US20130096041A1 - Lubricant compositions for motor vehicle transmissions - Google Patents

Lubricant compositions for motor vehicle transmissions Download PDF

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Publication number
US20130096041A1
US20130096041A1 US13/806,063 US201113806063A US2013096041A1 US 20130096041 A1 US20130096041 A1 US 20130096041A1 US 201113806063 A US201113806063 A US 201113806063A US 2013096041 A1 US2013096041 A1 US 2013096041A1
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United States
Prior art keywords
molybdenum
lubricant composition
composition according
wear
complex
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Abandoned
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US13/806,063
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English (en)
Inventor
Emmanuel Matray
Richard Vernay
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.)
Total Marketing Services SA
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Total Raffinage Marketing SA
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Assigned to TOTAL RAFFINAGE MARKETING reassignment TOTAL RAFFINAGE MARKETING ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATRAY, EMMANUEL, VERNAY, RICHARD
Publication of US20130096041A1 publication Critical patent/US20130096041A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C10M105/68—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
    • 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
    • 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
    • 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • 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
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/02—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
    • 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
    • C10M2219/10—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
    • 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
    • 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
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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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • 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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    • 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
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    • 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
    • C10N2030/40—Low content or no content compositions
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    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions

Definitions

  • the present invention relates to lubricant compositions, in particular for automobile transmissions, particularly lubricant compositions for manual gear boxes.
  • the prevention of this phenomenon requires a reduction in the contact stresses by means of a suitable geometry of the parts, and by reduction of friction, while avoiding adhesion.
  • the lubricant is involved in this prevention process, mainly by the physic-chemical reactivity of its additives. Generally sulfur, phosphorous, phosphor-sulfur or borate anti-wear and extreme pressure additives are added in order to provide the transmission oils with properties which are protective against flaking.
  • the other additives present in the lubricant may also have a positive or negative impact on the propagation of cracks inside the parts and therefore on the flaking phenomenon.
  • these components include a cone and ring device between which frictions have to be specifically controlled: the friction should be sufficient for synchronization of the gears, but the cone and the ring must have then have the possibility of disengaging, because otherwise blocking of the synchronizer takes place. Moreover, if the friction level is not adapted to the geometry of the parts, wear occurs on the cone-ring assembly.
  • the friction level may be adjusted by adding friction modifiers in these oils for gear boxes.
  • oils for manual gear boxes anti-wear, extreme pressure additives and friction modifiers may co-exist, all having an action at the surface of the parts and potentially an effect on both the friction level and the flaking phenomenon.
  • the oil formulation for a manual gear box having both high protection against flaking, avoiding wear and blocking of the synchronizers and allowing easy changing of gears, is based on a selection and specific dosage of the friction modifiers, of the anti-wear and extreme pressure additives.
  • 6,806,241 discloses a lubricant composition
  • a lubricant composition comprising a molybdenum complex prepared by the reaction of 1 mole of a fat which may be a glyceride or a fatty acid, of 1 to 2.5 moles of diethanolamine, and of a molybdenum source in a sufficient amount in order to obtain a complex containing from 0.1 to 12% by weight of molybdenum based on the weight of the complex, a thiadiazole compound and optionally a phosphorodithioate.
  • No specific example is given of a composition comprising both molybdenum, at a mass content comprised between 90 and 350 ppm, sulfur and phosphorus.
  • EP Application 0874040 discloses lubricants for internal combustion engines comprising a molybdenum complex prepared by the reaction of 1 mole of fat which may be a glyceride or a fatty acid, of 1 to 2.5 moles of diethanolamine, and of a molybdenum source in a sufficient amount in order to obtain a complex containing from 0.1 to 12% by weight of molybdenum based on the weight of the complex, and of an organic sulfur compound selected from dimercaptothiadiazoles, bisdithiocarbamates, dithiocarbamates, phosphorodithioates.
  • WO 2005035700 discloses lubricant compositions comprising an organic molybdenum 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 anti-wear and extreme pressure agent.
  • the use of molybdenum in the form of dithiophosphates or dithiocarbamates is moreover capable of generating further problems of wear and/or blocking of the synchronizers, and possibly flaking.
