EP2475752A1 - Fat composition - Google Patents

Fat composition

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Publication number
EP2475752A1
EP2475752A1 EP10763021A EP10763021A EP2475752A1 EP 2475752 A1 EP2475752 A1 EP 2475752A1 EP 10763021 A EP10763021 A EP 10763021A EP 10763021 A EP10763021 A EP 10763021A EP 2475752 A1 EP2475752 A1 EP 2475752A1
Authority
EP
European Patent Office
Prior art keywords
composition according
grease composition
carbon atoms
grease
metal
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.)
Granted
Application number
EP10763021A
Other languages
German (de)
French (fr)
Other versions
EP2475752B1 (en
Inventor
Franck Bardin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
Total Raffinage Marketing SA
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Filing date
Publication date
Application filed by Total Raffinage Marketing SA filed Critical Total Raffinage Marketing SA
Priority to PL10763021T priority Critical patent/PL2475752T3/en
Publication of EP2475752A1 publication Critical patent/EP2475752A1/en
Application granted granted Critical
Publication of EP2475752B1 publication Critical patent/EP2475752B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
    • 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
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions 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
    • C10M2205/028—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
    • 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
    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285—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 containing hydroxy groups; Ethers thereof 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
    • 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
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • 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
    • C10N2010/16—Groups 8, 9, or 10
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to low friction coefficient grease compositions, particularly for use in constant velocity joints which are used in transmission lines of motor vehicles.
  • 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 constant velocity joints must not only have an anti-wear effect, but also have 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.
  • anti-wear additives which 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.
  • the application EP 0435 745 describes, for example, a homokinetic joint grease comprising a mineral oil, a polyurea thickener, 0.5 to 5% by weight of molybdenum dithiophosphate (MoDTP) and 0.5 to 5% by weight. mass of Molybdenum dithiocarbamate (MoDTC) as a friction modifier (MF), and 0.5 to 10% by weight of ZnDTP as EP agent, and 0.5 to 60% of a copolymer of ethylene and alpha olefin connected.
  • MoDTC molybdenum dithiocarbamate
  • EP 0708 172 also describes a low-friction grease for homokinetic joints comprising a base oil, a simple or complex lithium soap thickener, one or more organic components containing molybdenum, of the MoDTC or MoDTP type, at least one zinc dithiophosphate, a metal-free phospho-sulfur extreme pressure agent, a calcium salt of oxidized wax, petroleum sulfonate or aromatic alkylsulfonates.
  • Patent FR 1 421 105 thus describes the use, for lowering the coefficient of friction of greases, of lubricant solids with a laminated crystalline structure in combination with metal salts of oxygenated phosphorus acids.
  • WO 2007/085643 discloses low friction coefficient grease compositions for homokinetic joints comprising a base oil, one or more thiourea type thickeners, 0.1 to 5% by weight of particulate tungsten disulfide having an average size of less than 10 ⁇ (tanmikB marketed by Nippon Lubricant Ltd), and 0.1 to 5% by weight of one or more zinc dithiophosphates and / or molybdenum dithiocarbamate.
  • US-P-5,516,439 discloses a grease composition
  • a grease composition comprising (a) a base oil, (b) a lithium-based thickener, (c) a molybdenum compound which is a molybdenum dithiophosphate or a molybdenum dithiocarbamate, (d) ) a zinc dithiophosphate, (e) a metal salt.
  • Solid lubricants such as molybdenum disulfide (MoS 2) or tungsten (WS 2) in the form of a sheet or in the form of fullerene to lower the coefficient of friction of greases.
  • MoS 2 molybdenum disulfide
  • WS 2 tungsten
  • Harsh Conditions ", by Lev Rapoport, Fleischer Nieles, Reshef Tenne Adv. Mast. 2003 15, 651-655 thus compares the friction properties of a reference grease consisting of Lithium thickened base oil, then additive of WS2 slip and finally WS2 fullerene.
  • the Applicant has demonstrated a synergistic effect between solid friction modifiers of transition metal chalocogenides in the form of inorganic fullerenes, with anti-wear and extreme pressure compounds of organophospho-sulfur type, in thickened greases, especially in lithium soaps.
  • the present invention relates to fat compositions comprising:
  • the thickener (b) is composed mainly of at least one metal soap of fatty acid.
  • the metallic soap (s) of fatty acid constitutes at least 50%, preferably at least 80% by weight of the thickener (b) in said compositions.
  • one or more transition metal chalcogenides having an inorganic fullerene structure used in the grease compositions according to the invention are grafted onto the surface by inorganic phosphate groups.
  • the chalcogen of at least one solid lubricant (c) is selected from S, Se, Te.
  • the transition metals of at least one solid lubricant (c) are chosen from Mo, W, Zr,
  • At least one solid lubricant (c) is a transition metal dichalcogenide, preferably Molybdenum disulfide MoS2 or WS2 tungsten bisulfide with an inorganic fullerene structure.
  • the solid lubricants (c) consist of particles with a diameter of between 80 and 220 nm, preferably between 100 and 200 nanometers.
  • the grease composition according to the invention advantageously contains at least one anti-wear and / or extreme pressure additive (d) which is chosen from phosphoric, phosphorous, thiophosphoric or thiophosphorous acids, or their derivatives, dithiophosphates, preferentially zinc or molybdenum dithiophosphates, phosphorothionates, amine phosphates
  • d anti-wear and / or extreme pressure additive
  • the grease compositions according to the invention contain at least one anti-wear and / or extreme pressure additive (d) chosen from Zinc dithiophosphates of formula:
  • 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 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
  • the grease compositions according to one of the claims of the invention contain at least one antiwear and / or extreme pressure additive (d) is chosen from Molybdenum dithiophosphates of formula:
  • R5, R6, R7, R8 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to to 18 carbon atoms, optionally in combination with the above-mentioned anti-wear and / or extreme pressure additive, in particular the aforementioned Zinc dithiophosphates.
  • said metal soaps are simple fatty metal soaps comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or otherwise, and and / or complex metal soaps of one or more fatty acids comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or otherwise, in combination with one or more short chain hydrocarbon carboxylic acids comprising from 6 to 12 carbon atoms. carbon.
  • the metal fatty acid soaps are chosen from aluminum titanium soaps, or alkali and alkaline earth metals, preferably lithium, calcium, sodium, barium.
  • the grease compositions according to the invention contain at least one base oil (a) is an oil of synthetic origin, preferably chosen from polyalphaolefins
  • the base oil or the base oil mixture (a) of the grease compositions according to the invention has a kinematic viscosity at 40 ° C. according to ASTM D 445 of between 70 and 140 cSt, preferably between 90 and 100 cSt.
  • grease compositions according to the invention whose consistency according to ASTM D217 is between 265 and 385 tenths of a millimeter, preferably between 265 and 295, or between 310 and 340, or between 335 and 385 tenths of a millimeter. preferably between 310 and 340 tenths of millimeters.
  • the grease compositions according to the invention comprise:
  • the present invention also relates to the use of the aforementioned grease compositions in the constant velocity joints of motor vehicle transmissions.
  • the present invention also relates to a homokinetic joint containing a grease composition 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 VI 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, glycols, polybutene, polyalphaolefins (PAO).
  • synthetic oils such as certain esters, silicones, glycols, polybutene, polyalphaolefins (PAO).
  • 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 polyoaplphafine (PAO) type are present.
  • 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 40 and 140 cSt, preferably between 90 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 invention can be thickened with the thickeners conventionally used in the grease industry, namely mainly the metal fatty acid soaps, and optionally inorganic thickeners such as bentonite or alumino silicates, or even polyureas.
  • the thickeners conventionally used in the grease industry, namely mainly the metal fatty acid soaps, and optionally inorganic thickeners such as bentonite or alumino silicates, or even polyureas.
  • 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, 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.
  • One or more metal compounds may be used in the greases according to the invention. So we can associate soaps lithium, combined with calcium soaps to a lesser extent. This has the advantage of improving the water resistance of greases.
  • the metal soaps are used at levels of the order of 5 to 20% by weight, preferably 8 to 15% by weight, typically 12% by weight in the greases according to the invention.
  • the amount of metallic soap (s) is generally adjusted to obtain 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 soap of fatty acids, simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of the 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 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.
