotation des deux arbres sont égales.A transmission joint or mechanical coupling is a mechanical system consisting of several moving parts relative to each other, or deformable, which allows the mutual drive of two rotating parts whose axes of rotation occupy variable relative positions during operation. In other words, it is a link that transmits the rotation of an axis to another axis moving relative to the first. A transmission joint is called homokinetic if, at any moment, the rotation speeds of the two shafts are equal.

Les mouvements à l'intérieur des joints homocinétiques sont complexes, avec une combinaison de roulement, de glissement et de rotations. Il s'y produit une usure sur les surfaces de contact des composants, mais également des forces de friction significatives entre les surfaces. L'usure peut avoir pour résultats une défaillance des joints et les forces de friction peuvent entraîner du bruit, des vibrations et des a coup dans la ligne de transmission.The movements inside constant velocity joints are complex, with a combination of rolling, sliding and rotating. There is wear on the contact surfaces of the components, but also significant frictional forces between the surfaces. Wear can result in joint failure, and frictional forces can cause noise, vibration and clogging in the transmission line.

Ainsi, les graisses utilisées dans les joints homocinétiques doivent avoir un effet anti usure, et préférentiellement un faible coefficient de friction afin de réduire ou empêcher les bruits, les vibrations et les à-coups.Thus, the greases used in the constant velocity joints must have an anti-wear effect, and preferably a low coefficient of friction to reduce or prevent noise, vibration and jolts.

Différents additifs connus et aident à réduire l'usure et/ou la friction. Ainsi, les graisses pour joint homocinétiques connues contiennent fréquemment des additifs anti usure, qui sont par exemple des composés phosphorés ou phosphosoufrés, et des modificateurs de friction, par exemple des composés organiques contenant du molybdène, qui peuvent avoir des effets sur l'une ou l'autre de ces propriétés, voire les deux. Il est également connu d'employer, comme modificateurs de frottement, des lubrifiants solides tels que le bisulfure de molybdène (MoS2) ou de tungstène (WS2), ou le graphite.Various known additives and help to reduce wear and / or friction. Thus, known constant velocity joint greases frequently contain anti-wear additives, which are for example phosphorus or phosphorus compounds, and friction modifiers, for example organic compounds containing molybdenum, which may have effects on one or the other of these properties, or both. It is also known to use, as friction modifiers, solid lubricants such as molybdenum disulfide (MoS2) or tungsten (WS2), or graphite.

La demande FR 2 723 747 divulgue des graisses haute température pour joints homocinétiques comprenant des huiles de base minérales et/ou synthétiques, des épaississants polyurées et du MoS2 comme lubrifiant solide, ainsi que du graphite et au moins un composé organique du molybdène, préférentiellement dithiocarbamate de molybdène. Les lubrifiants solides graphite, MoDTC, PTFE, permettent d'abaisser la teneur en lubrifiant solide coûteux MoS2, mais sans toutefois s'y substituer complètement.Requirement FR 2,723,747 discloses high temperature greases for homokinetic joints comprising mineral and / or synthetic base oils, polyurea thickeners and MoS 2 as a solid lubricant, as well as graphite and at least one organic molybdenum compound, preferentially molybdenum dithiocarbamate. Graphite solid lubricants, MoDTC, PTFE, allow to lower the MoS 2 expensive solid lubricant content, but without substituting it completely.

Les lubrifiants solides de type MoS2 ont un prix élevé et introduisent une teneur élevée de métal dans les formules, ce qui n'est pas souhaitable pour des raisons environnementales. Rien dans cette demande ne suggère d'abaisser la teneur en métal (Mo) de la graisse en substituant totalement d'autres lubrifiants solides au MoS2. La teneur en molybdène des compositions divulguées est au moins de l'ordre de 5000 ppm.MoS 2 solid lubricants have a high price and introduce a high metal content into the formulas, which is undesirable for environmental reasons. Nothing in this application suggests lowering the metal (Mo) content of the fat by completely substituting other MoS 2 solid lubricants. The molybdenum content of the compositions disclosed is at least of the order of 5000 ppm.

Aucune mention n'est faite de teneurs spécifiques en molybdène et en graphite permettant d'optimiser les performances des graisses en usure et/ou en friction. Rien dans cette demande ne suggère non plus de substituer les savons de lithium aux polyurées comme épaississants.No mention is made of specific contents of molybdenum and graphite to optimize the performance of greases in wear and / or friction. Nothing in this application suggests either substituting lithium soap for polyureas as thickeners.

Les graisses épaissies aux polyurées sont plus compliquées techniquement à fabriquer, en particulier parce que les composants entrant dans leur fabrication, telles que les isocyanates et les amines, sont très toxiques et peu stables au stockage. Les précautions à prendre rendent les procédés de fabrication plus complexes et plus coûteux. La disponibilité des matières premières est également moindre par rapport à celles des graisses épaissies aux savons métalliques, en particulier Lithium et Lithium complexe. Les polyurées sont supérieures en tenue thermique, mais leur caractère thixiotrope pose également des problèmes de déstructuration sous contrainte mécanique et de durcissement au stockage. On préférera donc, pour formuler des graisses pour joint homocinétique techniquement plus faciles, et plus économique à fabriquer, à partir de matières non toxiques et non dangereuses, utiliser des savons métalliques d'acides gras comme épaississants.Polyurea thickened greases are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and have little storage stability. The precautions to be taken make the manufacturing processes more complex and more expensive. The availability of raw materials is also lower compared to those of greases thickened with metallic soaps, in particular Lithium and Lithium complex. The polyureas are superior in thermal behavior, but their thixiotropic character also poses problems of destructuring under mechanical stress and storage hardening. It will therefore be preferred, for formulating greases for homokinetic joint technically easier, and more economical to manufacture, from non-toxic and non-hazardous materials, use metal soaps of fatty acids as thickeners.

Certaines graisses commerciales pour joints homocinétiques sont par exemple formulées à partir d'huiles de bases minérales et/ou synthétiques, d'épaississants Lithium ou lithium complexe, et de bisulfure de molybdène MoS2, à hauteur d'environ 3% en masse, ce qui représente une teneur d'environ 18 000 ppm de Mo. En dessous de cette teneur en MoS2, les performances en usure et friction sont insuffisantes.Some commercial greases for constant velocity joints are, for example, formulated from mineral and / or synthetic base oils, lithium or complex lithium thickeners, and MoS 2 molybdenum disulfide, at a level of about 3% by weight. which represents a content of about 18,000 ppm Mo. Below this MoS 2 content, the wear and friction performances are insufficient.

Le brevet EP 0708 172 décrit une graisse à bas coefficient de frottement pour joints homocinétiques comprenant une huile de base, un épaississant savon de Lithium simple ou complexe, un ou plusieurs composants organiques contenant du molybdène, de type MoDTC ou MoDTP, au moins un dithiophosphate de zinc, un agent extrême pression phospho soufré exempt de métal, un sel de calcium de cire oxydée, de sulfonate de pétrole ou d'alkylsulfonates aromatiques. Les exemples de compositions divulguées ont soit une haute teneur en molybdène (environ 8500 ppm) et/ou une haute teneur en phosphore (environ 2000 ppm de phosphore), ce qui pose des problèmes environnementaux.The patent EP 0708 172 describes a low-friction grease for homokinetic joints comprising a base oil, a single or complex lithium soap thickener, one or more organic components containing molybdenum, of the MoDTC or MoDTP type, at least one zinc dithiophosphate, an agent extreme metal-free phospho-sulfur pressure, a calcium salt of oxidized wax, petroleum sulfonate or aromatic alkylsulfonates. Examples of compositions disclosed have either a high molybdenum content (about 8500 ppm) and / or a high phosphorus content (about 2000 ppm phosphorus), which poses environmental problems.

Aucune mention n'est faite de la possibilité de substituer en partie les composés comprenant du molybdène et/ou du phosphore par d"autres additifs pour abaisser la teneur en métal des compositions, ni d'une teneur optimale en molybdène permettant de conserver ou améliorer les propriétés de ces graisses, notamment en usure et en friction.No mention is made of the possibility of partially substituting the compounds comprising molybdenum and / or phosphorus by other additives for lowering the metal content of the compositions, nor an optimum molybdenum content making it possible to conserve or improve the properties of these greases, especially in wear and friction.

