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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
  • C10M125/06—Sulfur
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/06—Mixtures of thickeners and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/04—Elements
  • C10M2201/041—Carbon; Graphite; Carbon black
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/04—Elements
  • C10M2201/041—Carbon; Graphite; Carbon black
  • C10M2201/0416—Carbon; Graphite; Carbon black used as thickening agents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/026—Butene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
  • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
  • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/08—Groups 4 or 14
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives

Definitions

• the present invention relates to grease compositions for use in the homokinetic joints of transmission lines of motor vehicles, or other gear mechanisms for which low friction greases are desired.
• a transmission joint or mechanical coupling is a mechanical system composed of several moving parts relative to each other, or deformable, which allows the mutual training of two rotating parts whose axes of rotation occupy variable relative positions during the operation.
• it is a link which makes it possible to transmit the rotation of an axis to another axis which is the first one. If the speed of rotation of the two shafts is equal at any given moment, the speed of rotation of the two shafts is constant.
• the greases used in the constant velocity joints must have an anti-wear effect, and preferably a low coefficient of friction to reduce or prevent noise, vibration and jolts.
• known constant velocity joint greases frequently contain anti-wear additives, which are for example phosphorus or phosphorus compounds, and frictio n modifiers, for example molybdenum-containing organic compounds, which may have effects on one or both of these properties, or both. It is also known to use, as friction modifiers, solid lubricants such as molybdenum disulfide (MoS2) or tungsten (WS2), or graphite.
• anti-wear additives which are for example phosphorus or phosphorus compounds
• frictio n modifiers for example molybdenum-containing organic compounds, which may have effects on one or both of these properties, or both.
• Frictio n modifiers for example molybdenum-containing organic compounds
• the application FR 2 723 747 discloses high temperature greases for homokinetic joints comprising mineral and / or synthetic base oils, polyurea thickeners and MoS 2 as solid lubricant, as well as graphite and at least one organic molybdenum compound, preferentially molybdenum dithiocarbamate.
• Graphite solid lubricants, MoDTC, PTFE allow to lower the MoS 2 expensive solid lubricant content, but it is necessary to completely replace it.
• MoS 2 solid lubricants have a high price and introduce a high content of meta l in the formulas, which is undesirable for environmental reasons. None in this application suggests lowering the metal (Mo) content of the fat by completely substituting other MoS 2 solid lubricants.
• the molybdenum content of the disclosed compounds is in the order of 5000 ppm.
• Fats thickened with polyureas are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and have little storage stability. The precautions to be taken make the manufacturing processes more complex and more expensive. The availability of raw materials is also lower compared to those of greases thickened with metallic soaps, in particular Lithium and Lithium complex.
• the polyureas are superior in thermal behavior, but their thixiotropic character also poses problems of destructuring under mechanical control and storage hardening. It will therefore be preferred, for formulating greases for homokinetic joint technically easier, and more economical to manufacture, from non-toxic and non-hazardous materials, use metal soaps of fatty acids as thickeners.
• Some commercial greases for constant velocity joints are, for example, formulated from mineral and / or synthetic base oils, lithium or complex lithium thickeners, and MoS 2 molybdenum disulfide, at about 3% by weight, which represents a content of approximately 18,000 ppm Mo. Below this MoS 2 content, the wear and friction performances are insufficient.
• EP 0708 172 discloses 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, such as MoDTC or MoDTP, at least one dithiophosphate. zinc, a phosphor sulfur extreme pressure agent, a metal salt of oxidized wax, petroleum sulphonate or aromatic alkyl sulphonates.
• molybdenum such as MoDTC or MoDTP
• zinc a phosphor sulfur extreme pressure agent
• a metal salt of oxidized wax petroleum sulphonate or aromatic alkyl sulphonates.
• Examples of compositions disclosed have either a high molybdenum content (about 8500 ppm) and / or a high phosphorus content (about 2000 ppm phosphorus), which poses environmental problems.