  • the improvement of the friction properties observed during the introduction of inorganic fullerene friction modifiers in polyurea-thickened fats is less.
  • the greases according to the invention exclusively contain simple or complex fatty acid metal soaps as thickeners.
  • the solid lubricants used in the greases according to the invention are transition metal chalcogenides having an inorganic fullerene structure.
  • fullerene denotes a closed convex polyhedron nanostructure composed of carbon atoms.
  • Fullerenes are similar to graphite, composed of linked hexagonal ring sheets, but they contain pentagonal, and sometimes heptagonal rings, which prevent the structure from being flat.
  • EP 0580 019 also describes these structures and their method of synthesis.
  • inorganic fullerenes are generally attributable to their quasi-spherical structure and onions, which allows them, instead of adhering to contacts during friction, such as sheet structures, to exfoliate little by little or to mechanically deform, hence their recommendation as solid lubricants.
  • This spherical onion structure exists in all transition metal chalcogenides with an inorganic fullerene structure (see, for example, Tenne, R. Nature Nanotech, 2006, 1, 103 cited above).
  • the inorganic fullerenes with onion structure are thus preferred in the field of lubrication and in greases according to the invention. These are typically spheres of the order of 80 to 220 nm, and containing a few tens of concentric layers, typically 25 to 100 or 150 layers, or beyond.
  • the solid lubricants used in the greases according to the invention are chalcogenides of transition metals.
  • the transition metals may be, for example, tungsten, molybdenum, zirconium, hafnium, platinum, rhenium, titanium, tantalum, niobium, preferably molybdenum or tungsten, and the chalcogen may be, for example, sulfur, selenium or tellurium. , preferably sulfur or tellurium.
  • the transition metal chalcogenides may be for example MoS2, MoSe2, MoTe2, WS2, WSe2, ZrS2, ZrSe2, HfS2, HfSe2, PtS2, ReS2, ReSe2, TiS3, ZrS3, ZrSe3, HfS3, HfSe3, TiS2, TaS2, TaSe2.
  • these are dichalcogenides, preferentially WS2, WSe2,
  • chalcogenides may also contain several transition metals, such as, for example, the compounds described in application WO 2009/034572.
  • They can also be surface-grafted with polymers, for example polystyrene, polymethylmethacrylate, etc. to improve their dispersion, or phosphate groups, so as to reinforce their anti-wear action.
  • polymers for example polystyrene, polymethylmethacrylate, etc. to improve their dispersion, or phosphate groups, so as to reinforce their anti-wear action.
  • these compounds are often in the form of pastes containing about 75% by weight of fullerene metal chalcogenides and about 25% by weight of lubricating oil.
  • the weight percentages given in this application refer, unless otherwise stated, to metal chalcogenides alone.
  • the grease compositions according to the invention preferably comprise from 0.1 to 5% by weight of transition metal chalcogenides of fullerene structure, preferably from 0.2 to 2% by weight.
  • Organo phospho sulfur and / or organophosphorus compounds The phospho sulfur and / or phosphorus compounds used in the greases according to the invention are preferably chosen from the phospho-sulfur antiwear and extreme pressure additives used in the formulation of greases and lubricants.
  • thiophosphoric acid thiophosphorous acid
  • esters of these acids their salts
  • dithiophosphates particularly the dithiophosphates of zinc or molybdenum.
  • the organo phospho sulfur and organophosphorus compounds are better dispersed in the oily medium and more effective.
  • Inorganic compounds such as for example calcium phosphates, can also be used in fats, but rather as thickeners.
  • Examples which may be mentioned as examples of phospho-sulfur-containing anti-wear and extreme pressure additives are those containing from 1 to 3 sulfur atoms, such as monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, triethylthiophosphate, triphenylthiophosphate, trilaurylthiophosphate, monobutylthiophosphite, monooctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite and their salts.
  • sulfur atoms such as monobutyl
  • salts of thiophosphoric acid esters and thiophosphorous acid are those obtained by reaction with a nitrogen compound such as ammonia or an amine, for example amine phosphate, or zinc oxide or zinc chloride.
  • the phosphorothionates for example the triphenylphosphorothionates, more preferably those in which the phenyl groups are substituted with alkyl groups, are preferably used for preventing organophosphorus-containing wear.
  • organophospho sulfur-containing anti-wear compounds will be preferred in the greases according to the invention, since the presence of sulfur promotes the extreme pressure properties of the greases.
  • the lubricant compositions according to the present invention may also contain organophosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphorous acid mono, di and triesters and phosphoric acid, and their salts.
  • 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 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
  • R5, R6, R7, R8 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
  • 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, for example polyisobutene (PIB), at contents generally of between 5 and 10%, which imparts improved cohesiveness to fats, which is 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.
  • PIB polyisobutene
  • 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.
  • the mixture is then kneaded 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 fluid or semi-fluid greases with a consistency greater than 265 tenths of a millimeter, preferably between 265 and 385 tenths of a millimeter according to ASTM D217.
  • they are NLGI grade 0, 1 or 2, that is to say that their consistency is respectively between 335 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
  • Grease compositions containing various friction modifiers and / or organo phospho sulfur compounds are prepared from a grease foot comprising mineral and synthetic base oils thickened with complex lithium soap.
  • the composition of the mixture leading to this foot of fat 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.
  • the base oil mixture is set so that its viscosity at 40 ° C. according to ASTM D 445 is between 40 and 140 cSt, preferably between 90 and 100 cSt.
  • the weight% indicated is that of a paste composed of 75% by weight of nanometric WS2 fullerenes dispersed in a synthetic base oil (PAO 6).
  • Example 1 The greases prepared in Example 1 were evaluated by measuring their coefficient of friction on Cameron Plint cylinder / plane tribometer friction.
  • test conditions on the tribometer are as follows:
  • Grease temperature 75 ° C (representative of operating temperatures).
  • Mobile pin (cylinder) steel C with a roughness of 25 nm
  • the anti-wear properties of the greases prepared in Example 1 were evaluated using the 4-ball wear test, according to ASTM D2266.
  • the weight% indicated is that of a pulp composed of 75% by weight of nanoscale WS2 fullerenes dispersed in a synthetic base oil (PAO 6)

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Abstract

The invention relates to a fat composition comprising: (a) at least one synthetic or natural mineral-based oil, (b) a thickener, (c) at least one solid lubricant consisting of at least one transition metal chalcogenide having an inorganic fullerene structure, and (d) at least one anti-wear and/or extreme pressure organophosphate and/or organophosphosulfate additive. The invention also relates to the use of a fat composition as defined above in homokinetic joints of motor vehicle transmissions. The invention relates to a homokinetic joint containing such a fat.

Description

COMPOSITION DE GRAISSE  FAT COMPOSITION
La présente invention est relative à des compositions de graisse à bas coefficient de friction, notamment utilisables dans les joints homocinétiques qui sont utilisés dans les lignes de transmission des véhicules à moteur. The present invention relates to low friction coefficient grease compositions, particularly for use in constant velocity joints which are used in transmission lines of motor vehicles.
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 non seulement avoir un effet anti usure, mais également avoir un faible coefficient de friction afin de réduire ou empêcher les bruits, les vibrations et les à-coups.  Thus, the greases used in constant velocity joints must not only have an anti-wear effect, but also have 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.  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.
La demande EP 0435 745 décrit, par exemple, une graisse pour joints homocinétiques comprenant une huile minérale, un épaississant de type polyurée, de 0,5 à 5 % en masse de dithiophosphate de molybdène ( MoDTP) et 0,5 à 5 % en masse de dithiocarbamate de molybdène (MoDTC) à titre de modificateur de friction ( MF), et 0,5 à 10 % en masse de ZnDTP comme agent EP, et 0,5 à 60 % d'un copolymère d'ethylène et d'alpha oléfine branchée. The application EP 0435 745 describes, for example, a homokinetic joint grease comprising a mineral oil, a polyurea thickener, 0.5 to 5% by weight of molybdenum dithiophosphate (MoDTP) and 0.5 to 5% by weight. mass of Molybdenum dithiocarbamate (MoDTC) as a friction modifier (MF), and 0.5 to 10% by weight of ZnDTP as EP agent, and 0.5 to 60% of a copolymer of ethylene and alpha olefin connected.
