EP2585564B1 - Compositions lubrifiantes pour transmissions automobiles - Google Patents

Compositions lubrifiantes pour transmissions automobiles Download PDF

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Publication number
EP2585564B1
EP2585564B1 EP11738312.5A EP11738312A EP2585564B1 EP 2585564 B1 EP2585564 B1 EP 2585564B1 EP 11738312 A EP11738312 A EP 11738312A EP 2585564 B1 EP2585564 B1 EP 2585564B1
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EP
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Prior art keywords
molybdenum
carbon atoms
lubricant composition
composition according
preferentially
Prior art date
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EP11738312.5A
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German (de)
English (en)
French (fr)
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EP2585564A1 (fr
Inventor
Emmanuel Matray
Richard Vernay
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C10M105/46—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
    • C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
    • C10M105/64—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/68—Amides; Imides
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing 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
    • 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
    • C10M141/10—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 phosphorus-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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • 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
    • C10M2201/087—Boron oxides, acids or 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
    • 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
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    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • 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
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    • 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
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • C10M2223/047—Thioderivatives not containing metallic elements
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
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    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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    • C10M2227/09—Complexes with metals
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    • 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
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions

Definitions

  • the present invention relates to lubricating compositions, in particular for automotive transmissions, particularly lubricating compositions for manual gearboxes.
  • the transmission components of motor vehicles operate under heavy load and high speeds.
  • the oils for these transmissions must therefore be particularly effective in protecting the parts against wear and fatigue, and in particular protecting the gear teeth against the phenomenon of chipping.
  • the prevention of this phenomenon involves a reduction of contact stresses thanks to an appropriate geometry of the parts, and the reduction of friction, avoiding adhesion.
  • Lubricant is involved in this prevention process, mainly by the physicochemical reactivity of its additives.
  • Sulfur, phosphorus, phospho sulfur or borated anti-wear and extreme pressure additives are generally added to give the transmission oils peel protection properties.
  • the other additives present in the lubricant can also have an impact, positive or negative, on the propagation of cracks inside the parts and thus on the phenomenon of chipping.
  • these members comprise a cone and ring device between which the friction must be precisely controlled: the friction must be sufficient for the synchronization of speeds, but it is necessary that the cone and the ring can then disengage, because otherwise there is a lock of the synchronizer.
  • the level of friction can be adjusted by adding friction modifiers in these gearbox oils.
  • compositions comprising organo-molybdenum friction-modifying compounds with organophosphorus and / or organosulfur and / or organophosphorus-sulfur anti-wear and extreme pressure compounds, in particular for improving the anti-wear properties of these oils.
  • the patent US 6806241 discloses a lubricating composition
  • a lubricating composition comprising a molybdenum complex prepared by reaction of 1 mole of fatty substance which may be a glyceride or a fatty acid, from 1 to 2.5 moles of diethanolamine, and a source of molybdenum in an amount sufficient to obtain a complex containing from 0.1 to 12% by weight of molybdenum with respect to the weight of complex, a thiadiazole compound, and optionally a phosphorodithioate.
  • No specific example of a composition comprising both molybdenum, at a mass content of between 90 and 350 ppm, sulfur and phosphorus is given.
  • EP 0874040 discloses internal combustion engine lubricants comprising a molybdenum complex prepared by reacting 1 mole of fatty substance which may be a glyceride or a fatty acid, 1 to 2.5 moles of diethanolamine, and a molybdenum source in sufficient quantity to obtain a complex containing from 0.1 to 12% by weight of molybdenum with respect to the weight of complex, and of an organo-sulfur compound chosen from dimercaptothiadiazoles, bisdithiocarbamates, dithiocarbamates and phosphorodithioates.
  • organo-sulfur compound chosen from dimercaptothiadiazoles, bisdithiocarbamates, dithiocarbamates and phosphorodithioates.
  • WO 2005035700 discloses lubricating compositions comprising an organomolybdenum compound selected from molybdenum dithiophosphates or dithiocarbamates, and an anti-wear compound, which may be a dimercaptothiadiazole. This application does not disclose the combination of a specific molybdenum content with the use of a thiazole as an antiwear and extreme pressure agent.
  • molybdenum in the form of dithiophosphates or dithiocarbamates, is also likely to generate more wear problems and / or blocking synchronizers, and possibly scaling.