  • the compositions of the prior art based on molybdenum, sulfur and/or phosphorus relate to the field of anti-oxidants and anti-wear agents, mainly for formulating oils for internal combustion engines.
  • compositions of the prior art do not have a specific dosage of element Mo, and a sufficient presence of sulfur and phosphorus allowing them to have both properties for protection against flaking, the wear of the synchronizers and avoiding blockings of the synchronizers in a satisfactory way.
  • These compositions are therefore not adapted to the lubrication of gear boxes of automobile vehicles, in particular manual gear boxes.
  • borate oils have an excellent compromise between the different properties listed above.
  • oils may be formulated without any sulfur, phosphorus or phosphor-sulfur compounds, and up to now no technology based on sulfur, phosphorus or phosphor-sulfur additives gave the possibility of attaining the performance level obtained with borates as regards protection against flaking and wear of the synchronizers.
  • borates are however not desirable since there is a risk of contamination of the lubricant by water.
  • inorganic borates being partly soluble in water, the amount of water present in the molecule may increase which has the effect of changing the structure of the borate.
  • the structure of the borate being thereby modified, they may crystallize and form crystals as knives with sizes greater than 100 nm.
  • the borates may block the synchronization systems in the gear boxes.
  • borate oils therefore requires a particular design of the manual gear boxes with a waterproof system, which has complexity and a cost which should desirably be avoided. Therefore there exists a need for oils for gear boxes of automobile vehicles, in particular manual gear boxes, giving both protection against the flaking phenomenon on the gear teeth, allowing limitation of the wear of the synchronizers and avoiding their blocking, allowing easy change of the gears, and insensitive to water (they may not contain borates or else a reduced level of borates).
  • the object of the present invention is lubricant compositions, comprising a molybdenum complex of the ester-amide type, combined with a sulfur-containing extreme pressure additive and a phosphorus-containing or phosphor-sulfur extreme pressure additive and to their use for lubricating gear boxes, in particular for automobile vehicles.
  • a particularly relevant use relates to manual gear boxes of automobile vehicles.
  • the object of the present invention is lubricant compositions comprising:
  • the lubricant composition has a molybdenum mass content comprised between 90 and 350 ppm.
  • the lubricant compositions according to the invention have a molybdenum mass content comprised between 100 and 200 ppm, preferentially between 140 and 180 ppm.
  • the lubricant compositions according to the invention have a phosphorus mass content comprised between 500 and 700 ppm, still more preferentially between 520 and 650 ppm.
  • the lubricant compositions according to the invention comprise at least one thiophosphate, preferentially at least one dithiophosphate, preferentially at least one amine dithiophosphate, as a compound (c).
  • the lubricant compositions according to the invention comprise at least one thiadiazole, preferentially at least one dimercaptothiadiazole as a compound (b).
  • the lubricant compositions according to the invention may comprise between 0.35% and 1% by mass of thiazole, preferentially between 0.35 and 1% by mass of dimercaptothiadiazole.
  • the lubricant compositions according to the invention comprise as a compound (a), at least one organic complex of molybdenum, obtained by reaction:
  • the compound (ii) is diethanolamine or 2-(2-aminoethyl)aminoethanol.
  • the fat (i) is a mono-, di- or tri-glyceride of fatty acids including from 4 to 28 carbon atoms, preferentially from 8 to 18 carbon atoms, or a fatty acid including from 4 to 28 carbon atoms, preferentially from 8 to 18 carbon atoms.
  • the molybdenum complex (a) consists of at least one of the following compounds, either alone or as a mixture:
  • X1 and X2 are either O or else N, and
  • R1 and R2 are fatty hydrocarbon chains comprising between 3 and 27 carbon atoms, preferentially between 7 and 17 carbon atoms.
  • the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula:
  • R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferentially between 7 and 27 carbon atoms.
  • the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula:
  • R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferentially between 7 and 27 carbon atoms.
  • the present invention also relates to the use of the composition described above for lubricating gear boxes, in particular of automobile vehicles. According to a preferred embodiment, the present invention relates to the use of the composition described above for lubricating manual gear boxes, in particular manual gear boxes for automobile vehicles.