• WO 2007/085643 discloses polyurethane-thickened homokinetic joint grease compositions comprising from 0.1 to 5% by weight of WS2, and from 0.1 to 5% by weight of zinc dithiophosphate and / or dithiocarbamate. molybdenum. This application also discloses the possibility of using as an additive in greases graphite or MoS 2 . However, the use of graphite (or MoS 2 ) in combination with MoDTC is disadvised because this combination has, according to this application, an adverse effect on the anti-wear properties and the coefficient of friction of the greases.
• the demand is reflected in the fact that the thickened homokinetic properties are added to the metal fatty acid soaps and include graphite in combination with molybdenum dithiocarbamate meet the need outlined above.
• the present invention relates to grease compositions comprising
• the grease compositions according to the invention have a molybdenum content of between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferentially between 1700 and 2300, preferably between 2000 and 2200 ppm.
• the grease compositions according to the invention comprise between 0.5 and 3.0% by weight of graphite, preferably between 0.7 and 2.0%.
• the grading compositions according to the invention have an Mo / [graphite] ratio between the molybdenum content in ppm and the mass percentage of graphite in said compositions, inclusive. between 1250 and 1550, preferably between 1300 and 1500.
• the grease compositions according to the invention comprise phosphorus at a content of less than 1500 ppm, preferably less than 1200 ppm.
• the grease compositions according to the invention comprise zinc at a content of less than 1500 ppm.
• the grease compositions according to the invention are free of MoS 2 solid lubricant. According to another preferred embodiment, the grease compositions according to the invention are free of polytetrafluoroethylene solid lubricant.
• the grease compositions according to the invention comprise exclusively one or more simple metal or complex fatty acid soaps as a thickener.
• the grease compositions according to the invention comprise at least one simple soap or complex of lithium, sodium, calcium, barium, or titanium, alone or as a mixture, as a thickener.
• the grease compositions according to the invention comprise one or more single or complex lithium soaps as thickeners.
• the grease compositions according to the invention comprise a mineral base oil (a), and a synthetic base oil (a), preferably chosen from polyalphaolefins.
• the grease compositions according to the invention further comprise a polymer (e) preferably chosen from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
• a polymer (e) preferably chosen from polyisobutenes, olefin copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
• the grease compositions according to the invention may furthermore comprise one or more anti-wear and / or extreme pressure phosphosulfide (f) additives, preferentially chosen from zinc dithiophosphates.
• f extreme pressure phosphosulfide
• the grease compositions according to the invention have a phosphorus content of between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.
• compositions according to the invention have a zinc content of between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 800 and 1000 ppm.
• the grease compositions according to the invention comprise:
• the grease compositions according to the invention comprise: • From 70 to 94% of base oils (a),
• the optional residue consisting of one or more polymers (e) selected from polyisobutenes, olefins copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
• the grease compositions according to the invention comprise:
• phosphosulfur anti-wear and / or extreme pressure additives preferably chosen from zinc dithiophosphates.
• the grease compositions according to the invention comprise:
• phosphorus or phosphosulfur anti-wear additives preferably chosen from zinc dithiophosphates.
• the optional residue consisting of one or more polymers (e) selected from polyisobutenes, olefins copolymers, polymethacrylates, polyalphaolefins, preferably polyisobutenes.
• the present invention also relates to the use of grease compositions as described above as greases for homokinetic joints of motor vehicle transmissions.
• the present invention also relates to one of the homokinetic joints filled with grease compositions as described above.
• DETAILED DESCRIPTION
• the other base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (American Petroleum Institute).
• the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
• the base oils of the grease compositions according to the present invention may also be synthetic oils, such as esters, silicones, polyalkylene glycols, polyols, polyolefins (PAOs), alkylbenzene, and the like. , alkylnaphthalene.
• synthetic oils such as esters, silicones, polyalkylene glycols, polyols, polyolefins (PAOs), alkylbenzene, and the like. , alkylnaphthalene.