  • compositions of the prior art based on molybdenum, sulfur and / or phosphorus relate to the fields of antioxidants and antiwear, mainly for the formulation of oil for internal combustion engines.
  • compositions of the prior art do not have a specific dosage of Mo element, and a sufficient presence of sulfur and phosphorus allowing them to have both protective properties against flaking, wear and tear. synchronizers and avoiding synchronizer locks satisfactorily. These compositions are therefore not suited to the lubrication of gearboxes of motor vehicles, in particular manual gearboxes.
  • borated oils have an excellent compromise between the various properties listed above. These oils can be formulated without sulfur, phosphorus or phosphorus compounds, and until now no technology based on sulfur, phosphorus or phospho sulfur additives has made it possible to achieve the level of performance obtained with borates in terms of protection against chipping and wear of synchronizers.
  • the use of borates is not desirable when there is a risk of contamination of the lubricant with water.
  • the inorganic borates being partially soluble in water, the amount of water present in the molecule can increase which has the effect of changing the borate structure.
  • the borate structure being thus modified they can crystallize and form crystals in the form of knives of sizes greater than 100 .
  • the borates can block the synchronization systems in the gearboxes.
  • borated oils therefore requires a particular design manual gearbox with watertight system, which has a complexity and cost that it is desirable to avoid.
  • the lubricant compositions according to the invention have a phosphorus content by mass of between 520 and 650 ppm.
  • the lubricant compositions according to the invention comprise at least one thiophosphate, preferably at least one dithiophosphate, preferably at least one amine dithiophosphate, as compound (c).
  • the lubricating compositions according to the invention may comprise between 0.35 and 1% by weight of dimercaptothiadiazole.
  • the compound (ii) is diethanolamine or 2- (2-aminoethyl) aminoethanol.
  • the fatty substance (i) is a mono-, di- or tri-glyceride of fatty acids containing from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, or a fatty acid containing from 4 to 28 carbon atoms. carbon atoms, preferably 8 to 18 carbon atoms.
  • the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula: where R 1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.
  • the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula: where R 1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.
  • the present invention also relates to the use of the compositions described above for the lubrication of gearboxes, in particular motor vehicles.
  • the present invention relates to the use of the compositions described above for the lubrication of manual gearboxes, in particular gearboxes manual for motor vehicles.
  • the lubricating compositions can comprise any oil-soluble organomolybdenum compound, in particular and not limited to molybdenum dithiophosphates and dithiocarbamates, and various organic molybdenum complexes such as carboxylates, esters, molybdenum amides, which can be obtained by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides or fatty acids, or of fatty acid derivatives (esters, amines, amides, etc.).
  • organomolybdenum compound in particular and not limited to molybdenum dithiophosphates and dithiocarbamates, and various organic molybdenum complexes such as carboxylates, esters, molybdenum amides, which can be obtained by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides or fatty acids, or of fatty acid derivatives (esters, amines,
  • the lubricating compositions comprise sulfur and phosphorus-free molybdenum complexes, with amide ligands, mainly prepared by reaction of a molybdenum source, which may be, for example, molybdenum trioxide, and an amine and fatty acid derivative comprising, for example, from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, such as for example the fatty acids contained in vegetable or animal oils.
  • a molybdenum source which may be, for example, molybdenum trioxide
  • an amine and fatty acid derivative comprising, for example, from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, such as for example the fatty acids contained in vegetable or animal oils.
  • the organomolybdenum compound of the compositions according to the invention consists of at least one of the following compounds (IV) or (V), alone or as a mixture: where R 1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.
  • the content of organomolybdenum compound in the compositions according to the invention is adjusted so that the mass content of molybdenum of said compositions is between 90 and 180 ppm, preferably between 140 and 180 ppm.
  • Too low a molybdenum content generates synchro blocking problems, and potentially wear of the cone-ring assembly of the synchronizer.
  • Thia (di) azoles are compounds that contain both a sulfur and a nitrogen atom in a five-membered ring. Benzothiazoles are a special type of thia (di) azoles. This thia (di) azole term includes, in addition to the cyclic compounds containing one sulfur atom and one nitrogen atom per 5 atom ring, also the thiadiazoles which contain sulfur and two nitrogen atoms in such a ring.
  • These compounds may be unsubstituted or substituted by hydrocarbon compounds which increase their solubility in the oil.
  • the thia (di) azoles of the lubricating compositions are unsubstituted benzothiazoles, thiazoles, thiadiazoles.
  • the thiadiazoles of the compositions according to the invention are dimercaptothiadiazoles, for example 2,5 dimercapto 1,3,4-thiadiazole, 3,5 dimercapto1,2,4 thiadiazole, 3,4 dimercapto1,2,4 thiadiazole, 4,5 dimercapto, 1,2,3-thiadiazole, 3-methylmercapto, 5-mercapto, 1,2,4-thiadiazole.
  • compositions according to the invention contain between 0.35 and 1%, preferably between 0.35 and 0.45% by weight of dimercaptothiadiazoles.