La publication «Effect of graphite on friction and wear characteristics of molybdenum dithiocarbamate », Y. Yamamoto et al., Tribology Letters, Vol 17, N°1, July 2004 , divulgue l'effet booster du graphite sur les performances du MoDTC, dans une huile lubrifiante spécifique, le squalane. Cette amélioration est surtout notable en présence de dispersant succinimide. Ce document ne concerne pas le domaine des graisses. Cette étude est limitée à une seule huile lubrifiante naturelle et n'aborde pas le domaine des graisses. Aucune combinaison spécifique d'huile de base, de graphite et de MoDTC avec d'autres composants nécessaires à la formulation des graisses, en particulier les épaississants n'est divulguée. Il n'est donc absolument pas possible de déduire de cette publication si l'effet booster du graphite sur les performances friction et usure du MoDTC sera reproduit dans une graisse comprenant tel ou tel épaississant. Aucune optimisation des teneurs en molybdène et graphite n'est effectuée.The publication "Effect of graphite on friction and wear characteristics of molybdenum dithiocarbamate", Y. Yamamoto et al., Tribology Letters, Vol 17, No. 1, July 2004 , discloses the booster effect of graphite on the performance of MoDTC, in a specific lubricating oil, squalane. This improvement is especially noticeable in the presence of succinimide dispersant. This document does not concern the field of fats. This study is limited to one natural lubricating oil and does not address the field of fat. No specific combination of base oil, graphite and MoDTC with other components necessary for the formulation of greases, especially thickeners is disclosed. It is therefore absolutely not possible to deduce from this publication whether the booster effect of graphite on the friction and wear performance of the MoDTC will be reproduced in a grease comprising one or other thickener. No optimization of the molybdenum and graphite contents is carried out.

La demande WO 2007/085643 divulgue des compositions de graisse pour joints homocinétiques épaissie aux polyurées, comprenant de 0,1 à 5% en poids de WS2, et de 0,1 à 5 % en poids de dithiophosphate de zinc et/ou dithiocarbamate de molybdène. Cette demande divulgue également la possibilité d'utiliser comme additif dans les graisses du graphite ou du MoS2. Toutefois, l'utilisation du graphite (ou du MoS2) en combinaison avec du MoDTC est déconseillée, car cette association a, selon cette demande, un effet adverse sur les propriétés anti usure et le coefficient de friction des graisses. Les documents WO 2010/114209 et JP 2009138055 divulguent des compositions de graisse pour joints homocinétiques. Il existe donc un besoin pour des graisses pour joints homocinétiques, contenant des matières premières non toxiques, disponibles et peu coûteuses, simples à fabriquer, présentant un taux réduit en molybdène (Mo) et en phosphore (P), et présentant des propriétés anti usure et des propriétés en friction (bas coefficient de friction) adéquates pour cette application.Requirement WO 2007/085643 discloses polyurethane thickened homokinetic joint grease compositions comprising from 0.1 to 5% by weight of WS2, and from 0.1 to 5% by weight of zinc dithiophosphate and / or molybdenum dithiocarbamate. This application also discloses the possibility of using as an additive in greases graphite or MoS 2 . However, the use of graphite (or MoS 2 ) in combination with MoDTC is disadvised because this combination has, according to this application, an adverse effect on the anti-wear properties and the coefficient of friction of greases. The documents WO 2010/114209 and JP 2009138055 disclose grease compositions for homokinetic joints. There is therefore a need for greases for constant velocity joints, containing non-toxic raw materials, available and inexpensive, simple to manufacture, having a reduced rate of molybdenum (Mo) and phosphorus (P), and having anti-wear properties. and friction properties (low coefficient of friction) adequate for this application.

La demanderesse a mis en évidence que des graisses pour joints homocinétiques épaissies aux savons métalliques d'acide gras et comprenant du graphite en combinaison avec du dithiocarbamate de molybdène permettent de répondre au besoin exposé ci-dessus.The Applicant has shown that grease for constant velocity joints thickened metal soap fatty acid and comprising graphite in combination with molybdenum dithiocarbamate meet the need outlined above.

Ces graisses selon l'invention présentent des propriétés antiusure améliorées par rapport aux graisses pour joints homocinétiques connues à base de savon lithium. Les propriétés de friction sont équivalentes à celles des graisses connues. Ces graisses peuvent par ailleurs atteindre ces performances avec un taux de molybdène et éventuellement de phosphore inférieur aux graisses de l'art antérieur.These greases according to the invention have improved antiwear properties compared with greases for known constant velocity joints based on lithium soap. The friction properties are equivalent to those of known greases. These fats can moreover achieve these performances with a molybdenum content and possibly phosphorus lower than the fats of the prior art.

Brève description de l'invention :Brief description of the invention

La présente invention est relative à des compositions de graisse comprenant

  1. a. Une ou plusieurs huiles de base minérale ou synthétiques, seules ou en mélange
  2. b. Un ou plusieurs savons métalliques simples ou complexes d'acides gras à titre d'épaississant,
  3. c. Au moins un dithiocarbamate de molybdène,
  4. d. Du gaphite et telle que définie dans la revendication 1.
Les compositions de graisse selon l'invention ont une teneur en molybdène comprise entre 1000 et 2800 ppm, préférentiellement comprise entre 1500 et 2500 ppm, préférentiellement entre 1700 et 2300, préférentiellement entre 2000 et 2200 ppm. Les compositions de graisse selon l'invention comprennent entre 0,5 et 3,0 % en masse de graphite, préférentiellement entre 0,7 et 2,0%. Les compositions de graisse selon l'invention ont un rapport Mo/[graphite], entre la teneur en molybdène, en ppm, et le pourcentage massique de graphite dans lesdites compositions, compris entre 1250 et 1550, préférentiellement entre 1300 et 1500.The present invention relates to grease compositions comprising
  1. at. One or more mineral or synthetic base oils, alone or in admixture
  2. b. One or more simple or complex metal fatty acid soaps as a thickener,
  3. vs. At least one molybdenum dithiocarbamate,
  4. d. Gaphite and as defined in claim 1.
The grease compositions according to the invention have a molybdenum content of between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferentially between 2000 and 2200 ppm. The grease compositions according to the invention comprise between 0.5 and 3.0% by weight of graphite, preferably between 0.7 and 2.0%. The grease compositions according to the invention have a Mo / [graphite] ratio, between the molybdenum content, in ppm, and the mass percentage of graphite in said compositions, ranging between 1250 and 1550, preferably between 1300 and 1500.

Selon un mode de réalisation, les compositions de graisse selon l'invention comprennent du phosphore, à une teneur inférieure à 1500 ppm, préférentiellement inférieure à 1200 ppm.According to one embodiment, the grease compositions according to the invention comprise phosphorus at a content of less than 1500 ppm, preferably less than 1200 ppm.

Selon un mode de réalisation, les compositions de graisse selon l'invention comprennent du zinc, à une teneur inférieure à 1500 ppm. Les compositions de graisse selon l'invention sont exemptes de lubrifiant solide MoS2.According to one embodiment, the grease compositions according to the invention comprise zinc at a content of less than 1500 ppm. The grease compositions according to the invention are free of MoS 2 solid lubricant.

Selon un autre mode préféré, les compositions de graisse selon l'invention sont exemptes de lubrifiant solide polytetrafluoroethylene.According to another preferred embodiment, the grease compositions according to the invention are free of polytetrafluoroethylene solid lubricant.

Préférentiellement, les compositions de graisse selon l'invention comprennent exclusivement un ou plusieurs savons métalliques simples ou complexes d'acides gras à titre d'épaississant.Preferably, the grease compositions according to the invention comprise exclusively one or more simple metal or complex fatty acid soaps as a thickener.

Préférentiellement, les compositions de graisses selon l'invention comprennent au moins un savon simple ou complexe de lithium, sodium, calcium, baryum, ou titane, seuls ou en mélange, à titre d'épaississant.Preferably, the grease compositions according to the invention comprise at least one simple soap or complex of lithium, sodium, calcium, barium, or titanium, alone or as a mixture, as a thickener.