Le brevet EP 0708 172 décrit également 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.  EP 0708 172 also describes a low-friction grease for homokinetic joints comprising a base oil, a simple or complex lithium soap thickener, one or more organic components containing molybdenum, of the MoDTC or MoDTP type, at least one zinc dithiophosphate, a metal-free phospho-sulfur extreme pressure agent, a calcium salt of oxidized wax, petroleum sulfonate or aromatic alkylsulfonates.
Le brevet FR 1 421 105 décrit ainsi l'utilisation, pour abaisser le coefficient de friction des graisses, de produits solides lubrifiants à structure cristalline feuilletée en combinaison avec des sels métalliques d'acides oxygénés du phosphore.  Patent FR 1 421 105 thus describes the use, for lowering the coefficient of friction of greases, of lubricant solids with a laminated crystalline structure in combination with metal salts of oxygenated phosphorus acids.
La demande WO 2007/085643 décrit des compositions de graisse à bas coefficient de friction pour joints homocinétiques comprenant une huile de base, un ou plusieurs épaississants de type thiourée, 0,1 à 5% en poids de disulfure de tungstène sous forme de particules ayant une taille moyenne de moins de 10 μηι (tanmikB commercialisé par Nippon Lubricant Ltd), et 0,1 à 5% en poids d'un ou plusieurs dithiophosphates de zinc et/ou dithiocarbamate de molybdène.  WO 2007/085643 discloses low friction coefficient grease compositions for homokinetic joints comprising a base oil, one or more thiourea type thickeners, 0.1 to 5% by weight of particulate tungsten disulfide having an average size of less than 10 μηι (tanmikB marketed by Nippon Lubricant Ltd), and 0.1 to 5% by weight of one or more zinc dithiophosphates and / or molybdenum dithiocarbamate.
US-P-5,516,439 décrit une composition de graisse comprenant (a) une huile de base, (b) un épaississant à base de lithium, (c) un composé de molybdène qui est un dithiophosphate de molybdène ou un dithiocarbamate de molybdène, (d) un dithiophosphate de zinc, (e) un sel métallique.  US-P-5,516,439 discloses a grease composition comprising (a) a base oil, (b) a lithium-based thickener, (c) a molybdenum compound which is a molybdenum dithiophosphate or a molybdenum dithiocarbamate, (d) ) a zinc dithiophosphate, (e) a metal salt.
Il est également connu d'employer, comme modificateurs de frottement, des lubrifiants solides tels que le bisulfure de molybdène (MoS2) ou de tungstène (WS2) sous forme de feuillet ou sous forme de fullerène pour abaisser le coefficient de frottement des graisses.  It is also known to employ, as friction modifiers, solid lubricants such as molybdenum disulfide (MoS 2) or tungsten (WS 2) in the form of a sheet or in the form of fullerene to lower the coefficient of friction of greases.
Certaines publications font état de l'utilisation de dichalcogénures métalliques sous forme de fullerènes inorganiques pour abaisser le coefficient de frottement et améliorer les propriétés anti usure d'huiles lubrifiantes et de graisse.  Some publications mention the use of metal dichalcogenides in the form of inorganic fullerenes to lower the coefficient of friction and improve the anti-wear properties of lubricating oils and grease.
La publication « Fullerène like WS2 Nanoparticles : superior lubricants for The publication "Fullerene like WS2 Nanoparticles: superior lubricants for
Harsh Conditions », par Lev Rapoport , Nieles Fleischer, Reshef Tenne Adv. Mat. 2003, 15, 651 -655 compare ainsi les propriétés de friction d'une graisse de référence constituée d' huile de base épaissie au Lithium, puis additivées de WS2 feuillet et enfin de WS2 fullerène. Harsh Conditions ", by Lev Rapoport, Fleischer Nieles, Reshef Tenne Adv. Mast. 2003 15, 651-655 thus compares the friction properties of a reference grease consisting of Lithium thickened base oil, then additive of WS2 slip and finally WS2 fullerene.
La publication « Modification of contact surfaces by fullerène -like solid lubricant nanoparticules », par L. Rapoport, V. Leshchinski, Yu. Volovik, M. Lvovsky, O. Nepomnyashchy, Y. Feldman, R. Popovitz-Biro, R. Tenne, Surface and Coating Technology 163-164 (2003) 405-412, effectue des comparaisons des mêmes produits au titre de leurs propriétés anti usure.  The publication "Modification of contact surfaces by fullerene -like solid lubricant nanoparticles", by L. Rapoport, V. Leshchinski, Yu. Volovik, M. Lvovsky, O. Nepomnyashchy, Y. Feldman, R. Popovitz-Biro, R. Tenne Surface and Coating Technology 163-164 (2003) 405-412 compares the same products for their anti-wear properties.
Toutefois, aucune combinaison spécifique de dichalcogenures métalliques sous forme fullerène inorganique avec d'autres composants des graisses n'est divulguée. En particulier, les effets des interactions des chalcogénures métalliques de type fullerènes inorganiques avec les épaississants, et les additifs anti usure, et éventuellement extrême pression, nécessaires à la formulation des graisses commerciales ne sont pas divulgués dans l'art antérieur. Ces effets pourraient se révéler bénéfiques ou antagonistes.  However, no specific combination of metal dichalcogenides in inorganic fullerene form with other components of the fats is disclosed. In particular, the effects of inorganic fullerene-type metal chalcogenide interactions with thickeners, and anti-wear, and possibly extreme pressure additives, required for formulating commercial greases are not disclosed in the prior art. These effects could be beneficial or antagonistic.
II existe donc toujours un besoin pour des graisses formulées ayant un coefficient de friction encore plus bas que les graisses de l'art antérieur. Il existe également un besoin pour de telles graisses à très bas coefficient de friction, présentant simultanément des propriétés anti usure équivalentes ou améliorées par rapport aux graisses de l'art antérieur.  There is therefore still a need for formulated fats having a coefficient of friction even lower than the greases of the prior art. There is also a need for such greases with a very low coefficient of friction, simultaneously having equivalent or improved anti-wear properties compared to the greases of the prior art.
De façon surprenante, la demanderesse a mis en évidence un effet synergique entre des modificateurs de frottement solides de chalocogénures de métaux de transition sous forme de fullerènes inorganiques, avec des composés anti usure et extrême pression de type organophospho soufrés, dans des graisses épaissies notamment aux savons de lithium.  Surprisingly, the Applicant has demonstrated a synergistic effect between solid friction modifiers of transition metal chalocogenides in the form of inorganic fullerenes, with anti-wear and extreme pressure compounds of organophospho-sulfur type, in thickened greases, especially in lithium soaps.
La combinaison de ces composés dans des graisses permet d'abaisser le coefficient de frottement desdites graisses bien en dessous en dessous de celui des graisses contenant individuellement l'un ou l'autre de ces composés.  The combination of these compounds in fats makes it possible to lower the coefficient of friction of said fats well below that of fats containing individually one or other of these compounds.
Les performances anti usure de ces graisses sont maintenues par rapport aux graisses connues contenant comme modificateurs de frottement des composés organiques au molybdène et comme additifs anti usure des composés organo phosphorés ou organophospho soufrés. Brève description de l'invention : The anti-wear performance of these greases is maintained with respect to known greases containing as friction modifiers of molybdenum organic compounds and as anti-wear additives for organophosphorus or organophospho sulfur compounds. Brief description of the invention
La présente invention est relative à des compositions de graisse comprenant :  The present invention relates to fat compositions comprising:
(a) une ou plusieurs huiles de base minérales, synthétiques ou naturelles, (b) un épaississant,  (a) one or more mineral, synthetic or natural base stocks, (b) a thickener,
(c) au moins un lubrifiant solide constitué d'un ou plusieurs chalcogénures de métaux de transition à structure de fullerène inorganique,  (c) at least one solid lubricant consisting of one or more transition metal chalcogenides with an inorganic fullerene structure,
(d) un ou plusieurs additifs anti usure et/ou extrême pression organophosphorés et/ou organo phospho soufrés.  (d) one or more organophosphorus and / or organo phospho sulfur wear and / or extreme pressure additives.
Préférentiellement, dans les compositions de graisse selon l'invention, l'épaississant (b) est composé majoritairement d'au moins un savon métallique d'acide gras.  Preferably, in the grease compositions according to the invention, the thickener (b) is composed mainly of at least one metal soap of fatty acid.