  • the phosphorus compounds of the lubricating compositions according to the present invention are anti-wear and extreme pressure additives such as phosphates, phosphites, or phosphonates. These terms refer to both phosphoric, phoporous, phosphonic acids their mono, di and triesters, for example alkyl phosphates, alkyl phosphonates, alkyl phosphonates, and their salts, for example amines.
  • the anti-wear and extreme pressure phospho-sulfur additives used in the present invention are (mono or di) thiophosphates and thiophosphites, these terms including thiophosphoric and thiophosphorous acids, esters of these acids, their salts, dithiophosphites and dithiophosphates.
  • Particularly preferred compounds are dithiophosphates (X3 and X4 are sulfur), preferably zinc or amine. Amine dithiophosphates are particularly preferred compounds.
  • phospho sulfur the monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, trioctylthiophosphate, triphenylthiophosphate, trilaurylthiophosphate, monobutylthiophosphite, monooctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite , trioctylthiophosphite, triphenylthiophosphite, trilaurylthiophosphite and their salts.
  • salts of thiophosphoric acid esters and thiophosphorous acid are those obtained by reaction with a nitrogen
  • the amount of these additives is adjusted so that the phosphorus mass content of the oils according to the invention is between 500 and 700 ppm, preferably between 520 and 650 ppm.
  • compositions according to the invention may contain any type of mineral lubricating base, synthetic or natural, animal or vegetable adapted (s) to their use.
  • the 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 (or their equivalents according to the ATIEL classification) as summarized herein. below, alone or mixed.
  • 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 compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
  • the polyo-olefins used as base oils for example, are obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C of between 1.5 and 15 Cst. Their weight average molecular weight is typically between 250 and 3000. Mixtures of synthetic and mineral oils may also be employed.
  • Such or such lubricating base for producing the compositions according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulfur content. , resistance to oxidation ... adapted for use in a gearbox, in particular for motor vehicles, in particular manual gearbox.
  • the lubricating bases represent at least 50%, preferably at least 60%, or at least 70% by weight of the lubricating compositions according to the invention. Typically, they represent between 75 and 90% by weight of the compositions according to the invention.
  • the lubricant compositions according to the invention comprise Group I and / or III mineral bases, or Group IV synthetic bases according to the API classification.
  • the lubricant compositions according to the invention may also contain any type of additive suitable for their use, for example amino or phenolic antioxidants such as diphenylamines, or phenols substituted on at least one of their ortho positions, with groups alkyl, detergents, for example sulfonates.
  • additives suitable for their use, for example amino or phenolic antioxidants such as diphenylamines, or phenols substituted on at least one of their ortho positions, with groups alkyl, detergents, for example sulfonates.
  • Viscosity index improvers are preferably present at contents of between 5 and 25% by weight, so as to confer viscometric properties suitable for use in gearboxes, in particular gearboxes for automobile gearboxes.
  • preferentially manual such as, for example, polymethacrylates (PMA), polyisobutenes (PIB), or fatty acid esters ...
  • the synchro-blocking test is passed if, during the 10,125 gear-change cycles, the number of cycles in which the disengagement between the cone and the ring requires the application of a counter torque greater than 2 mN is not more than 100 cycles.
  • oils A and B are oils according to the invention; oils C to N are oils outside the invention. Oils C and D are borated oils, sensitive to water. Oils A and B have a level of synchronizing wear performance equivalent to that of borated oils, and pass blocking and peeling tests in the same manner.
  • Oil E contains the same antiwear and extreme pressure additives as oil A, with phosphorus / phosphate phosphorus compounds as well; This E oil does not contain a molybdenum friction modifier. Synchronous wear is at an unacceptable level (0.84 mm).
  • oils F, G, H have the same additive in anti-wear and extreme pressure sulfur and phospho sulfur as the oils according to the invention, but contain various friction modifiers without molybdenum. Synchronizer wear is very important with these oils.
  • the oils I and L have the same additive in sulfur and phospho sulfur antiwear and extreme pressure as the oils according to the invention, and contain an amide ester molybdenum friction modifier.
  • the mass content in Mo of oil I is 400 ppm, and this oil is flaking.
  • the mass content in Mo of oil L is 80 ppm, and this oil is fail in synchro blocking.
  • the oil J has the same additive in anti-wear and extreme pressure sulfur and phospho sulfur as the oils according to the invention, but does not contain molybdenum.
  • a fatty acid monoester is present as a friction modifier. This oil is fail in synchro blocking.
  • the oil K has the same additive in anti-wear and extreme pressure sulfur and phospho sulfur as the oils according to the invention, and does not contain molybdenum. It contains no friction modifier. This oil is fail in synchro blocking.
  • M and N oils do not contain thiazole as the sulfur compound.
  • M oil is also free of molybdenum. These oils have achieved a particularly catastrophic chipping result. It should be noted that these oils do not contain dimercaptothiadiazole.
  • Table 1 Mass Composition and Properties ⁇ / b> AT B VS D E F BOY WUT H I J K