Encore plus préférentiellement, les compositions de graisse selon l'invention comprennent un ou plusieurs savons de lithium simples ou complexes à titre d'épaississant.Even more preferentially, the grease compositions according to the invention comprise one or more single or complex lithium soaps as thickeners.

Selon un mode de réalisation, les compositions de graisse selon l'invention comprennent une huile de base (a) minérale, et une huile de base (a) synthétique, préférentiellement choisie parmi les polyalphaoléfines.According to one embodiment, the grease compositions according to the invention comprise a mineral base oil (a), and a synthetic base oil (a), preferably chosen from polyalphaolefins.

Selon un mode préféré, les compositions de graisse selon l'invention comprennent en outre un polymère (e) préférentiellement choisi parmi les polyisobutènes, les oléfines copolymères, les polyméthacrylates, les polyalphaoléfines, préférentiellement les polyisobutènesAccording to one preferred embodiment, the grease compositions according to the invention further comprise a polymer (e) preferably chosen from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.

Les compositions de graisse selon l'invention peuvent comprendre en outre un ou plusieurs additifs antiusure et/ou extrême pression phosphosoufrés (f), préférentiellement choisis parmi les dithiophosphates de Zinc.The grease compositions according to the invention may also comprise one or more phosphosulfur anti-wear and / or extreme pressure additives (f), preferably chosen from zinc dithiophosphates.

Préférentiellement, les Compositions de graisse selon l'invention ont une teneur en phosphore comprise entre 300 et 1200 ppm, préférentiellement entre 400 et 1000 ppm, préférentiellement entre 500 et 900 ppm.Preferably, the grease compositions according to the invention have a phosphorus content of between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.

Préférentiellement, les compositions selon l'invention ont une teneur en zinc comprise entre 500 et 1400 ppm, préférentiellement entre 600 et 1300 ppm, préférentiellement entre 800 et 1000 ppm.Preferably, the compositions according to the invention have a zinc content of between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 800 and 1000 ppm.

Selon un mode de réalisation, les compositions de graisse selon l'invention comprennent :

  • De 70 à 94 % d'huiles de base (a),
  • De 5 à 25 % d'épaississant (b),
  • De 1 à 5 % du mélange MoDTC (c) et graphite (d).
According to one embodiment, the grease compositions according to the invention comprise:
  • From 70 to 94% of base oils (a),
  • 5 to 25% thickener (b),
  • From 1 to 5% of the mixture MoDTC (c) and graphite (d).

Selon un autre mode de réalisation, les compositions de graisse selon l'invention comprennent :

  • De 70 à 94 % d'huiles de base (a),
  • De 5 à 25 % d'épaississant (b),
  • De 1 à 5 % du mélange MoDTC (c) et graphite (d),
  • Le reste éventuel étant constitué d'un ou plusieurs polymères (e) choisis parmi les polyisobutenes, les oléfines copolymères, les polyméthacrylates, les polyalphaoléfines, préférentiellement les polyisobutenes.
According to another embodiment, the grease compositions according to the invention comprise:
  • From 70 to 94% of base oils (a),
  • 5 to 25% thickener (b),
  • From 1 to 5% of the mixture MoDTC (c) and graphite (d),
  • The remainder being composed of one or more polymers (e) chosen from polyisobutenes, olefins copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.

Selon un mode préféré, les compositions de graisse selon l'invention comprennent :

  • De 70 à 93,9 % d'huiles de base (a),
  • De 5 à 23,5 % d'épaississant (b),
  • De 1 à 5 % du mélange MoDTC et graphite (c) et (d),
  • De 0,1 à 1,5 % d'un ou plusieurs additifs antiusure et/ou extrême pression phosphosoufrés (f), préférentiellement choisis parmi les dithiophosphates de zinc.
According to a preferred embodiment, the grease compositions according to the invention comprise:
  • From 70 to 93.9% of base oils (a),
  • From 5 to 23.5% thickener (b),
  • From 1 to 5% of the mixture MoDTC and graphite (c) and (d),
  • 0.1 to 1.5% of one or more phosphosulfur anti-wear and / or extreme pressure additives (f), preferably chosen from zinc dithiophosphates.

Selon un autre mode préféré, les compositions de graisse selon l'invention comprennent :

  • De 70 à 93,9 % d'huiles de base (a),
  • De 5 à 23,5 % d'épaississant (b),
  • De 1 à 5 % du mélange MoDTC et graphite (c) et (d),
  • De 0,1 à 1,5 % d'un ou plusieurs additifs antiusure phosphorés ou phosphosoufrés (f), préférentiellement choisis parmi les dithiophosphates de zinc.
  • Le reste éventuel étant constitué d'un ou plusieurs polymères (e) choisis parmi les polyisobutenes, les oléfines copolymères, les polyméthacrylates, les polyalphaoléfines, préférentiellement les polyisobutènes.
According to another preferred embodiment, the grease compositions according to the invention comprise:
  • From 70 to 93.9% of base oils (a),
  • From 5 to 23.5% thickener (b),
  • From 1 to 5% of the mixture MoDTC and graphite (c) and (d),
  • 0.1 to 1.5% of one or more phosphorus or phosphosulfur anti-wear additives (f), preferably chosen from zinc dithiophosphates.
  • The remainder consisting of one or more polymers (e) selected from polyisobutenes, olefins copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.

La présente invention est également relative à l'utilisation de compositions de graisse telles que décrites ci-dessus comme graisses pour joints homocinétiques des transmissions de véhicules automobiles.The present invention also relates to the use of grease compositions as described above as greases for homokinetic joints of motor vehicle transmissions.

La présente invention est également relative à un des joints homocinétiques remplis de compositions de graisse telles que décrites ci dessus.The present invention also relates to one of the homokinetic joints filled with grease compositions as described above.

DESCRIPTION DETAILLEE : DETAILED DESCRIPTION : Huiles de base lubrifiantes (a)Lubricating base oils (a)

La ou les autres huiles de base utilisées dans les compositions selon la présente invention peuvent être des huiles d'origine minérales ou synthétiques des groupes I à V selon les classes définies dans la classification API (American Petroleum Institute).The other base oil (s) used in the 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 (American Petroleum Institute).

Les huiles de base minérales selon l'invention incluent tous types de bases obtenues par distillation atmosphérique et sous vide du pétrole brut, suivies d'opérations de raffinage tels qu'extraction au solvant, désalphatage, déparaffinage au solvant, hydrotraitement, hydrocraquage et hydroisomérisation, hydrofinition.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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.

Les huiles de bases des compositions de graisses selon la présente invention peuvent également être des huiles synthétiques, tels certains esters, silicones, polyalkyleneglycols, polybutène, polyalphaoléfines (PAO), alkylbenzene, alkylnaphtalene.The base oils of the grease compositions according to the present invention may also be synthetic oils, such as certain esters, silicones, polyalkylene glycols, polybutene, polyalphaolefins (PAO), alkylbenzene, alkylnaphthalene.

Les huiles de bases peuvent également être des huiles d'origine naturelle, par exemple des esters d'alcool et d'acides carboxyliques, pouvant être obtenus à partir de ressources naturelles telles qu l'huile de tournesol, de colza, de palme, ....The base oils may also be oils of natural origin, for example esters of alcohol and carboxylic acids, obtainable from natural resources such as sunflower oil, rapeseed oil, palm oil. ...

Préférentiellement, dans les compositions selon l'invention, des huiles synthétiques de type polyoaplphaléfines (PAO) sont présentes en combinaison avec des huiles minérales. Les polyalphaoléfines sont par exemple obtenues à partir de monomères ayant de 4 à 32 atomes de carbone (par exemple octène, decène). Leur masse moléculaire moyenne en poids est typiquement comprise entre 250 et 3000.Preferentially, in the compositions according to the invention, synthetic oils of the polyoaplphadefin (PAO) type are present in combination with mineral oils. The polyalphaolefins are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene). Their weight average molecular weight is typically between 250 and 3000.