Encore plus préférentiellement, le(s) savon(s) métallique(s) d'acide gras constitue au moins 50 %, préférentiellement au moins 80 % en poids de l'épaississant (b) dans lesdites compositions.  Even more preferably, the metallic soap (s) of fatty acid constitutes at least 50%, preferably at least 80% by weight of the thickener (b) in said compositions.
Selon un mode de réalisation, un ou plusieurs chalcogénures de métaux de transition à structure de fullerène inorganique utilisés dans les compositions de graisse selon l'invention sont greffés en surface par des groupements phosphates inorganiques.  According to one embodiment, one or more transition metal chalcogenides having an inorganic fullerene structure used in the grease compositions according to the invention are grafted onto the surface by inorganic phosphate groups.
Préférentiellement, dans les compositions de graisse selon l'invention, le chalcogène d'au moins un lubrifiant solide (c) est choisi parmi S, Se, Te.  Preferably, in the grease compositions according to the invention, the chalcogen of at least one solid lubricant (c) is selected from S, Se, Te.
Préférentiellement, dans les compositions de graisse selon l'invention, les métaux de transition d'au moins un lubrifiant solide (c) sont choisis parmi Mo, W, Zr, Preferably, in the grease compositions according to the invention, the transition metals of at least one solid lubricant (c) are chosen from Mo, W, Zr,
Hf, Pt, Re, Ti, Ta, Nb, préférentiellement Mo et W. Hf, Pt, Re, Ti, Ta, Nb, preferably Mo and W.
Selon un mode particulièrement préféré, dans les compositions de graisse selon l'invention, au moins un lubrifiant solide (c) est un dichalcogenure de métaux de transition, préférentiellement le bisulfure de Molybdène MoS2 ou le bisulfure de tungstène WS2 à structure fullerène inorganique.  According to a particularly preferred embodiment, in the grease compositions according to the invention, at least one solid lubricant (c) is a transition metal dichalcogenide, preferably Molybdenum disulfide MoS2 or WS2 tungsten bisulfide with an inorganic fullerene structure.
Préférentiellement, dans les compositions de graisse selon l'invention, les lubrifiants solides (c) sont constitués de particules de diamètre compris entre 80 et 220 nm, préférentiellement entre 100 et 200 nano mètres.  Preferably, in the grease compositions according to the invention, the solid lubricants (c) consist of particles with a diameter of between 80 and 220 nm, preferably between 100 and 200 nanometers.
Les composition de graisse selon l'invention contiennent avantageusement au moins un additif anti/usure et/ou extrême pression (d) qui est choisi parmi les esters des acides phosphorique, phosphoreux, thiophosphorique ou thiophosphoreux, ou leurs dérivés, les dithiophosphates, préférentiellement les dithiophosphates de zinc ou de molybdène, les phosphorothionates, les phosphates d'amines The grease composition according to the invention advantageously contains at least one anti-wear and / or extreme pressure additive (d) which is chosen from phosphoric, phosphorous, thiophosphoric or thiophosphorous acids, or their derivatives, dithiophosphates, preferentially zinc or molybdenum dithiophosphates, phosphorothionates, amine phosphates
Selon un mode particulièrement préféré, les compositions de graisse selon l'invention contiennent au moins un additif anti/usure et/ou extrême pression (d) choisi parmi les dithiophosphates de Zinc de formule :  According to a particularly preferred embodiment, the grease compositions according to the invention contain at least one anti-wear and / or extreme pressure additive (d) chosen from Zinc dithiophosphates of formula:
(R10)(R20)PS2 ZnS2P(R30)(R40), où  (R10) (R20) PS2 ZnS2P (R30) (R40), where
RI , R2, R3, R4 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.  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 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
Selon un autre mode de réalisation, les composition de graisse selon l'une revendications l'invention contiennent où au moins un additif anti/usure et/ou extrême pression (d) est choisi parmi les dithiophosphates de Molybdène de formule :  According to another embodiment, the grease compositions according to one of the claims of the invention contain at least one antiwear and / or extreme pressure additive (d) is chosen from Molybdenum dithiophosphates of formula:
(R50)(R60)SPS(MoS2)2 SPS(R70)(R80), où  (R50) (R60) SPS (MoS2) 2 SPS (R70) (R80), where
R5, R6, R7, R8 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone, en combinaison éventuelle avec les un additif anti/usure et/ou extrême pression précités, en particulier les dithiophosphates de Zinc précités.  R5, R6, R7, R8 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to to 18 carbon atoms, optionally in combination with the above-mentioned anti-wear and / or extreme pressure additive, in particular the aforementioned Zinc dithiophosphates.
Préférentiellement, dans les compositions de graisse selon l'invention épaissies aux savons métalliques d'acide gras, lesdits savons métalliques sont des savons métalliques simples d'acides gras comprenant de 14 à 28 atomes de carbone, saturés ou non, hydroxylés ou non, et/ou des savons métalliques complexes d'un ou plusieurs acides gras comprenant de 14 à 28 atomes de carbone, saturés ou non, hydroxylés ou non, en combinaison avec un ou plusieurs acides carboxyliques à chaîne hydrocarbonée courte comprenant au de 6 à 12 atomes de carbone.  Preferably, in the grease compositions according to the invention, which are thickened with fatty acid metal soaps, said metal soaps are simple fatty metal soaps comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or otherwise, and and / or complex metal soaps of one or more fatty acids comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or otherwise, in combination with one or more short chain hydrocarbon carboxylic acids comprising from 6 to 12 carbon atoms. carbon.
Préférentiellement dans lesdites compositions de graisse selon l'invention, les savons métalliques d'acides gras sont choisis parmi les savons de titane, d'aluminium, ou de métaux alcalins et alcalino terreux, de préférence le lithium, le calcium, le sodium, le baryum. Preferentially in said grease compositions according to the invention, the metal fatty acid soaps are chosen from aluminum titanium soaps, or alkali and alkaline earth metals, preferably lithium, calcium, sodium, barium.
Selon un mode préféré, les composition de graisse selon l'invention contiennent au moins une huile de base (a) est une huile d'origine synthétique, préférentiellement choisie parmi les polyalphaoléfïnes  According to a preferred embodiment, the grease compositions according to the invention contain at least one base oil (a) is an oil of synthetic origin, preferably chosen from polyalphaolefins
Préférentiellement, l'huile de base ou le mélange d'huiles de base (a) des compositions de graisse selon l'invention, a une viscosité cinématique à 40 °C selon la norme ASTM D 445 comprise entre 70 et 140 cSt, préférentiellement entre 90 et 100 cSt.  Preferably, the base oil or the base oil mixture (a) of the grease compositions according to the invention has a kinematic viscosity at 40 ° C. according to ASTM D 445 of between 70 and 140 cSt, preferably between 90 and 100 cSt.
On préférera formuler des composition de graisse selon l'invention dont la consistance selon la norme ASTM D217, est comprise entre 265 et 385 dixièmes de millimètres, préférentiellement entre 265 et 295, ou entre 310 et 340, ou entre 335 et 385 dixièmes de millimètres, préférentiellement comprise entre 310 et 340 dixièmes de millimètres.  It will be preferred to formulate grease compositions according to the invention whose consistency according to ASTM D217 is between 265 and 385 tenths of a millimeter, preferably between 265 and 295, or between 310 and 340, or between 335 and 385 tenths of a millimeter. preferably between 310 and 340 tenths of millimeters.
Préférentiellement, les compositions de graisse selon l'invention comprennent : Preferably, the grease compositions according to the invention comprise:
• de 70 à 94,8 % en masse d'une ou plusieurs huiles de base (a)From 70 to 94.8% by weight of one or more base oils (a)
• de 5 à 20 % en masse d'un ou plusieurs épaississants (b)From 5 to 20% by weight of one or more thickeners (b)
• de 0,1 à 5 % d'un ou plusieurs lubrifiant solide (c)From 0.1 to 5% of one or more solid lubricants (c)
• de 0,1 à 5% d'un ou plusieurs additifs anti usure et/ou extrême pression organophosphorés et/ou organo phospho soufrés (d). From 0.1 to 5% of one or more organophosphorus and / or organophospho-sulfur anti-wear and / or extreme pressure additives (d).