  • the lubricant compositions according to the invention may comprise any organic molybdenum compound soluble in oil, notably and not in a limiting way, molybdenum dithiophosphates and dithiocarbamates and various organic complexes of molybdenum such as molybdenum carboxylates, esters, amides, which may be obtained by reaction of molybdenum oxide or of ammonium molybdates with fats, glycerides or fatty acids, or with fatty acid derivatives (esters, amines, amides . . . ).
  • the lubricant compositions according to the invention comprise complexes of molybdenum free of sulfur and of phosphorus, with ligands of the amide type, mainly prepared by reaction of a molybdenum source, which may for example be molybdenum trioxide, an amine and fatty acid derivative for example comprising from 4 to 28 carbon atoms, preferentially from 8 to 18 carbon atoms, such as for example fatty acids contained in vegetable or animal oils.
  • a molybdenum source which may for example be molybdenum trioxide, an amine and fatty acid derivative for example comprising from 4 to 28 carbon atoms, preferentially from 8 to 18 carbon atoms, such as for example fatty acids contained in vegetable or animal oils.
  • a molybdenum source which may for example be molybdenum trioxide
  • an amine and fatty acid derivative for example comprising from 4 to 28 carbon atoms, preferentially from 8 to 18 carbon atoms, such as for example fatty acids contained
  • the organic molybdenum compound of the compositions according to the invention consists of at least one of the following compounds, alone or as a mixture:
  • X1 and X2 are either O or else N, and
  • R1 and R2 are fatty hydrocarbon chains comprising between 3 and 27 carbon atoms, preferentially between 7 and 17 carbon atoms.
  • the molybdenum complexes of the compositions according to the invention are prepared by reaction:
  • the organic molybdenum 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.
  • R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferentially between 7 and 27 carbon atoms.
  • the content of organic molybdenum compound in the compositions according to the invention is adjusted so that the molybdenum mass content of said compositions is comprised between 90 and 350 ppm, preferentially between 100 and 200 ppm, even more preferentially between 140 and 180 ppm.
  • a too low molybdenum content generates problems of synchronizer blocking and potential wear of the cone-ring assembly of the synchronizer.
  • a too strong molybdenum content on the other hand has an unfavorable effect on flaking.
  • Thia(di)azoles are compounds which contain both a sulfur and a nitrogen atom in a ring of five atoms. Benzothiazoles are a particular type of thia(di)azoles. This term of thia(di)azole includes, in addition to the cyclic compounds containing a sulfur atom and a nitrogen atom per ring of 5 atoms, also thiadiazoles which contain sulfur and two nitrogen atoms in such a ring. These compounds may be non-substituted or substituted with hydrocarbon compounds which increase their solubility in oil.
  • the thia(di)azoles of the lubricant compositions according to the invention are non-substituted benzothiazoles, thiazoles, thiadiazoles.
  • the thia(di)azoles of the compositions according to the invention are dimercaptothiadiazoles, for example 2,5-dimercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,4-thiadiazole, 4,5-dimercapto-1,2,3-thiadiazole, 3-methylmercapto-, 5-mercapto-1,2,4-thiadiazole.
  • thia(di)azoles represent between 0.35 and 1% by mass of the compositions according to the invention.
  • the compositions according to the invention contain between 0.35 and 1%, preferentially between 0.34 and 0.45% by mass of dimercaptothiadiazoles.
  • Phosphorus-containing compounds of the lubricant compositions according to the present invention are anti-wear and extreme pressure additives such as phosphates, phosphites, or phosphonates. These terms both designate phosphoric, phosphorous, phosphonic acids, their mono-, di- and tri-esters, for example alkyl phosphates, alkyl phosphonates, alkyl phosphonates, and their salts, for example amine salts.
  • the phosphor-sulfur anti-wear and extreme pressure additives used in the present invention are (mono- or di-)thiophosphates and thiophosphites, these terms including thiophosphoric and thiophosphorous acids, the esters of these acids, their salts, dithiophosphites and dithiophosphates.
  • the phosphor-sulfur anti-wear and extreme pressure additives of the compositions according to the invention are thiophosphates, corresponding to the formula (VI)
  • More preferred compounds are the dithiophosphates (X3 and X4 are sulfur), preferentially of zinc or of an amine. Amine dithiophosphates are more preferred compounds.