Le mélange d'huiles de bases est calé de façon à ce que sa viscosité à 40 °C selon la norme ASTM D 445 soit comprise entre 30 et 140 cSt, préférentiellement entre 50 et 100 cSt. A cet effet, on peut utiliser une large gamme de polyalphaoléfines, légères, comme par exemple la PAO 6 (31 cSt à 40°C), la PAO 8 (48 cSt à 40°C), ou lourdes, comme la PAO 40 (400 cSt à 40°C), ou la PAO 100 (1000 cSt à 40°C).The base oil mixture is set so that its viscosity at 40 ° C according to ASTM D 445 is between 30 and 140 cSt, preferably between 50 and 100 cSt. For this purpose, a wide range of light polyalphaolefins can be used, such as for example PAO 6 (31 cSt at 40 ° C), PAO 8 (48 cSt at 40 ° C), or heavy, such as PAO 40 ( 400 cSt at 40 ° C), or PAO 100 (1000 cSt at 40 ° C).

Epaississants (b)Thickeners (b)

Les graisses selon la présente invention sont épaissies aux savons métalliques d'acides gras.The greases according to the present invention are thickened with metal fatty acid soaps.

Les savons métalliques d'acides gras peuvent êtres préparés séparément, ou in situ lors de la fabrication de la graisse (dans ce dernier cas, on dissout le ou les acides gras dans l'huile de base, puis on ajoute l'hydroxyde de métal approprié). Ces épaississants sont des produits couramment employés dans le domaine des graisses, facilement disponibles et bon marché. Ils présentent le meilleur compromis technique, en réunissant à la fois de bonnes propriétés mécaniques, une bonne tenue thermique, et une bonne tenue à l'eau.Metallic fatty acid soaps can be prepared separately, or in situ during the manufacture of the fat (in the latter case, the fatty acid (s) are dissolved in the base oil, and then the metal hydroxide is added. appropriate). These thickeners are commonly used products in the field of fats, readily available and inexpensive. They present the best technical compromise, by combining both good mechanical properties, good thermal resistance, and good water resistance.

On utilise préférentiellement des acides gras à chaîne longue comprenant typiquement de 10 à 28 atomes de carbone, saturée ou insaturée, éventuellement hydroxylée.Long-chain fatty acids typically comprising from 10 to 28 carbon atoms, saturated or unsaturated, optionally hydroxylated, are preferably used.

Les acides gras à chaîne longue (comprenant typiquement de 10 à 28 atomes de carbone), sont par exemple les acides capriques, laurique, myristiques, palmitiques, stéarique, arachidique, béhénique, oléiques, linoléique, éruciques, et leurs dérivés hydroxylés. L'acide 12 hydroxystéarique est le dérivé le plus connu de cette catégorie, et préféré.Long-chain fatty acids (typically comprising from 10 to 28 carbon atoms) are, for example, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, oleic, linoleic and erucic acids, and their hydroxylated derivatives. Hydroxystearic acid 12 is the best known derivative of this class, and preferred.

Ces acides gras à chaîne longue proviennent généralement d'huiles végétales, par exemple huile de palme, de ricin, de colza, de tournesol,... ou de graisses animales (suif, huile de baleine...).These long-chain fatty acids generally come from vegetable oils, for example palm oil, castor oil, rapeseed oil, sunflower oil, ... or animal fats (tallow, whale oil, etc.).

On peut former des savons dits simples en utilisant un ou plusieurs acides gras à chaîne longue.So-called simple soaps can be formed using one or more long-chain fatty acids.

On peut également former des savons dits complexes en utilisant un ou plusieurs acides gras à chaîne longue en combinaison avec un ou plusieurs acides carboxyliques à chaîne hydrocarbonée courte comprenant au plus 8 atomes de carbone.So-called complex soaps can also be formed by using one or more long-chain fatty acids in combination with one or more short-chain hydrocarbon carboxylic acids having at most 8 carbon atoms.

L'agent de saponification utilisé pour faire le savon peut être un composé métallique de Lithium, Sodium, Calcium, Baryum, Titane, Aluminium, préférentiellement Lithium et Calcium, et de préférence un hydroxyde, oxyde ou un carbonate de ces métaux. Les savons métalliques, en particulier de Lithium, Sodium, Calcium, Baryum, Titane, forment une structure fibreuse, à l'exception des savons d'aluminium, simples ou complexes, qui ont une structure de gel sphérique.The saponification agent used to make the soap may be a metal compound of Lithium, Sodium, Calcium, Barium, Titanium, Aluminum, preferably Lithium and Calcium, and preferably a hydroxide, oxide or carbonate of these metals. Metal soaps, in particular Lithium, Sodium, Calcium, Barium, Titanium, form a fibrous structure, with the exception of simple or complex aluminum soaps, which have a spherical gel structure.

On peut employer un ou plusieurs composés métalliques, ayant ou non le même cation métallique, dans les graisses selon l'invention. On peut ainsi associer des savons au lithium, combinés avec des savons au calcium dans une moindre proportion. Ceci présente l'avantage d'améliorer la tenue à l'eau des graisses.One or more metal compounds, with or without the same metal cation, may be used in the greases according to the invention. It is thus possible to associate lithium soaps, combined with calcium soaps to a lesser extent. This has the advantage of improving the water resistance of greases.

Les savons métalliques sont employés à des teneurs de l'ordre de 5 à 20 % en poids, préférentiellement de 8 à 15 % en poids, préférentiellement de 10 à 12 %, typiquement 11 % en poids dans les graisses selon l'invention. La quantité de savon(s) métallique(s) est généralement ajustée de manière à obtenir des graisses de grade 00, de grade 0, de grade 1 ou de grade 2 selon la classification NLGI.The metal soaps are employed at levels of the order of 5 to 20% by weight, preferably 8 to 15% by weight, preferably 10 to 12%, typically 11% by weight in the greases according to the invention. The amount of metallic soap (s) is generally adjusted to obtain Grade 00, Grade 0, Grade 1 or Grade 2 fats according to the NLGI classification.

Préférentiellement, les graisses selon l'invention contiennent majoritairement des savons métalliques d'acides gras à titre d'épaississant. On entend par là que les savons métalliques d'acides gras, simples ou complexes, représentent ensemble le plus fort pourcentage en poids dans les graisses selon l'invention, comparé au pourcentage en poids des autres matières épaississantes.Preferably, the greases according to the invention mainly contain metal fatty acid soaps as thickeners. This means that Metallic fatty acid soaps, simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.

Préférentiellement, les graisses selon l'invention contiennent majoritairement des savons de Lithium simples ou complexes à titre d'épaississant. On entend par là que les savons de lithium, simples ou complexes, représentent ensemble le plus fort pourcentage en poids dans les graisses selon l'invention, comparé au pourcentage en poids des autres matières épaississantes.Preferably, the greases according to the invention mainly contain simple or complex lithium soaps as thickeners. By this is meant that lithium soaps, simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.

Préférentiellement, la quantité du ou des savons métalliques d'acides gras, simples ou complexes, constitue au moins 50 %, encore plus préférentiellement au moins 80 % en poids par rapport au poids total de matières épaississantes, dans les compositions de graisse selon l'invention.Preferably, the quantity of the metal soap or fatty acids, simple or complex, constitutes at least 50%, more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention. invention.

Préférentiellement, la quantité de savons de lithium, simples ou complexes, constitue au moins 50 %, encore plus préférentiellement au moins 80 % en poids par rapport au poids total de matières épaississantes, dans les compositions de graisse selon l'invention.Preferably, the amount of lithium soap, simple or complex, constitutes at least 50%, even more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention.

Selon un mode de réalisation, les graisses selon l'invention peuvent contenir comme épaississant majoritaire des savons métalliques d'acides gras simples ou complexes, et de moindres quantités d'autres épaississants, tels que les polyurées, ou des épaississants inorganiques, type bentonite ou alumino silicates.According to one embodiment, the greases according to the invention may contain, as the major thickener, metal soap of simple or complex fatty acids, and smaller amounts of other thickeners, such as polyureas, or inorganic thickeners, such as bentonite or alumino silicates.

Préférentiellement, les graisses selon l'invention sont exemptes d'épaississants de type polyurées, qui sont plus compliqués techniquement à fabriquer, en particulier parce que les composants entrant dans leur fabrication, telles que les isocyanates et les aminés, sont très toxiques et peu stables au stockage.Preferably, the greases according to the invention are free of polyurea thickeners, which are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and unstable. in storage.