La présente invention est également relative à l'utilisation des compositions de graisse précitées dans les joints homocinétiques des transmissions de véhicules à moteur.  The present invention also relates to the use of the aforementioned grease compositions in the constant velocity joints of motor vehicle transmissions.
La présente invention est également relative à joint homocinétique contenant une composition de graisse telle que décrite précédemment. The present invention also relates to a homokinetic joint containing a grease composition as described above.
DESCRIPTION DETAILLEE : DETAILED DESCRIPTION :
Huile de base lubrifiantes Lubricant base oil
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 VI 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 VI 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, glycols, polybutène, polyalphaoléfines (PAO).  The base oils of the grease compositions according to the present invention may also be synthetic oils, such as certain esters, silicones, glycols, polybutene, polyalphaolefins (PAO).
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 polyoaplphaléfînes (PAO) sont présentes. 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 polyoaplphafine (PAO) type are present. 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 40 et 140 cSt, préférentiellement entre 90 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 40 and 140 cSt, preferably between 90 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 Thickening
Les graisses selon l'invention peuvent être épaissies avec les épaississants utilisés conventionnellement dans l'industrie des graisses, à savoir principalement les savons métalliques d'acides gras, et éventuellement des épaississants inorganiques tels que la bentonite ou les alumino silicates, ou encore les polyurées. The greases according to the invention can be thickened with the thickeners conventionally used in the grease industry, namely mainly the metal fatty acid soaps, and optionally inorganic thickeners such as bentonite or alumino silicates, or even polyureas.
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, 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.  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.
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. So we can associate soaps lithium, 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, typiquement 12 % 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 0, de grade 1 ou de grade 2 selon la classification NLGI.  The metal soaps are used at levels of the order of 5 to 20% by weight, preferably 8 to 15% by weight, typically 12% by weight in the greases according to the invention. The amount of metallic soap (s) is generally adjusted to obtain 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. By this is meant that the metal soap of fatty acids, simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of the 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.
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 polyurée. L'amélioration des propriétés de frottement constatée lors de l'introduction de modificateurs de frottement de type fullerène inorganique dans les graisses épaissies aux polyurées est moindre.  Preferably, the greases according to the invention are free of polyurea thickeners. The improvement of the friction properties observed during the introduction of inorganic fullerene friction modifiers in polyurea-thickened fats is less.
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.
Lubrifiant solide Solid lubricant
Les lubrifiants solides utilisés dans les graisses selon l'invention sont des chalcogénures de métaux de transition à structure fullerène inorganique. Initialement, le terme fullerène désigne une nanostructure de polyèdre convexe fermé, composée d'atomes de carbone. Les fullerènes sont similaires au graphite, composé de feuilles d'anneaux hexagonaux liées, mais ils contiennent des anneaux pentagonaux, et parfois heptagonaux, qui empêchent la structure d'être plate. The solid lubricants used in the greases according to the invention are transition metal chalcogenides having an inorganic fullerene structure. Initially, the term fullerene denotes a closed convex polyhedron nanostructure composed of carbon atoms. Fullerenes are similar to graphite, composed of linked hexagonal ring sheets, but they contain pentagonal, and sometimes heptagonal rings, which prevent the structure from being flat.
Dans la présente demande, on distingue les fullerènes, structures fermées, des nanotubes, structures ouvertes formées sur le même principe.  In the present application, there are fullerenes, closed structures, nanotubes, open structures formed on the same principle.
Des études sur les structures de type fullerène ont montré que cette structure n'était pas limitée aux matériaux carbonés, mais était susceptible de se produire dans toutes les nanoparticules de matériaux sous forme de feuillets, en particulier les chalcogénures de métaux de transition.  Studies of fullerene-type structures have shown that this structure was not limited to carbonaceous materials, but was likely to occur in all nanoparticles of sheet-like materials, particularly transition metal chalcogenides.
Ces structures sont analogues à celle des fullerènes de carbone et sont nommées fullerènes inorganiques ou « Inorganic Fullerène like materials », encore désignés par « IF ».  These structures are similar to that of carbon fullerenes and are called inorganic fullerenes or "Inorganic Fullerene like materials", also referred to as "IF".
Il existe une abondante littérature décrivant la structure et les procédés de synthèse de ces fullerènes inorganiques, notamment :  There is an abundant literature describing the structure and synthesis processes of these inorganic fullerenes, including:
- Tenne, R., Margulis, L., Genut M. Hodes, G. Nature 1992, 360, 444,  - Tenne, R., Margulis, L., Gen. M. Hodes, G. Nature 1992, 360, 444,
- Feldman, Y.,Wasserman,E.,Srolovitz, D.J. & Tenne, R. Science 1995, 267, 222, Feldman, Y., Wasserman, E., Srolovitz, D.J. & Tenne, R. Science 1995, 267, 222,
- Tenne, R. Nature Nanotech. 2006, 1, 103. - Tenne, R. Nature Nanotech. 2006, 1, 103.
Le brevet EP 0580 019 décrit également ces structures et leur procédé de synthèse. EP 0580 019 also describes these structures and their method of synthesis.
Ces structures fermées ont le plus souvent une forme rappelant celle d'une sphère, plus ou moins parfaite selon les procédés de synthèse utilisés, constituées de plusieurs couches concentriques (structure en « onions » ou « polyèdre emboîté »).  These closed structures most often have a shape reminiscent of a sphere, more or less perfect according to the synthetic processes used, consisting of several concentric layers (structure "onions" or "polyhedron nested").
Les propriétés tribologiques des fullerènes inorganiques sont généralement attribuables à leur structure quasi sphérique et en oignons, ce qui leur permet, au lieu d'adhérer aux contacts lors de frottements, comme les structures en feuillet, de s'exfolier petit à petit ou de se déformer mécaniquement, d'où leur préconisation comme lubrifiants solides. Cette structure sphérique en oignon existe chez tous les chalcogénures de métaux de transition à structure fullerène inorganique (voir par exemple Tenne, R. Nature Nanotech. 2006, 1, 103 cité supra). Les fullerenes inorganiques à structure oignons sont ainsi préférées dans le domaine de la lubrification et dans les graisses selon l'invention. Ce sont typiquement des sphères de l'ordre de 80 à 220 nm, et contenant quelques dizaines de couches concentriques, typiquement de 25 à 100 ou 150 couches, ou au-delà. The tribological properties of inorganic fullerenes are generally attributable to their quasi-spherical structure and onions, which allows them, instead of adhering to contacts during friction, such as sheet structures, to exfoliate little by little or to mechanically deform, hence their recommendation as solid lubricants. This spherical onion structure exists in all transition metal chalcogenides with an inorganic fullerene structure (see, for example, Tenne, R. Nature Nanotech, 2006, 1, 103 cited above). The inorganic fullerenes with onion structure are thus preferred in the field of lubrication and in greases according to the invention. These are typically spheres of the order of 80 to 220 nm, and containing a few tens of concentric layers, typically 25 to 100 or 150 layers, or beyond.
Les lubrifiants solides utilisés dans les graisses selon l'invention sont des chalcogenures de métaux de transition.  The solid lubricants used in the greases according to the invention are chalcogenides of transition metals.
Les métaux de transition peuvent être par exemple le tungstène, le molybdène, zirconium, hafnium, platine, rhénium, titane, tantale, niobium, préférentiellement le molybdène ou le tungstène, et le chalcogène peut être par exemple le soufre, le sélénium, le tellure, préférentiellement le soufre ou le tellure.  The transition metals may be, for example, tungsten, molybdenum, zirconium, hafnium, platinum, rhenium, titanium, tantalum, niobium, preferably molybdenum or tungsten, and the chalcogen may be, for example, sulfur, selenium or tellurium. , preferably sulfur or tellurium.
Les chalcogénures de métaux de transition peuvent être par exemple MoS2, MoSe2, MoTe2, WS2, WSe2, ZrS2, ZrSe2, HfS2, HfSe2, PtS2, ReS2, ReSe2, TiS3, ZrS3, ZrSe3, HfS3, HfSe3, TiS2, TaS2, TaSe2, NbS2, NbSe2, NbTe2, étudiés pour leurs propriétés tribologiques.  The transition metal chalcogenides may be for example MoS2, MoSe2, MoTe2, WS2, WSe2, ZrS2, ZrSe2, HfS2, HfSe2, PtS2, ReS2, ReSe2, TiS3, ZrS3, ZrSe3, HfS3, HfSe3, TiS2, TaS2, TaSe2. NbS2, NbSe2, NbTe2, studied for their tribological properties.