  • phosphor-sulfur anti-wear and extreme pressure additives mention may be made of monobutylthiophosphate, monooctylthiophosphate, monolaurylthiophosphate, dibutylthiophosphate, dilaurylthiophosphate, tributylthiophosphate, trioctylthiophosphate, triphenylthiophosphate, trilaurylthiophosphate, monobutylthiophosphite, monooctylthiophosphite, monolaurylthiophosphite, dibutylthiophosphite, dilaurylthiophosphite, tributylthiophosphite, trioctylthiophosphite, triphenylthiophosphite,
  • the amount of these additives is adjusted so that the phosphorus mass content of the oils according to the invention is comprised between 500 and 700 ppm, preferentially between 520 and 650 ppm.
  • a too low content of the anti-wear and extreme pressure element (sulfur and phosphorus) will generate flaking problems.
  • a too strong content of anti-wear and extreme pressure elements, (as well as of a friction modifier, including an organic molybdenum compound) will have an unfavorable effect on changing gears: the cone-ring friction coefficient will be too low, which prevents synchronization of the gears and therefore changing of the gears.
  • compositions according to the invention may contain any type of animal or plant, synthetic or natural mineral lubricant base, adapted 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 the groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification), as summarized below, alone or as a mixture.
  • 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 extraction with a solvent, deasphalting, deparaffining with a solvent, 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 polyalphaolefins used as base oils, are for example obtained from monomers having from 4 to 32 carbon atoms (for example octane, decene), and a viscosity of 100° C. comprised between 1.5 and 15 cSt.
  • compositions according to the invention typically comprised between 250 and 3,000. Mixtures of synthetic and mineral oils may also be used. There is no limitation as to the use of such and such lubricant base for producing the compositions according to the invention, if not that they should have properties, notably of viscosity, viscosity index, sulfur content, resistance to oxidation . . . adapted to a use in a gear box, in particular for automobile vehicles, in particular a manual gear box.
  • the lubricant bases represent at least 50%, preferentially at least 60%, or further at least 70% by mass of the lubricant compositions according to the invention. Typically, they represent between 75 and 90% by mass of the compositions according to the invention.
  • the lubricant compositions according to the invention comprise mineral bases of Group I and/or III, or synthetic bases of Group IV according to the API classification.
  • the lubricant compositions according to the invention may also contain any type of additive adapted to their use, for example amine or phenol antioxidants such as diphenylamines, or phenols substituted on at least one of their ortho positions with alkyl groups, detergents, for example sulfonates.
  • Agents for improving the viscosity index are preferentially present at contents comprised between 5 and 25% by mass, so as to impart viscosimetric properties adapted to the use in a gear box, in particular an automobile gear box, preferentially a manual gear box, such as for example polymethacrylates (PMA), polyisobutenes (PIB), or fatty acid esters . . . .
  • the synchro blocking test is passed, if, during 10125 gear-changing cycles, the number of cycles wherein disengagement between the cone and the ring requires the application of a counter-torque of more than 2 mN is at most 100 cycles.
  • the axial wear of the synchronizer ring/gear cone pair is measured in mm. It should be at most of the order of 0.30 mm in order to be acceptable (pass). A wear of less than 0.15 mm is an excellent performance. A wear of more than 1 mm is disqualifying (guard compensation).
  • the oils A and B are oils according to the invention: the oils C and D are borate oils, sensitive to water.
  • the oils A and B have a performance level as regards wear of synchronizers, equivalent to that of borate oils, and pass the tests of blocking and of flaking in the same way.
  • the oil E contains the same anti-wear and extreme pressure additives as oil A, also with phosphorus-containing compounds of the phosphite/phosphate type; this oil E does not contain any friction modifier with molybdenum.
  • the wear of the synchronizers is at an unacceptable level (0.84 mm).
  • the oils F, G, H have the same additivation in sulfur-containing and phosphor-sulfur anti-wear and extreme pressure agents as the oils according to the invention, but contain various friction modifiers without molybdenum.
  • the wear of the synchronizers is very significant with these oils.