Encore plus préférentiellement, les graisses selon l'invention contiennent exclusivement des savons métalliques d'acides gras simples ou complexes à titre d'épaississant.Even more preferentially, the greases according to the invention exclusively contain simple or complex fatty acid metal soaps as thickeners.

Encore plus préférentiellement, les graisses selon l'invention contiennent exclusivement des savons métalliques d'acides gras simples ou complexes de Lithium à titre d'épaississant.Even more preferentially, the greases according to the invention exclusively contain metal soaps of simple or complex fatty acids of lithium as thickeners.

Dithiocarbamate de molybdène et graphite :Molybdenum dithiocarbamate and graphite:

Les compositions de graisse selon l'invention contiennent du graphite et du dithiocarbamate de molybdène, ce qui leur confère des propriétés antiusure améliorées par rapport aux graisses commerciales connues. Ces propriétés peuvent être atteintes avec une teneur en molybdène inférieur à celui des graisses connues. La teneur en molybdène des graisses selon l'invention est comprise entre 1000 et 2800 ppm. Le rapport Mo/[graphite], entre la teneur en molybdène, en ppm, et le pourcentage massique de graphite dans lesdites composition, est compris entre 1250 et 1550. En effet constaté que, lorsque ces composés sont présents dans les proportions mentionnées ci-dessus, les compositions de graisse ont également de très bonnes propriétés antiusure et friction, équivalentes à celles des graisses commerciales connues. Ces bonnes propriétés sont par ailleurs atteintes avec un taux de molybdène, et éventuellement un taux d'autres éléments métalliques tels que le zinc ou un taux d'élément phosphore, inférieur à ceux des graisses connues.The grease compositions according to the invention contain graphite and molybdenum dithiocarbamate, which gives them anti-wear properties. improved compared to known commercial fats. These properties can be achieved with a lower molybdenum content than known fats. The molybdenum content of the greases according to the invention is between 1000 and 2800 ppm. The ratio Mo / [graphite], between the content of molybdenum, in ppm, and the mass percentage of graphite in said composition, is between 1250 and 1550. Indeed, it is found that, when these compounds are present in the proportions mentioned above. above, the grease compositions also have very good anti-wear and friction properties, equivalent to those of known commercial greases. These good properties are also achieved with a molybdenum content, and possibly a level of other metallic elements such as zinc or a phosphorus element level, lower than those of known fats.

Ces performances peuvent être atteintes sans qu'il soit besoin d'ajouter aux compositions de graisse selon l'invention des additifs lubrifiants solides tels que des poudres de MoS2, ou de polytetrafluoroethylene (PTFE). Les teneurs éventuelles en additifs phosphorés, notamment antiusure, peuvent également être faibles.These performance can be achieved without the need to add to the grease compositions according to the invention solid lubricating additives such as MoS2 powders, or polytetrafluoroethylene (PTFE). The possible contents of phosphorus additives, especially anti-wear, may also be low.

Dithiocarbamate de molybdène (DTCMo) (c)Molybdenum Dithiocarbamate (DTCMo) (c)

Les compositions selon l'invention contiennent des dithiocarbamates de molybdène, additifs modificateurs de friction biens connus de l'homme du métier.The compositions according to the invention contain molybdenum dithiocarbamates, friction modifying additives well known to those skilled in the art.

Ces modificateurs de frottement organométalliques dithiocarbamate de molybdène peuvent par exemple être des dialkyldithiocarbamates de molybdène répondant à la formule (I) :

Figure imgb0001
Où X1, X2, X3, X4 sont des chaînes alkyl, comportant préférentiellement de 2 à 13 atomes de carbone, préférentiellement de 2 à 6 atomes de carbone.These molybdenum dithiocarbamate organometallic friction modifiers may for example be dialkyldithiocarbamates of molybdenum corresponding to formula (I):
Figure imgb0001
 Where X 1 , X 2 , X 3 , X 4 are alkyl chains, preferably containing 2 to 13 carbon atoms, preferably 2 to 6 carbon atoms.

La quantité de MoDTC des compositions selon l'invention est ajustée de manière à ce que leur teneur en molybdène soit comprise entre 1000 et 2800 ppm, préférentiellement entre 1500 et 2500 ppm, préférentiellement entre 1700 et 2300, préférentiellement entre 2000 et 2200 ppm.The amount of MoDTC of the compositions according to the invention is adjusted so that their molybdenum content is between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm.

Cette teneur peut être mesurée selon les techniques usuelles, plasma, absorption atomique, flurescence X.This content can be measured according to the usual techniques, plasma, atomic absorption, flurescence X.

Il n'est pas souhaitable d'utiliser le MoDTC comme seul additif (antiusure), dans une composition de graisse. En effet, il est connu que le MoDTC nécessite une température minimale d'activation et la présence d'autres additifs (antiusure, extrême pression) pour être efficace.It is not desirable to use MoDTC as the only additive (antiwear) in a fat composition. Indeed, it is known that the MoDTC requires a minimum activation temperature and the presence of other additives (antiwear, extreme pressure) to be effective.

Des graisses comprenant du MoDTC sans autre additif antiusure et/ou extrême pression ne seraient pas efficaces, en particulier à basse température. Dans les graisses de l'art antérieur, le MoDTC est ainsi associé à des additifs phosphorés, par exemple dithiophosphates.Greases comprising MoDTC without other antiwear and / or extreme pressure additives would not be effective, especially at low temperatures. In the greases of the prior art, MoDTC is thus associated with phosphorus additives, for example dithiophosphates.

Dans les graisses selon l'invention, le MoDTC est combiné a du graphite, ce qui permet de produire des graisses ayant de très bonnes propriétés en usure et friction, avec un taux de molybdène et de phosphore faible.In the greases according to the invention, the MoDTC is combined with graphite, which makes it possible to produce fats having very good properties in wear and friction, with a low molybdenum and phosphorus content.

Lorsque la teneur en Mo est trop faible, les propriétés anti usure (notamment sous forte charge), seront insuffisantes pour les applications joints homocinétiques.When the Mo content is too low, anti-wear properties (especially under heavy load) will be insufficient for homokinetic joint applications.

Lorsque la teneur en MoDTC est trop élevée (au détriment du graphite), on constate que les performances des graisses en friction sont dégradées.When the content of MoDTC is too high (at the expense of graphite), it is found that the performance of the friction greases are degraded.

Par ailleurs, il n'est pas souhaitable, pour des raisons environnementales, d'avoir de trop fortes teneurs en élément Mo dans les graisses. Au-delà des seuils en Mo mentionnés ci-dessus, on n'observe pas de gain en usure significatif.Moreover, it is undesirable, for environmental reasons, to have excessive levels of Mo element in the greases. Beyond the thresholds in Mo mentioned above, no significant wear gain is observed.

Graphite (d)Graphite (d)

Les compositions de graisse selon l'invention contiennent du graphite. La présence de graphite, connu pour ses propriétés comme lubrifiant solide, permet de diminuer la teneur en additifs modificateur de frottement et antiusure contenant du molybdène (et éventuellement du phosphore), sans apporter d'élément métallique, et en maintenant les propriétés d'usure et de friction convenant à l'application joints homocinétiques.The grease compositions according to the invention contain graphite. The presence of graphite, known for its properties as a solid lubricant, makes it possible to reduce the content of friction modifying and anti-wear additives containing molybdenum (and possibly phosphorus), without adding a metallic element, and by maintaining the wear properties. and friction suitable for applying homokinetic joints.

La substitution intégrale de ces additifs au molybdène par le graphite n'est toutefois pas souhaitable, car le graphite n'est pas très efficace sous forte charge et des problèmes d'usure pourraient survenir dans de telles graisses. On constate de même une augmentation de l'usure lorsque la quantité de graphite est trop importante au détriment du molybdène.However, the complete substitution of these additives for molybdenum by graphite is not desirable because graphite is not very efficient under heavy load and wear problems could occur in such greases. There is also an increase in wear when the amount of graphite is too important at the expense of molybdenum.