• the base oils may also be oils of natural origin, for example esters of alcohol and carboxylic acids, obtainable from natural resources such as sunflower oil, rapeseed oil, palm oil. ...
• synthetic polyolepipeldefin (PAO) hulls are present in combination with mineral oils.
• the polyalphaolefins are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene). Their weight average molecular weight is typically between 250 and 3000.
• the base oil mixture is set so that its viscosity at 40 ° C according to ASTM D 445 is between 30 and 140 cSt, preferably between 50 and 100 cSt.
• a wide range of light polyalphaolefins can be used, such as PAO 6 (31 cSt at 40 ° C), PAO 8 (48 cSt at 40 ° C), or heavy, such as PAO 40 (400 cSt at 40 ° C), or PAO 100 (1000 cSt at 40 ° C).
• the greases according to the present invention are thickened with metal fatty acid soaps.
• Metallic fatty acid soaps can be prepared separately, or in situ during the manufacture of the fat (in the latter case, the fatty acid (s) are dissolved in the base oil, and then the metal hydroxide is added. appropriate).
• These thickeners are commonly used products in the field of fats, readily available and inexpensive. They present the best technical compromise, by combining both good mechanical properties, good thermal resistance, and good water resistance.
• Long-chain fatty acids typically comprising from 10 to 28 carbon atoms, saturated or unsaturated, optionally hydroxylated, are preferably used.
• Long-chain fatty acids are, for example, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, oleic, linoleic and erucic acids, and their hydroxylated derivatives.
• Hydroxystearic acid 12 is the best known derivative of this class, and preferred.
• These long-chain fatty acids generally come from vegetable oils, for example palm oil, castor oil, rapeseed oil, sunflower oil, ... or animal fats (tallow, whale oil, etc.).
• So-called simple soaps can be formed using one or more long-chain fatty acids.
• So-called complex soaps can also be formed by using one or more long-chain fatty acids in combination with one or more short-chain hydrocarbon carboxylic acids having at most 8 carbon atoms.
• the saponification agent used to make the soap may be a monomeric compound of lithium, sodium, calcium, aluminum, lithium, luminium, preferably lithium and calcium, and preferably a hydroxide oxide or a carbonate of these metals.
• Metal soaps in particular Lithium, Sodium, Calcium, Barium, Titanium, form a fibrous structure, with the exception of simple or complex aluminum soaps, which have a spherical gel structure.
• One or more metal compounds may be used in the greases according to the invention. It is thus possible to associate lithium soaps, combined with calcium soaps to a lesser extent. This has the advantage of improving the water resistance of greases.
• the metal soaps are employed at levels of the order of 5 to 20% by weight, preferably 8 to 15% by weight, preferably 10 to 12%, typically 11% by weight in the greases according to the invention.
• the amount of metallic soap (s) is generally adjusted to obtain Grade 00, Grade 0, Grade 1 or Grade 2 fats according to the NLGI classification.
• the greases according to the invention mainly contain metal fatty acid soaps as thickeners.
• metal fatty acid soaps simple or complex, together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
• the greases according to the invention mainly contain simple or complex lithium soaps as thickeners.
• lithium soaps, simple or complex together represent the highest percentage by weight in the greases according to the invention, compared to the percentage by weight of other thickening materials.
• the quantity of the metal soap or fatty acids, simple or complex constitutes at least 50%, more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention. invention.
• the amount of lithium soap, simple or complex constitutes at least 50%, even more preferably at least 80% by weight relative to the total weight of thickening materials, in the grease compositions according to the invention.
• the greases according to the invention may contain as the major thickener metal soaps of fatty acids whether mple or complex, and smaller amounts of other thickeners, such as polyureas, or inorganic thickeners. type bentonite or alumino silicates.
• the greases according to the invention are free of polyurea thickeners, which are more technically complicated to manufacture, in particular because the components used in their manufacture, such as isocyanates and amines, are very toxic and unstable. in storage.
• the greases according to the invention contain exclusively metal salts of simple or complex fatty acids as thickeners.