  • the oils I and L have the same additivation as regards sulfur-containing and sulfur-phosphor anti-wear and extreme pressure agents as the oils according to the invention, and contain a friction modifier with molybdenum of the ester amide type.
  • the ester Mo content of the oil I is 400 ppm, and this oil fails as regards flaking.
  • the mass Mo content of the oil L is 80 ppm, and this oil fails as regards synchroblocking.
  • Oil J has the same additivation of sulfur-containing and phosphor-sulfur anti-wear and extreme pressure agents as the oils according to the invention, but do not contain any molybdenum.
  • a fatty acid mono-ester is present as a friction modifier. This oil fails as regards synchronizer blocking.
  • the oil K has the same additivation of sulfur-containing and phosphor-sulfur anti-wear and extreme pressure agents as the oils according to the invention, and does not contain any molybdenum. It does not contain any friction modifier. This oil fails as regards synchroblocking.
  • oils M and N do not contain any thiazole as a sulfur-containing compound.
  • the oil M is also free of molybdenum. These oils have obtained a particularly catastrophic result as regards flaking. It should be noted that these oils do not contain any dimercaptothiadiazole.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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US13/806,063 2010-06-25 2011-06-24 Lubricant compositions for motor vehicle transmissions Abandoned US20130096041A1 (en)

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FR1055108A FR2961823B1 (fr) 2010-06-25 2010-06-25 Compositions lubrifiantes pour transmissions automobiles
FR1055108 2010-06-25
PCT/IB2011/052801 WO2011161662A1 (fr) 2010-06-25 2011-06-24 Compositions lubrifiantes pour transmissions automobiles

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US9334462B2 (en) 2011-12-16 2016-05-10 Total Marketing Services Lubricant compositions for transmissions
CN106367169A (zh) * 2016-08-08 2017-02-01 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
CN108884407A (zh) * 2016-03-31 2018-11-23 出光兴产株式会社 润滑油组合物和使用其的精密减速器
US10604717B2 (en) 2012-05-04 2020-03-31 Total Marketing Services Lubricant composition for an engine
CN111356754A (zh) * 2017-08-29 2020-06-30 巴斯夫欧洲公司 变速器润滑剂组合物
US10752858B2 (en) 2012-11-16 2020-08-25 Total Marketing Services Lubricant composition
US11015141B2 (en) 2014-02-28 2021-05-25 Total Marketing Services Lubricant composition based on metal nanoparticles
CN114874760A (zh) * 2022-01-27 2022-08-09 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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FR3009309B1 (fr) * 2013-08-02 2016-10-07 Total Marketing Services Compositions lubrifiantes pour transmissions
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

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US9334462B2 (en) 2011-12-16 2016-05-10 Total Marketing Services Lubricant compositions for transmissions
US10604717B2 (en) 2012-05-04 2020-03-31 Total Marketing Services Lubricant composition for an engine
US10752858B2 (en) 2012-11-16 2020-08-25 Total Marketing Services Lubricant composition
US11015141B2 (en) 2014-02-28 2021-05-25 Total Marketing Services Lubricant composition based on metal nanoparticles
CN108884407A (zh) * 2016-03-31 2018-11-23 出光兴产株式会社 润滑油组合物和使用其的精密减速器
CN106367169A (zh) * 2016-08-08 2017-02-01 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
CN111356754A (zh) * 2017-08-29 2020-06-30 巴斯夫欧洲公司 变速器润滑剂组合物
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BR112012032500A2 (pt) 2018-02-27
FR2961823B1 (fr) 2013-06-14
CA2818935C (fr) 2018-06-19
EP2585564A1 (fr) 2013-05-01
KR101843950B1 (ko) 2018-03-30
JP2013529699A (ja) 2013-07-22
JP5739525B2 (ja) 2015-06-24
KR20130096168A (ko) 2013-08-29
CN102959061A (zh) 2013-03-06
RU2564673C2 (ru) 2015-10-10
CN102959061B (zh) 2016-02-10
RU2012155783A (ru) 2014-07-27
ES2644530T3 (es) 2017-11-29
FR2961823A1 (fr) 2011-12-30
BR112012032500B1 (pt) 2019-01-22
CA2818935A1 (fr) 2011-12-29
PT2585564T (pt) 2017-11-03

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