Préférentiellement, le graphite employé dans les compositions selon l'invention est une poudre de taille micrométrique, avec des tailles de particules comprises environ entre 1 et 15 µm, et par exemple une distribution de taille caractérisée par un diamètre D50 compris entre 3 et 8 µm, préférentiellement entre 5 et 7 µm.Preferably, the graphite employed in the compositions according to the invention is a powder of micrometric size, with particle sizes included approximately between 1 and 15 microns, and for example a size distribution characterized by a diameter D50 of between 3 and 8 microns, preferably between 5 and 7 microns.

Les Composition de graisse selon l'invention comprennent entre 0,5 et 3,0 % en masse de graphite, préférentiellement entre 0,7 et 2,0%, préférentiellement entre 0,75 et 1,7 %, préférentiellement entre 1,0 et 1,5% en masse de graphite.The fat composition according to the invention comprises between 0.5 and 3.0% by weight of graphite, preferably between 0.7 and 2.0%, preferentially between 0.75 and 1.7%, preferably between 1.0 and 1.0%. and 1.5% by weight of graphite.

Composés phospho soufrés (f)Phospho sulfur compounds (f)

Les graisses selon l'invention contiennent optionnellement des additifs anti usure et extrême pression phospho soufrés utilisés couramment dans la formulation de graisses et de lubrifiants.The greases according to the invention optionally contain sulfur-phosphorus anti wear and extreme pressure additives commonly used in the formulation of greases and lubricants.

Ce sont par exemple et non limitativement l'acide thiophosphorique, l'acide thiophosphoreux, les esters de ces acides, leurs sels, et les dithiophosphates, particulièrement les dithiophosphates de Zinc.These are, for example and not limited to, thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, particularly zinc dithiophosphates.

On préférera en particulier les dithiophosphates de Zinc de formule (II) :

Figure imgb0002
Zinc dithiophosphates of formula (II) are particularly preferred:
Figure imgb0002

Où R1, R2, R3, R4 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 14 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.Wherein R 1 , R 2 , R 3 and R 4 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 14 carbon atoms, or optionally substituted aryl groups containing from 6 to 30, preferably 8 to 18 carbon atoms.

Ces différents composés peuvent être employés seuls ou en mélange dans les compositions de graisse selon l'invention. Leur pourcentage massique dans les compositions selon l'invention est préférentiellement compris entre 0,5 et 5 % en poids, préférentiellement entre 0,7 et 2 % en poids, ou encore entre 0,8 et 1,5 % en poids par rapport au poids total de la composition. Leur quantité sera ajustée de manière à respecter les teneurs limites en éléments molybdène et phosphore des compositions selon l'invention.These different compounds can be used alone or as a mixture in the grease compositions according to the invention. Their mass percentage in the compositions according to the invention is preferably between 0.5 and 5% by weight, preferably between 0.7 and 2% by weight, or between 0.8 and 1.5% by weight relative to the total weight of the composition. Their quantity will be adjusted so as to respect the limiting levels in molybdenum and phosphorus elements of the compositions according to the invention.

La teneur en molybdène (Mo) des compositions selon l'invention est comprise entre 1000 et 2800 ppm préférentiellement entre 1500 et 2500 ppm, préférentiellement entre 1700 et 2300, préférentiellement entre 2000 et 2200 ppm.The molybdenum (Mo) content of the compositions according to the invention is between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm.

La teneur en phosphore (P) des compositions selon l'invention est préférentiellement inférieure à 1500 ppm, préférentiellement inférieure à 1200 ppm, préférentiellement comprise entre 300 et 1200 ppm, préférentiellement entre 400 et 1000 ppm, préférentiellement entre 500 et 900 ppm.The phosphorus content (P) of the compositions according to the invention is preferably less than 1500 ppm, preferentially less than 1200 ppm, preferably between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.

Cette teneur peut être mesurée selon les techniques usuelles, plasma, absorption atomique.This content can be measured according to the usual techniques, plasma, atomic absorption.

Préférentiellement, lorsque les compositions comprennent du dithiophosphate de Zinc, la teneur en zinc des compositions selon l'invention est inférieure à 1500 ppm, préférentiellement comprise entre 500 et 1400 ppm, préférentiellement entre 600 et 1300 ppm, préférentiellement entre 700 et 1200 ppm, préférentiellement entre 800 et 1000 ppm.Preferably, when the compositions comprise zinc dithiophosphate, the zinc content of the compositions according to the invention is less than 1500 ppm, preferably between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 700 and 1200 ppm, preferentially between 800 and 1000 ppm.

Les compositions lubrifiantes selon la présente invention peuvent également contenir des additifs anti usure et extrême- pression phosphorés, tels que par exemple les phosphates d'alkyle ou phosphonates d'alkyle, l'acide phosphorique, l'acide phopsphoreux, les mono, di et triesters de l'acide phosphoreux et de l'acide phosphorique, et leurs selsThe lubricating compositions according to the present invention may also contain phosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono, di and triesters of phosphorous acid and phosphoric acid, and their salts

Les compositions lubrifiantes selon la présente invention peuvent également contenir des additifs anti usure et extrême- pression soufrés, tels que les dithiocarbamates, thiadiazoles et benzothiazoles, les oléfines soufrées.The lubricating compositions according to the present invention may also contain sulfur-containing wear and extreme pressure additives, such as dithiocarbamates, thiadiazoles and benzothiazoles, sulfur-containing olefins.

Autres additifs :Other additives:

Les graisses selon l'invention peuvent également contenir tous type d'additifs adaptés à leur utilisation, par exemple des antioxydants, tels que les aminés ou phénoliques, des antirouille qui peuvent être des composés oxygénés tels que les esters, des passivants cuivre.The greases according to the invention may also contain any type of additive suitable for their use, for example antioxidants, such as amines or phenolics, antirust which may be oxygenated compounds such as esters, copper passivates.

Ces différents composés sont généralement présents à des teneurs inférieures à 1%, ou encore à 0,5% en masse dans les graisses.These various compounds are generally present at levels of less than 1%, or else at 0.5% by weight in fats.

Les graisses selon l'invention peuvent également contenir des polymères (e), par exemple des polyoléfines, polyisobutène (PIB), ds polyethylenes, polypropylene, des PAO lourdes, des oléfines copolymères (OCP) par exemple diène - styrene hydrogéné, des polyméthacrylates (PMA), à des teneurs généralement comprises entre 1 et 35%. On utilisera par exemple des PIB de masse molaire comprise entre 15 000 et 25 000 dalton à des teneurs généralement comprises entre 2 et 15% en masse, ou entre 5 et 10% en masse.The greases according to the invention may also contain polymers (e), for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example hydrogenated diene styrene, polymethacrylates ( PMA) at levels generally between 1 and 35%. For example, molar mass PIBs between 15,000 and 25,000 daltons at levels generally between 2 and 15% by weight, or between 5 and 10% by weight.

Ces polymères sont utilisés pour améliorer la cohésivité des graisses, qui résistent ainsi mieux à la centrifugation. Ces polymères entraînent également une meilleure adhésivité de la graisse aux surfaces, et augmentent la viscosité de la fraction huile de base, donc l'épaisseur du film d'huile entre les pièces en frottement.These polymers are used to improve the cohesiveness of the greases, which are thus more resistant to centrifugation. These polymers also result in better adhesiveness of the grease to the surfaces, and increase the viscosity of the base oil fraction, thus the thickness of the oil film between the friction parts.

Procédé de préparation des graisses :Process for preparing greases

Les graisses selon l'invention sont préférentiellement fabriquées en formant le savon métallique in situ.The greases according to the invention are preferably manufactured by forming the metal soap in situ.

On dissout ou plusieurs acides gras dans une fraction de l'huile de base ou du mélange d'huile de base à température ambiante. Cette fraction est généralement de l'ordre de 50 % de la quantité totale d'huile contenue dans la graisse finale. Les acides gras peuvent être des acides longs, comprenant de 14 à 28 atomes de carbone, pour former un savon simples, éventuellement combinés à des acides gras courts, comprenant de 6 à 12 atomes de carbone, pour former des savons complexes.One or more fatty acids are dissolved in a fraction of the base oil or base oil mixture at room temperature. This fraction is generally of the order of 50% of the total amount of oil contained in the final fat. The fatty acids can be long acids, comprising from 14 to 28 carbon atoms, to form a simple soap, optionally combined with short fatty acids, comprising from 6 to 12 carbon atoms, to form complex soaps.