Préférentiellement, ce sont des dichalcogenures, préférentiellement WS2, WSe2, Preferentially, these are dichalcogenides, preferentially WS2, WSe2,
MoS2, MoSe2. MoS2, MoSe2.
Ces chalcogenures peuvent également contenir plusieurs métaux de transition, tels que par exemple les composés décrits dans la demande WO 2009/034572.  These chalcogenides may also contain several transition metals, such as, for example, the compounds described in application WO 2009/034572.
Ils peuvent également être greffés en surface par des polymères, par exemple polystyrène, polyméthacrylate de méthyle ... pour améliorer leur dispersion, ou des groupements phosphate, de manière à renforcer leur action antiusure.  They can also be surface-grafted with polymers, for example polystyrene, polymethylmethacrylate, etc. to improve their dispersion, or phosphate groups, so as to reinforce their anti-wear action.
Commercialement, ces composés se présentent souvent sous forme de pâtes contenant environ 75 % en poids de chalcogenures métalliques de structure fullerène et environ 25 % en poids d'huile lubrifiante. Les pourcentages massiques indiqués dans la présente demande se réfèrent, sauf précision contraire, aux chalcogenures métalliques seuls.  Commercially, these compounds are often in the form of pastes containing about 75% by weight of fullerene metal chalcogenides and about 25% by weight of lubricating oil. The weight percentages given in this application refer, unless otherwise stated, to metal chalcogenides alone.
Les compositions de graisse selon l'invention comprennent préférentiellement de 0,1 à 5% en poids de chalcogenures de métaux de transition de structure fullerène, préférentiellement de 0,2 à 2 % en poids. Composés organo phospho soufrés et/ou organophosphorés Les composés phospho soufrés et/ou phosphorés utilisés dans les graisses selon l'invention sont préférentiellement choisis parmi les additifs anti usure et extrême pression phospho soufrés utilisés dans la formulation de graisses et de lubrifiants. The grease compositions according to the invention preferably comprise from 0.1 to 5% by weight of transition metal chalcogenides of fullerene structure, preferably from 0.2 to 2% by weight. Organo phospho sulfur and / or organophosphorus compounds The phospho sulfur and / or phosphorus compounds used in the greases according to the invention are preferably chosen from the phospho-sulfur antiwear and extreme pressure additives 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 ou de Molybdène.  These are for example and not limited to thiophosphoric acid, thiophosphorous acid, esters of these acids, their salts, and dithiophosphates, particularly the dithiophosphates of zinc or molybdenum.
Dans les graisses selon l'invention, on ne retiendra, notamment parmi les composés cités cidessus, comme additif anti usure, et éventuellement extrême pression, que les composés organo phospho soufrés et organophosphorés, mieux dispersés dans le milieu huileux et plus efficaces. Les composés inorganiques, tels que par exemple les phosphates de calcium, peuvent être également employés dans les graisses, mais plutôt en tant qu'épaississants.  In the greases according to the invention, particular mention will be made, especially among the compounds mentioned above, as an antiwear additive, and possibly extreme pressure, that the organo phospho sulfur and organophosphorus compounds, better dispersed in the oily medium and more effective. Inorganic compounds, such as for example calcium phosphates, can also be used in fats, but rather as thickeners.
On peut citer, à titre d'exemples d'additifs anti usure et extrême pression phospho soufrés, ceux qui comportent de 1 à 3 atomes de soufre, tels que le monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, trio ctylthiopho sphate , triphenylthiopho sphate , trilaurylthiopho sphate , monobutylthiophosphite, monooctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite et leurs sels.  Examples which may be mentioned as examples of phospho-sulfur-containing anti-wear and extreme pressure additives are those containing from 1 to 3 sulfur atoms, such as monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, triethylthiophosphate, triphenylthiophosphate, trilaurylthiophosphate, monobutylthiophosphite, monooctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite and their salts.
Des exemples de sels des esters de l'acide thiophosphorique et de l'acide thiophosphoreux sont ceux obtenus par réaction avec un composé azoté tels que l'ammoniac ou une aminé, par exemple les phosphate d'amine, ou l'oxyde de zinc ou le chlorure de zinc.  Examples of salts of thiophosphoric acid esters and thiophosphorous acid are those obtained by reaction with a nitrogen compound such as ammonia or an amine, for example amine phosphate, or zinc oxide or zinc chloride.
O n p ourra é g ale me nt emp lo yer , à t itre de c o mp o s é anti usure organophosphosoufré, les phosphorothionates, par exemple les triphenyl phosphorothionates, plus préférentiellement ceux où les groupements phenyls sont substitués par des groupements alkyl.  The phosphorothionates, for example the triphenylphosphorothionates, more preferably those in which the phenyl groups are substituted with alkyl groups, are preferably used for preventing organophosphorus-containing wear.
Les composés anti usure organophospho soufrés seront préférés dans les graisses selon l'invention, car la présence de soufre favorise les propriétés extrême pression des graisses. Les compositions lubrifiantes selon la présente invention peuvent également contenir des additifs anti usure et extrême- pression organophosphorés, tels que par exemple les phosphates d'alkyle ou phosphonates d'alkyle, les mono, di et triesters de l'acide phosphoreux et de l'acide phosphorique, et leurs sels. The organophospho sulfur-containing anti-wear compounds will be preferred in the greases according to the invention, since the presence of sulfur promotes the extreme pressure properties of the greases. The lubricant compositions according to the present invention may also contain organophosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphorous acid mono, di and triesters and phosphoric acid, and their salts.
On préférera en particulier les dithiophosphates de Zinc de formule :  Zinc dithiophosphates of formula:
(R10)(R20)PS2 ZnS2P(R30)(R40), où  (R10) (R20) PS2 ZnS2P (R30) (R40), where
RI , R2, R3, R4 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.  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 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
Une autre classe de composés préférés sont les dithiophosphates de Molybdène de formule :  Another class of preferred compounds are the molybdenum dithiophosphates of formula:
(R50)(R60)SPS(MoS2)2 SPS(R70)(R80), où  (R50) (R60) SPS (MoS2) 2 SPS (R70) (R80), where
R5, R6, R7, R8 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.  R5, R6, R7, R8 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
Ces différents composés peuvent être employés seuls ou en mélange dans les compositions de graisse selon l'invention. Leur % massique 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  These different compounds can be used alone or as a mixture in the grease compositions according to the invention. Their mass% 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.
Autre 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, par exemple des polyisobutène (PIB), à des teneurs généralement comprises entre 5 et 10%, qui confèrent une cohésivité améliorée aux 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. Procédé de préparation des graisses : The greases according to the invention may also contain polymers, for example polyisobutene (PIB), at contents generally of between 5 and 10%, which imparts improved cohesiveness to fats, which is 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. 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 1 10 °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 malaxe ensuite pendant un temps suffisant pour obtenir une composition de graisse homogène.  The mixture is then kneaded 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 fluides ou semi fluide, de consistance supérieure à 265 dixièmes de millimètre, préférentiellement comprises entre 265 et 385 dixièmes de millimètre selon ASTM D217. Préférentiellement, elles sont de grade NLGI 0, 1 ou 2, c'est-à-dire que leur consistance est respectivement comprise entre 335 et 385, ou 310 et 340, ou 265 et 295 dixièmes de millimètres selon ASTM D217. The greases according to the invention are preferably fluid or semi-fluid greases with a consistency greater than 265 tenths of a millimeter, preferably between 265 and 385 tenths of a millimeter according to ASTM D217. Preferably, they are NLGI grade 0, 1 or 2, that is to say that their consistency is respectively between 335 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
Exemples Examples
Exemple 1 : préparation des compositions de graisse Example 1: Preparation of fat compositions
On prépare des compositions de graisse contenant divers modificateurs de friction et/ou composé organo phospho soufrés, à partir d'un pied de graisse comprenant des huiles de bases minérales et synthétiques, épaissies au savon de Lithium complexe. La composition du mélange conduisant à ce 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.  Grease compositions containing various friction modifiers and / or organo phospho sulfur compounds are prepared from a grease foot comprising mineral and synthetic base oils thickened with complex lithium soap. The composition of the mixture leading to this foot of fat 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.