• the greases according to the invention contain exclusively metallic soaps of simple or complex fatty acids of lithium as thickeners.
• the grease compositions according to the invention contain graphite and molybdenum dithiocarbamate, which gives them anti-wear properties. improved compared to known commercial fats. These properties can be achieved with a lower molybdenum content than known fats.
• the molybdenum content of the greases according to the invention is between 1000 and 2800 ppm.
• the ratio Mo / [graphite], between the content of molybdenum, in ppm, and the mass percentage of graphite in said composition is between 1250 and 1550.
• the grease compositions also have very good anti-wear and friction properties, equivalent to those of known commercial greases. These good properties are also achieved with a molybdenum content, and possibly a level of other metallic elements such as zinc or a phosphorus element level, lower than those of known fats.
• compositions according to the invention contain molybdenum dithiocarbamates, friction modifying additives well known to those skilled in the art.
• molybdenum dithiocarbamate organometallic friction modifiers may for example be dialkyldithiocarbamates of molybdenum corresponding to formula (I):
• X 1 , X 2 , X 3 , X 4 are alkyl chains, preferably having 2 to 13 carbon atoms, preferably 2 to 6 carbon atoms.
• the amount of MoDTC of the compositions according to the invention is adjusted so that their molybdenum content is between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm. This content can be measured according to the usual techniques, plasma, atomic absorption, flurescence X.
• MoDTC as the only additive (antiwear) in a fat composition. Indeed, it is known that the MoDTC requires a minimum activation temperature and the presence of other additives (antiwear, extreme pressure) to be effective.
• Greases comprising MoDTC without other antiwear and / or extreme pressure additives would not be effective, especially at low temperatures.
• MoDTC is thus associated with phosphorus additives, for example dithiophosphates.
• the MoDTC is combined with graphite, which makes it possible to produce fats having very good properties in wear and friction, with a low molybdenum and phosphorus content.
• the grease compositions according to the invention contain graphite.
• graphite known for its properties as a solid lubricant, makes it possible to reduce the content of friction modifying and anti-wear additives containing molybdenum (and possibly phosphorus), without adding a metallic element, and by maintaining the wear properties. and friction suitable for applying homokinetic joints.
• the graphite employed in the compositions according to the invention is a micrometric gauge, with particle sizes being approximately between 1 and 15 ⁇ , and for example a size distribution characterized by a diameter D50 of between 3 and 8 ⁇ , preferably between 5 and 7 ⁇ .
• the fat composition according to the invention preferably comprises between 0.5 and 3.0% by weight of graphite, preferably between 0.7 and 2.0%, preferably between 0.75 and 1.7%, preferentially between 1, 0 and 1.5% by weight of graphite.
• the greases according to the invention optionally contain sulfur-phosphorus anti wear and extreme pressure additives commonly used in the formulation of greases and lubricants.
• thiophosphoric acid thiophosphorous acid
• esters of these acids their salts
• dithiophosphates particularly zinc dithiophosphates.
• Zinc dithiophosphates of formula (II) are particularly preferred:
• R 1, R 2 , R 3 and R 4 are, independently of one another, linear or branched alkyl groups comprising from 1 to 24, preferably from 3 to 14 carbon atoms or optionally substituted aryl groups containing from 6 to 30, preferably from 8 to 18 carbon atoms.
• compositions according to the invention can be used alone or as a mixture in the grease compositions according to the invention.
• Their mass percentage in the compositions according to the invention is preferably between 0.5 and 5% by weight, preferably between 0.7 and 2% by weight, or between 0.8 and 1.5% by weight relative to the total weight of the composition.
• Their quantity will be adjusted so as to respect the limiting levels in molybdenum and phosphorus elements of the compositions according to the invention.
• the molybdenum (Mo) content of the compositions according to the invention is preferably between 1000 and 2800 ppm, preferably between 1500 and 2500 ppm, preferably between 1700 and 2300, preferably between 2000 and 2200 ppm.