On ajoute, à une température d'environ 60 à 80 °C, des composés métalliques, préférentiellement de type hydroxyde métallique.At a temperature of about 60 to 80 ° C are added metal compounds, preferably metal hydroxide type.

On peut ajouter ainsi un seul type de métal ou combiner plusieurs métaux. Le métal préféré des compositions selon l'invention est le Lithium, éventuellement combiné, dans une moindre proportion, à du Calcium.One type of metal can be added together or several metals can be combined. The preferred metal of the compositions according to the invention is lithium, possibly combined, to a lesser extent, with calcium.

On laisse se dérouler la réaction de saponification des acides gras par le ou les composés métalliques à une température d'environ 100 à 110°C.The saponification reaction of the fatty acids is allowed to proceed with the metal compound (s) at a temperature of about 100 to 110 ° C.

L'eau formée est ensuite évaporée par cuisson du mélange à une température d'environ 200°C. La graisse est ensuite refroidie par la fraction restante d'huile de base.The water formed is then evaporated by cooking the mixture at a temperature of about 200 ° C. The grease is then cooled by the remaining fraction of base oil.

On incorpore ensuite les additifs à environ 80°C.The additives are then incorporated at about 80 ° C.

On malaxage ensuite pendant un temps suffisant pour obtenir une composition de graisse homogène.Kneading is then carried out for a time sufficient to obtain a homogeneous fat composition.

Grade des graisses :Grade of fats:

La consistance d'une graisse mesure sa dureté ou sa fluidité au repos. Elle est chiffrée par la profondeur de pénétration d'un cône de dimensions et de masse donnée. La graisse est préalablement soumise à un malaxage. Les conditions de mesure de la consistance d'une graisse sont définies par la norme ASTM D 217.The consistency of a grease measures its hardness or fluidity at rest. It is quantified by the depth of penetration of a cone of given dimensions and mass. The fat is previously subjected to mixing. The conditions for measuring the consistency of a grease are defined by ASTM D 217.

Selon leur consistance, les graisses sont réparties en 9 classes ou 9 grades NLGI (National Lubricating Grease Institute) couramment utilisés dans le domaine des graisses. Ces grades sont indiqués dans le tableau ci-dessous.Depending on their consistency, the fats are divided into 9 classes or 9 NLGI grades (National Lubricating Grease Institute) commonly used in the field of fats. These grades are shown in the table below.

Les graisses selon l'invention sont préférentiellement des graisses de consistance comprise entre et 265 et 430, préférentiellement entre 265 et 385, préférentiellement entre 265 et 340 dixièmes de millimètre selon ASTM D217. Préférentiellement, elles sont de grade NLGI 00, 0, 1 ou 2, c'est-à-dire que leur consistance est respectivement comprise entre 400 et 430 , ou 335 et 385, ou 310 et 340, ou 265 et 295 dixièmes de millimètres selon ASTM D217. Grade de NLGI Consistance selon ASTM D 217 (dixième de millimètres) 000 445 - 475 00 400 - 430 0 335 - 385 1 310 - 340 2 265 - 295 3 220 - 250 4 175 - 205 5 130 - 160 6 85 - 115 The greases according to the invention are preferably greases with a consistency of between 265 and 430, preferably between 265 and 385, preferably between 265 and 340 tenths of a millimeter according to ASTM D217. Preferably, they are NLGI grade 00, 0, 1 or 2, that is to say that their consistency is respectively between 400 and 430, or 335 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217. NLGI Rank Consistency according to ASTM D 217 (tenth of a millimeter) 000 445 - 475 00 400 - 430 0 335 - 385 1 310 - 340 2 265 - 295 3 220 - 250 4 175 - 205 5 130 - 160 6 85 - 115

Grade des graisses.Grade of fats. Exemples :Examples: 1. préparation des compositions de graisses1. preparation of fat compositions

On prépare des compositions de graisse contenant divers additifs, notamment graphite et dithiocarbamate de molybdène, à partir d'un même pied de graisse comprenant des huiles de bases minérales et synthétiques, épaissies par un savon de Lithium simple préparé à partir de lithine (LiOH, H2O), et d'acide 12 hydroxystéarique. La composition du pied de graisse est indiquée dans le tableau 1 ce dessous. Le terme « pied de graisse » désigne couramment, pour l'homme du métier, une composition de graisse ne contenant que des huiles de base et des épaississants, et pas d'additif. Tableau 1 : composition du pied de graisse Composé % massique Huiles minérales 80,85 Huiles synthétiques (PAO) 9,00 Savon de lithium simple 10,15 Grease compositions containing various additives, in particular graphite and molybdenum dithiocarbamate, are prepared from the same grease base comprising mineral and synthetic base oils, thickened with a single lithium soap prepared from lithium hydroxide (LiOH). H2O), and 12-hydroxystearic acid. The composition of the fat foot is shown in Table 1 below. The term "grease foot" commonly refers to a person skilled in the art as a grease composition containing only base oils and thickeners, and no additive. <b> Table 1: fat foot composition </ b> Compound % mass Mineral oils 80.85 Synthetic oils (PAO) 9.00 Simple lithium soap 10.15

A partir de ce pied de graisse, on ajoute divers additifs : un polymère (PIB), pour améliorer la cohésivité et l'adhésivité, un anti usure (DTPZn), et divers lubrifiants solides : MoS2, graphite, MoDTC.

  • Le graphite employé est une poudre micrométrique, de diamètre D50 = 6µm
  • Le MoDTC employé est du di-n butyldithiocarbamate de molybdène, contenant 28% en masse de molybdène
  • Le MoS2 employé est une poudre micrométrique constituée de particules de taille comprise entre 0,5 et 8µm, de D50 environ 2 µm.
From this foot of fat, various additives are added: a polymer (PIB), to improve cohesiveness and adhesiveness, an anti-wear (DTPZn), and various solid lubricants: MoS 2 , graphite, MoDTC.
  • The graphite used is a micrometric powder, of diameter D50 = 6 μm
  • The MoDTC used is di-n-butyldithiocarbamate molybdenum, containing 28% by weight molybdenum
  • The MoS2 used is a micrometric powder consisting of particles having a size of between 0.5 and 8 μm and a D50 of around 2 μm.

Toutes les graisses préparées sont de grade 2 selon la classification NLGI.All prepared fats are grade 2 according to the NLGI classification.

La graisse A est une graisse commerciale pour joints homocinétiques, les graisses E, I et J sont selon l'invention.
Les compositions massiques des graisses sont données dans le tableau 2, ainsi que leurs propriétés en usure et en friction.Grease A is a commercial grease for constant velocity joints, greases E, I and J are according to the invention.
The mass compositions of greases are given in Table 2, as well as their properties in wear and friction.

Les propriétés en usure ont été évaluées en mesurant le diamètre d'usure (en mm) après le test 4 billes usure selon la norme ASTM D2266 (1 heure, charge 40 kg, 75 °C). Selon la spécification STL S71 3100, les graisses pour joint homocinétiques doivent conduire à un diamètre d'usure inférieur à 50 mm.The wear properties were evaluated by measuring the wear diameter (in mm) after the 4-ball wear test according to ASTM D2266 (1 hour, load 40 kg, 75 ° C). According to STL Specification S71 3100, CV greases must lead to a wear diameter of less than 50 mm.