Tableau 1 : composition du pied de graisse  Table 1: fat foot composition
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 40 et 140 cSt, préférentiellement entre 90 et 100 cSt.  The base oil mixture is set so that its viscosity at 40 ° C. according to ASTM D 445 is between 40 and 140 cSt, preferably between 90 and 100 cSt.
Les teneurs en acides gras et Lithine indiquées conduisent, après formation in situ, à des teneurs en savon dans le pied de graisse qui sont de 9,2 % en hydroxystéarate de Lithium et 1 ,91 % en azélaate de Lithium. Les compositions massiques des graisses sont données dans le tableau 2 : The contents of fatty acids and Lithine indicated lead, after in situ formation, to levels of soap in the foot of fat which are 9.2% lithium hydroxystearate and 1.91% lithium azela- late. The mass compositions of fats are given in Table 2:
1 : hors de l'invention  1: outside the invention
*le % massique indiqué est celui d'une pâte composée de 75 % en poids de fullerènes de WS2 nanométriques dispersés dans une huile de base synthétique (PAO 6).  the weight% indicated is that of a paste composed of 75% by weight of nanometric WS2 fullerenes dispersed in a synthetic base oil (PAO 6).
Exemple 2 : comparaison des propriétés en friction des graisses préparées.Example 2 Comparison of the Friction Properties of Prepared Greases
Les graisses préparées dans l'exemple 1 ont été évaluées en mesurant leur coefficient de friction sur tribomètre Cameron Plint cylindre/plan. The greases prepared in Example 1 were evaluated by measuring their coefficient of friction on Cameron Plint cylinder / plane tribometer friction.
Les conditions d'essais sur le tribomètre sont les suivantes :  The test conditions on the tribometer are as follows:
Charge : 50 - 100 - 150 - 200 N  Charge: 50 - 100 - 150 - 200 N
Température de la graisse: 75 °C (représentatif des températures en service). Pion mobile (cylindre) : acier C de rugosité 25 nm  Grease temperature: 75 ° C (representative of operating temperatures). Mobile pin (cylinder): steel C with a roughness of 25 nm
Vitesse de déplacement : 5 et 15 mm/s  Movement speed: 5 and 15 mm / s
Paliers : 50 N, 400 secondes à 5 mm/s  Bearings: 50 N, 400 seconds to 5 mm / s
50 N, 200 secondes à 15 mm s  50 N, 200 seconds to 15 mm s
100 N, 100 secondes à 5 mm s et 100 secondes à 15 mm/s 150 N, 100 secondes à 5 mm/s et 100 secondes à 15 mm/s 200 N, 100 secondes à 5 mm/s et 100 secondes à 15 mm/s Les résultats de ces essais sont présentés dans le tableau 3 ci-dessous. Les valeurs de coefficient de frottement correspondent à la moyenne sur les 40 dernières secondes de chaque palier. 100 N, 100 seconds at 5 mm s and 100 seconds at 15 mm / s 150 N, 100 seconds at 5 mm / s and 100 seconds at 15 mm / s 200 N, 100 seconds at 5 mm / s and 100 seconds at 15 mm / s The results of these tests are presented in Table 3 below. The coefficient of friction values are the average over the last 40 seconds of each level.
Tableau 3 : coefficient de frottement sur tribomètre Cameron Plint  Table 3: Cameron Plint tribometer friction coefficient
L'ajout de WS2 comme modificateur de friction dans une graisse Li Complexe, en remplacement du Mo DTC et en l'absence de DTPZn, permet un abaissement du coefficient de friction (cf. comparaison des graisses A et D à iso teneur en métal). The addition of WS2 as friction modifier in Li Complex grease, replacing Mo DTC and in the absence of DTPZn, allows a lowering of the coefficient of friction (see comparison of greases A and D with iso metal content) .
L'effet positif du WS2 fullerène sur le coefficient de frottement est moindre si on le substitue au DTCMo dans une graisse épaissie aux polyurées.  The positive effect of WS2 fullerene on the coefficient of friction is lower if it is substituted for DTCMo in a polyurea-thickened fat.
L'abaissement du coefficient de frottement constaté, dans une graisse Lithium complexe, avec un modificateur de frottement WS2 de type fullerène est toutefois nettement plus significatif lorsqu'il est utilisé en combinaison avec un additif organo phospho soufré, ici un DTPZn.  The lowering of the coefficient of friction observed in a complex lithium grease with a fullerene type WS2 friction modifier is, however, much more significant when it is used in combination with an organo-phospho-sulfur additive, here a DTPZn.
Exemple 3 : comparaison des propriétés en usure des graisses préparées.Example 3 Comparison of the Wear Properties of Prepared Greases
Les propriétés anti usure des graisses préparées dans l'exemple 1 ont été évaluées à l'aide du test 4 billes usure, selon la norme ASTM D2266. The anti-wear properties of the greases prepared in Example 1 were evaluated using the 4-ball wear test, according to ASTM D2266.
Dans ce test, on mesure l'usure, en millimètres : plus la valeur est faible, meilleure sont les propriétés anti usure. In this test, wear is measured in millimeters: the lower the value, the better the anti-wear properties.
(calculée, en ppm)  (calculated in ppm)
"ableau 4 : résultats en usure " ableau 4: wear results
*le % massique indiqué est celui d'une pâte composée de 75 % en poids de 5 fullerènes de WS2 nanométriques dispersés dans une huile de base synthétique (PAO 6) the weight% indicated is that of a pulp composed of 75% by weight of nanoscale WS2 fullerenes dispersed in a synthetic base oil (PAO 6)
On constate, que les performances de la graisse D, où des fullerènes inorganiques ont été substitués aux additifs anti usure et modificateurs de friction, a des performances en usure très médiocres. En revanche, les graisses B et C présentent des performances très bonnes.  It can be seen that the performance of the D-grease, where inorganic fullerenes have been substituted for the anti-wear additives and friction modifiers, has very poor wear performance. On the other hand, greases B and C have very good performances.
10  10

Claims

REVENDICATIONS
1. Composition de graisse comprenant : A fat composition comprising:
(a) une ou plusieurs huiles de base minérales, synthétiques ou naturelles, (b) un épaississant,  (a) one or more mineral, synthetic or natural base stocks, (b) a thickener,
(c) au moins un lubrifiant solide constitué d'un ou plusieurs chalcogénures de métaux de transition à structure de fullerène inorganique,  (c) at least one solid lubricant consisting of one or more transition metal chalcogenides with an inorganic fullerene structure,
(d) un ou plusieurs additifs anti usure et/ ou extrême pression organophosphorés et/ou organo phospho soufrés.  (d) one or more organophosphorus and / or organo phospho sulfur wear and / or extreme pressure additives.
2. Composition de graisse selon la revendication 1 où l'épaississant (b) est composé majoritairement d'au moins un savon métallique d'acide gras,  2. Fat composition according to claim 1, wherein the thickener (b) is composed mainly of at least one fatty acid metal soap,
3. Composition selon l'une des revendications 1 à 2 où le(s) savon(s) métallique(s) d'acide gras constitue au moins 50 %, préférentiellement au moins 80 % en poids de l'épaississant (b) dans ladite composition.  3. Composition according to one of claims 1 to 2 wherein the soap (s) metal (s) of fatty acid constitutes at least 50%, preferably at least 80% by weight of the thickener (b) in said composition.
4. Composition de graisse selon l'une des revendications 1 à 3 où un ou plusieurs chalcogenures de métaux de transition à structure de fullerène inorganique sont greffés en surface par des groupements phosphates inorganiques.  4. Grease composition according to one of claims 1 to 3 wherein one or more transition metal chalcogenides inorganic fullerene structure are grafted at the surface by inorganic phosphate groups.
5. Composition de graisse selon l'une des revendications 1 à 4 où le chalcogène d'au moins un lubrifiant solide (c) est choisi parmi S, Se, Te.  5. Grease composition according to one of claims 1 to 4 wherein the chalcogen of at least one solid lubricant (c) is selected from S, Se, Te.