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
EP11738312.5A 2010-06-25 2011-06-24 Compositions lubrifiantes pour transmissions automobiles Active EP2585564B1 (fr)

Applications Claiming Priority (2)

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FR1055108A FR2961823B1 (fr) 2010-06-25 2010-06-25 Compositions lubrifiantes pour transmissions automobiles
PCT/IB2011/052801 WO2011161662A1 (fr) 2010-06-25 2011-06-24 Compositions lubrifiantes pour transmissions automobiles

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JP (1) JP5739525B2 (pt)
KR (1) KR101843950B1 (pt)
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CA (1) CA2818935C (pt)
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FR2984348B1 (fr) 2011-12-16 2015-02-27 Total Raffinage Marketing Compositions lubrifiantes pour transmissions
FR2990213B1 (fr) 2012-05-04 2015-04-24 Total Raffinage Marketing Composition lubrifiante pour moteur
FR2998303B1 (fr) 2012-11-16 2015-04-10 Total Raffinage Marketing Composition lubrifiante
FR3009309B1 (fr) * 2013-08-02 2016-10-07 Total Marketing Services Compositions lubrifiantes pour transmissions
FR3018079B1 (fr) 2014-02-28 2017-06-23 Total Marketing Services Composition lubrifiante a base de nanoparticules metalliques
WO2017171019A1 (ja) * 2016-03-31 2017-10-05 出光興産株式会社 潤滑油組成物及びそれを使用した精密減速機
CN106367169B (zh) * 2016-08-08 2019-03-05 福建黑狮润滑油有限公司 一种全合成超载荷抗磨极压工业齿轮油及其制备方法
JP7247171B2 (ja) * 2017-08-29 2023-03-28 ビーエーエスエフ ソシエタス・ヨーロピア 変速機の潤滑剤組成物
FR3108914B1 (fr) * 2020-04-01 2022-07-01 Total Marketing Services Composition lubrifiante comprenant un composé 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate
CN112408483B (zh) * 2020-10-23 2023-01-17 天津科技大学 一种苯甲酸功能化修饰的非化学计量氧化钼纳米晶体及其制备方法与应用
CN114874760B (zh) * 2022-01-27 2023-07-18 深圳市利特能源技术有限公司 一种抗磨减阻剂主剂及其制备方法、抗磨减阻剂及其制备方法和应用

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BR112012032500B1 (pt) 2019-01-22
CA2818935C (fr) 2018-06-19
PT2585564T (pt) 2017-11-03
CA2818935A1 (fr) 2011-12-29
KR20130096168A (ko) 2013-08-29
MX2012015294A (es) 2013-05-30
BR112012032500A2 (pt) 2018-02-27
FR2961823A1 (fr) 2011-12-30
CN102959061B (zh) 2016-02-10
JP2013529699A (ja) 2013-07-22
ES2644530T3 (es) 2017-11-29
US20130096041A1 (en) 2013-04-18
MX349410B (es) 2017-07-27
WO2011161662A1 (fr) 2011-12-29
EP2585564A1 (fr) 2013-05-01
CN102959061A (zh) 2013-03-06
FR2961823B1 (fr) 2013-06-14
RU2012155783A (ru) 2014-07-27
RU2564673C2 (ru) 2015-10-10
KR101843950B1 (ko) 2018-03-30

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