Les propriétés de friction ont été évaluées en mesurant le coefficient de friction moyen sur tribomètre Cameron Plint cylindre-plan, dans les conditions ci après :

  • Pion mobile : cylindre SKF100C6(diamètre 7mm x longuer 7 mm)
  • Plan fixe : XC38 sans TTH polissage circulaire (Ra 0,8 µm)
  • Course : 2,5 mm
  • Fréquence : 5 niveaux entre 2,5 et 40 Hz, + réducteur 1/20
  • Charge : 3 niveaux, 10, 50, 110 N
  • Durée : 20 séquences, 1786 secondes au total
    • ∘ 16 paliers stabilisés de 80 secondes avec moyenne de frottement calculée sur les 40 dernières secondes
    • ∘ 2 acquisitions rapides sur 3 cycles de frottement instantané
    • ∘ 2 étapes fonctionnelles (rodage initial + changement de température)
  • Température : 2 phases : basse (50°c) puis haute température (100 °C)
  • Volume de graisse : 1g réparti en film mince et continu avant essai
The friction properties were evaluated by measuring the average friction coefficient on Cameron Plint cylinder-plane tribometer, under the following conditions:
  • Mobile pin: cylinder SKF100C6 (diameter 7mm x length 7mm)
  • Fixed plane: XC38 without TTH circular polishing (Ra 0.8 μm)
  • Stroke: 2.5 mm
  • Frequency: 5 levels between 2.5 and 40 Hz, + 1/20 reducer
  • Charge: 3 levels, 10, 50, 110 N
  • Duration: 20 sequences, 1786 seconds in total
    • ∘ 16 stabilized bearings of 80 seconds with average friction calculated over the last 40 seconds
    • ∘ 2 quick acquisitions on 3 cycles of instantaneous friction
    • ∘ 2 functional steps (initial break-in + temperature change)
  • Temperature: 2 phases: low (50 ° c) then high temperature (100 ° C)
  • Volume of grease: 1g distributed in thin film and continuous before test

Toutes les graisses contenant du MoDTC combiné à du graphite ont une teneur en molybdène très inférieure à celle de la graisse commerciale A, pour des performances en usure améliorées.
Les graisses E et I ont l'avantage supplémentaire de présenter des coefficients de friction faibles, de l'ordre de grandeur de ceux de la graisse commerciale A.

Figure imgb0003
All greases containing MoDTC combined with graphite have a much lower molybdenum content than commercial grease A for improved wear performance.
Greases E and I have the additional advantage of having low friction coefficients, of the order of magnitude of those of commercial grease A.
Figure imgb0003

Claims (15)

  1. A grease composition free of MoS2 solid lubricant comprising:
    a) one or several mineral or synthetic base oils, either alone or as a mixture,
    b) one or several simple or complex fatty acid metal soaps as a thickener,
    c) at least one molybdenum dithiocarbamate,
    d) graphite,
    comprising between 0.5 and 3.0% by mass of graphite, from 5 to 20% by weight of metal soap, having a molybdenum content comprised between 1,000 and 2,800 ppm, and
    wherein the Mo/[graphite] ratio, between the molybdenum content in ppm and the mass percentage of graphite in said composition, is comprised between 1,250 and 1,550.
  2. The grease composition according to claim 1 having a molybdenum content comprised between 1,500 and 2,500 ppm.
  3. The grease composition according to claim 1 having a molybdenum content comprised between 1,700 and 2,300, preferentially between 2,000 and 2,200 ppm.
  4. The grease composition according to one of claims 1 to 3 comprising by mass of graphite between 0.7 and 2.0%.
  5. The grease composition according to one of claims 1 to 4 wherein the Mo/[graphite] ratio, between the molybdenum content in ppm and the mass percentage of graphite in said composition, is comprised between 1,300 and 1,500.
  6. The grease composition according to one of claims 1 to 5 exclusively comprising one or several simple or complex fatty acid metal soaps as a thickener.
  7. The grease composition according to one of claims 1 to 6 comprising as a thickener, at least one simple or complex soap of lithium, sodium, calcium, barium, or titanium, either alone or as a mixture.
  8. The grease composition according to one of claims 1 to 7 comprising one or several simple or complex lithium soaps as a thickener.
  9. The grease composition according to one of claims 1 to 8 comprising a mineral base oil (a) and a synthetic base oil (a), preferentially selected from polyalphaolefins.
  10. The grease composition according to one of claims 1 to 9 further comprising a polymer (e) preferentially selected from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferentially polyisobutenes.
  11. The grease composition according to one of claims 1 to 10 further comprising one or several anti-wear and/or extreme pressure additives containing phosphorus and sulfur (f), preferentially selected from zinc dithiophosphates.
  12. The grease composition according to one of claims 1 to 11 comprising:
    • from 70 to 94% of base oils (a),
    • from 5 to 25% of thickener (b),
    • from 1 to 5% of the mixture of MoDTC (c) and graphite (d).
  13. The grease composition according to claim 11 comprising:
    • from 70 to 93.9% of base oils (a),
    • from 5 to 23.5% of thickener (b),
    • from 1 to 5% of the mixture of MoDTC (c) and graphite (d),
    • from 0.1 to 1.5% of one or several anti-wear additives containing phosphorus and sulfur (f), preferentially selected from zinc dithiophosphates,
    • the possible remainder consisting of one or several polymers (e) selected from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferentially polyisobutenes.
  14. Use of a grease composition according to one of claims 1 to 13 as grease for constant velocity joints of transmissions of automobile vehicles.
  15. A constant velocity joint filled with a grease according to one of claims 1 to 13.
EP11805228.1A 2010-12-13 2011-12-12 Grease composition Not-in-force EP2652099B1 (en)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2984348B1 (en) 2011-12-16 2015-02-27 Total Raffinage Marketing LUBRICATING COMPOSITIONS FOR TRANSMISSIONS
FR2984350B1 (en) 2011-12-16 2015-02-27 Total Raffinage Marketing FAT COMPOSITION
FR2990213B1 (en) 2012-05-04 2015-04-24 Total Raffinage Marketing LUBRICATING COMPOSITION FOR ENGINE
FR2998303B1 (en) 2012-11-16 2015-04-10 Total Raffinage Marketing LUBRICANT COMPOSITION
FR3018079B1 (en) * 2014-02-28 2017-06-23 Total Marketing Services LUBRICATING COMPOSITION BASED ON METALLIC NANOPARTICLES
JP6274435B2 (en) * 2014-09-22 2018-02-07 住鉱潤滑剤株式会社 Lubricant composition
JP6777285B2 (en) * 2016-11-30 2020-10-28 出光興産株式会社 Mixed grease
KR101964745B1 (en) * 2017-07-28 2019-08-13 주식회사 베어링아트 Grease composition
US20190382680A1 (en) * 2018-06-18 2019-12-19 Exxonmobil Research And Engineering Company Formulation approach to extend the high temperature performance of lithium complex greases
CN109504354B (en) * 2019-01-14 2021-03-09 中海石油(中国)有限公司上海分公司 Lubricant, drilling fluid and application thereof
CN110724577B (en) * 2019-09-29 2022-04-15 清研高装科技(天津)有限公司 Lubricating grease for robot and application thereof
JP7280800B2 (en) 2019-10-16 2023-05-24 協同油脂株式会社 Grease composition for reducer parts of automotive electrical equipment
JP2021130793A (en) * 2020-02-21 2021-09-09 出光興産株式会社 Deterioration measurement device, system and method, and lubricant composition
CN114317072A (en) * 2020-09-29 2022-04-12 惠州金永信五金制品有限公司 Lubricant suitable for metal stamping
CN113293052A (en) * 2021-05-25 2021-08-24 苏州安美润滑科技有限公司 Automobile ball cage lubricating grease and preparation method thereof
CN114703005A (en) * 2022-05-07 2022-07-05 辽宁国瑞新能科技有限公司 Nano-graphene extreme-pressure antiwear repair lubricating grease

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670461A (en) 1994-08-19 1997-09-23 Gkn Automotive Ag High temperature lubricating grease containing urea compounds
JP3320569B2 (en) 1994-10-21 2002-09-03 協同油脂株式会社 Grease composition for constant velocity joints
JP3954662B2 (en) * 1995-09-12 2007-08-08 昭和シェル石油株式会社 Grease composition for open gear
ZA988282B (en) * 1997-09-12 1999-03-09 Shell Int Research Lubricating compositions
JP2003105367A (en) * 2001-10-01 2003-04-09 Asahi Denka Kogyo Kk Lubricant composition
JP5386803B2 (en) * 2007-07-31 2014-01-15 Ｎｏｋクリューバー株式会社 Grease composition
JP4886304B2 (en) 2006-01-27 2012-02-29 昭和シェル石油株式会社 Grease composition
CN101353606B (en) * 2007-09-11 2011-04-20 威海旺润来润滑科技有限公司 Complex grease additive
JP2009138055A (en) * 2007-12-04 2009-06-25 Ntn Corp Lubricating grease
KR20100108905A (en) * 2009-03-31 2010-10-08 장암엘에스 주식회사 Grease composition having heat resistance and low friction force for constant velocity joints

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