6. Composition de graisse selon l'une des revendications 1 à 5 où les métaux de transition d'au moins un lubrifiant solide (c) sont choisis parmi Mo, W, Zr, Hf, Pt, Re, The grease composition according to one of claims 1 to 5, wherein the transition metals of at least one solid lubricant (c) are selected from Mo, W, Zr, Hf, Pt, Re,
Ti, Ta, Nb, préférentiellement Mo et W. Ti, Ta, Nb, preferably Mo and W.
7. Composition de graisse selon l'une des revendications 1 à 6 où au moins un lubrifiant solide (c) est un dichalcogenure de métaux de transition.  7. Grease composition according to one of claims 1 to 6 wherein at least one solid lubricant (c) is a transition metal dichalcogenide.
8. Composition de graisse selon l'une des revendications 1 à 7 où au moins un lubrifiant solide (c) est le bisulfure de Molybdène MoS2 ou le bisulfure de tungstène 8. The grease composition according to one of claims 1 to 7 wherein at least one solid lubricant (c) is molybdenum disulfide MoS2 or tungsten bisulfide.
WS2 à structure fullerène inorganique. WS2 with inorganic fullerene structure.
9. Composition de graisse selon l'une des revendications 1 à 8 où les lubrifiants solides (c) sont constitués de particules de diamètre compris entre 80 et 220 nm, préférentiellement entre 100 et 200 nanomètres. 9. Grease composition according to one of claims 1 to 8 wherein the solid lubricants (c) consist of particles with a diameter of between 80 and 220 nm, preferably between 100 and 200 nanometers.
10. Composition de graisse selon l'une revendications 1 à 9 où au moins un additif anti/usure et/ou extrême pression (d) est choisi parmi les esters des acides phosphorique, phosphoreux, thiophosphorique ou thiophosphoreux, ou leurs dérivés, les dithiophosphates, préférentiellement les dithiophosphates de zinc ou de molybdène, les phosphorothionates, les phosphates d'amines 10. Grease composition according to one of claims 1 to 9 wherein at least one anti-wear additive and / or extreme pressure (d) is selected from esters of phosphoric acid, phosphorous, thiophosphoric or thiophosphorous, or derivatives thereof, dithiophosphates , preferentially zinc or molybdenum dithiophosphates, phosphorothionates, amine phosphates
1 1. Composition de graisse selon la revendication 10 ou au moins un additif anti/usure et/ou extrême pression (d) est choisi parmi les dithiophosphates de Zinc de formule :  The grease composition according to claim 10 or at least one anti-wear and / or extreme pressure additive (d) is selected from Zinc dithiophosphates of the formula:
(R10)(R20)PS2 ZnS2P(R30)(R40), où  (R10) (R20) PS2 ZnS2P (R30) (R40), where
RI , R2, R3, R4 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.  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 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
12. Composition de graisse selon l'une revendications 10 à 1 1 où au moins un additif anti/usure et/ou extrême pression (d) est choisi parmi les dithiophosphates de 12. Grease composition according to one of claims 10 to 1 1 wherein at least one antiwear additive and / or extreme pressure (d) is selected from the dithiophosphates of
Molybdène de formule : Molybdenum of formula:
(R50)(R60)SPS(MoS2)2 SPS(R70)(R80), où  (R50) (R60) SPS (MoS2) 2 SPS (R70) (R80), where
R5, R6, R7, R8 sont, indépendamment les uns des autres, des groupements alkyl linéaires ou ramifiés comprenant de 1 à 24, préférentiellement de 3 à 20 atomes de carbone ou des groupements aryl éventuellement substitués comportant de 6 à 30, préférentiellement de 8 à 18 atomes de carbone.  R5, R6, R7, R8 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 20 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to at 18 carbon atoms.
13. Composition de graisse selon l'une des revendications 2 à 12 où les savons métalliques sont des savons métalliques simples d'acides gras comprenant de 14 à 28 atomes de carbone, saturés ou non, hydroxylés ou non, et/ou des savons métalliques complexes d'un ou plusieurs acides gras comprenant de 14 à 28 atomes de carbone, saturés ou non, hydroxylés ou ou non en combinaison avec un ou plusieurs acides carboxyliques à chaîne hydrocarbonée courte comprenant au de 6 à 12 atomes de carbone.  13. The grease composition according to one of claims 2 to 12 wherein the metal soaps are simple metal soaps of fatty acids comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or not, and / or metal soaps complexes of one or more fatty acids comprising from 14 to 28 carbon atoms, saturated or unsaturated, hydroxylated or otherwise in combination with one or more carboxylic acids having a short hydrocarbon chain comprising from 6 to 12 carbon atoms.
14. Composition de graisse selon les revendications 2 à 13 où les savons métalliques d'acides gras sont choisis parmi les savons de titane, d'aluminium, ou de métaux alcalins et alcalino terreux, de préférence le lithium, le calcium, le sodium, le baryum. 14. The grease composition according to claims 2 to 13, wherein the metal fatty acid soaps are chosen from titanium, aluminum, or alkali and alkaline earth metals, preferably lithium, calcium, sodium, barium.
15. Composition de graisse selon l'une des revendications 1 à 14 où au moins une huile de base (a) est une huile d'origine synthétique, préférentiellement choisie parmi les polyalphaoléfines  15. Grease composition according to one of claims 1 to 14, wherein at least one base oil (a) is an oil of synthetic origin, preferably chosen from polyalphaolefins.
16. Composition de graisse selon l'une des revendications 1 à 15 où l'huile de base ou le mélange d'huiles de base (a) a une viscosité cinématique à 40 °C selon la norme ASTM D 445 comprise entre 70 et 140 cSt, préférentiellement entre 90 et 100 cSt.  The grease composition according to one of claims 1 to 15, wherein the base oil or the base oil mixture (a) has a kinematic viscosity at 40 ° C according to ASTM D 445 between 70 and 140. cSt, preferably between 90 and 100 cSt.
17. Composition de graisse selon les revendications 1 à 16 dont la consistance selon la norme ASTM D217, est comprise entre 265 et 385 dixièmes de millimètres, préférentiellement entre 265 et 295, ou entre 310 et 340, ou entre 335 et 385 dixièmes de millimètres, préférentiellement comprise entre 310 et 340 dixièmes de millimètres.  17. Grease composition according to claims 1 to 16, the consistency of which according to ASTM D217 is between 265 and 385 tenths of a millimeter, preferably between 265 and 295, or between 310 and 340, or between 335 and 385 tenths of a millimeter. preferably between 310 and 340 tenths of millimeters.
18. composition de graisse selon l'une des revendications 1 à 17 comprenant :  The grease composition according to one of claims 1 to 17 comprising:
· de 70 à 94,8 % en masse d'une ou plusieurs huiles de base (a) · From 70 to 94.8% by weight of one or more base oils (a)
• de 5 à 20 % en masse d'un ou plusieurs épaississants (b)From 5 to 20% by weight of one or more thickeners (b)
• de 0,1 à 5 % d'un ou plusieurs lubrifiant solide (c)From 0.1 to 5% of one or more solid lubricants (c)
• de 0,1 à 5% d'un ou plusieurs additifs anti usure et/ou extrême pression organophosphorés et/ou organo phospho soufrés (d). From 0.1 to 5% of one or more organophosphorus and / or organophospho-sulfur anti-wear and / or extreme pressure additives (d).
19. Utilisation d'une composition de graisse selon l'une des revendications 1 à 19. Use of a grease composition according to one of claims 1 to
18 dans les joints homocinétiques des transmissions de véhicules à moteur. 18 in the homokinetic joints of motor vehicle transmissions.
20. Joint homocinétique contenant une graisse selon l'une des revendications 1 à 20. Homokinetic gasket containing a grease according to one of claims 1 to
19. 19.
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CN102482604A (en) 2012-05-30
ES2640399T3 (en) 2017-11-02
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CA2771772C (en) 2018-07-24
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IN2012DN01906A (en) 2015-07-24
FR2949786B1 (en) 2013-07-05
KR101774902B1 (en) 2017-09-05
CN102482604B (en) 2014-12-10
WO2011030315A1 (en) 2011-03-17
US20120165104A1 (en) 2012-06-28
BR112012005498A2 (en) 2020-07-21
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MX2012002923A (en) 2012-04-30
FR2949786A1 (en) 2011-03-11
JP5668069B2 (en) 2015-02-12
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CA2771772A1 (en) 2011-03-17
PL2475752T3 (en) 2017-12-29

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