• the phosphorus content (P) of the compositions according to the invention is preferably less than 1500 ppm, preferentially less than 1200 ppm, preferably between 300 and 1200 ppm, preferably between 400 and 1000 ppm, preferably between 500 and 900 ppm.
• This content can be measured according to the usual techniques, plasma, atomic absorption.
• the zinc content of the compositions according to the invention is less than 1500 ppm, preferably between 500 and 1400 ppm, preferably between 600 and 1300 ppm, preferably between 700 and 1200 ppm, preferentially between 800 and 1000 ppm.
• the lubricating compositions according to the present invention may also contain phosphorus anti-wear and extreme pressure additives, such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono- di and triesters of phosphorous acid and phosphoric acid, and their salts
• phosphorus anti-wear and extreme pressure additives such as, for example, alkyl phosphates or alkyl phosphonates, phosphoric acid, phopsphorous acid, mono- di and triesters of phosphorous acid and phosphoric acid, and their salts
• the lubricating compositions according to the present invention may also contain additives which are used extensively and which are highly preferred, such as dithiocarbamates, thiadiazoles and benzothiazoles, sulfurized olefins.
• the greases according to the invention may also contain any type of additives adapted to their use, for example antioxidants, such as mined or phenolic, antirust which may be oxygenated compounds such as esters, passivating copper.
• antioxidants such as mined or phenolic
• antirust which may be oxygenated compounds such as esters, passivating copper.
• the greases according to the invention may also contain polymers (e), for example polyolefins, polyisobutene (PIB), polyethylenes, polypropylene, heavy PAOs, copolymer olefins (OCP), for example diene-styrene hydrogenated, polymethacrylates. (PMA) at generally between 1 and 35%.
• polymers e
• PIB polyisobutene
• OCP copolymer olefins
• PMA diene-styrene hydrogenated, polymethacrylates.
• PMA polymers
• molar mass PIBs between 15,000 and 25,000 daltons at levels generally between 2 and 15% by weight, or between 5 and 10% by weight.
• These polymers are used to improve the cohesiveness of the greases, which are thus more resistant to centrifugation. These polymers also result in better adhesiveness of the grease to the surface, and increase the viscosity of the base oil fraction, and thus the thickness of the oil film between the friction parts.
• 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 may be long acids, comprising from 14 to 28 carbon atoms, for a cyclic form, 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 TM, optionally 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 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. 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.
• the greases according to the invention are preferably greases with a consistency of between 265 and 430, preferably between 265 and 385, preferably between 265 and 340 tenths of a millimeter according to ASTM D217.
• they are NLGI grade 00, 0, 1 or 2, that is to say that their consistency is respectively between 400 and 430, or 335 and 385, or 310 and 340, or 265 and 295 tenths of a millimeter according to ASTM D217.
• Grease compositions containing various additives are prepared from the same grease base comprising mineral and synthetic base oils, thickened with a single lithium soap prepared from lithium hydroxide (LiOH). H2O), and 12-hydroxystearic acid.
• the composition of the fat foot is shown in Table 1 below.
• the term "grease foot” commonly refers to a person skilled in the art as a grease composition containing only base oils and thickeners, and no additive.
• PIB polymer
• DTPZn anti-wear
• MoS 2 graphite
• the MoDTC used is di-n-butyldithiocarbamate molybdenum, containing 28% by mass of molybdenum
• the MoS2 used is a micrometric powder consisting of particles of size between 0.5 and 8 ⁇ , of D50 about 2 ⁇ .
• Grease A is a commercial grease for constant velocity joints
• greases E, I and J are according to the invention.
• the wear properties were evaluated by measuring the wear diameter (in mm) after the 4-ball wear test according to ASTM D2266 (1 hour, load 40 kg, 75 ° C). According to STL Specification S71 3100, CV greases must lead to a wear diameter of less than 50 mm.
• volume of fat lg distributed in thin film and continuous before test
• Fats E and I have the additional advantage of having low friction coefficients, the order of magnitude of those of commercial grease A.

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