EP2814918A1 - Compositions lubrifiantes pour transmissions - Google Patents

Compositions lubrifiantes pour transmissions

Info

Publication number
EP2814918A1
EP2814918A1 EP13703847.7A EP13703847A EP2814918A1 EP 2814918 A1 EP2814918 A1 EP 2814918A1 EP 13703847 A EP13703847 A EP 13703847A EP 2814918 A1 EP2814918 A1 EP 2814918A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
group
independently
compound
dithiocarbamate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13703847.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alain Bouffet
Goulven BOUVIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
Total Raffinage Marketing SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Total Raffinage Marketing SA filed Critical Total Raffinage Marketing SA
Publication of EP2814918A1 publication Critical patent/EP2814918A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/54—Fuel economy
    • 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
    • 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
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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 lubricating compositions for transmissions, in particular for manual gearboxes, bridges or double clutches.
  • the lubricant compositions according to the invention simultaneously have in particular good properties of extreme pressure, anti-wear and a low coefficient of friction.
  • additives such as diphosphites, which may be both friction modifiers and anti-wear components, react with the sulfur used as the extreme pressure agent to form thiophosphonic derivatives for example, whose properties are notably different from those of the original molecules.
  • sulfur used as the extreme pressure agent
  • thiophosphonic derivatives for example, whose properties are notably different from those of the original molecules.
  • many extreme-pressure components react with anti-wear additives or friction modifiers to give new chemical entities. These reactions are not controlled and the exact properties of the final product are also not controlled over time. Interactions can occur between the various extreme-pressure / anti-wear / friction modifier additives and lead to antagonistic effects on the final properties of the additive compositions.
  • the applicant company has developed a new lubricant composition comprising at least four essential additives to simultaneously obtain good extreme-pressure, anti-wear, friction and anti-seizing properties.
  • This specific combination of additives is based on the presence of at least one compound comprising a metal dithiocarbamate group, at least one compound comprising an amine dithiocarbamate group, at least one compound comprising a phosphite group and at least one compound comprising a dithiophosphate group.
  • the lubricating composition according to the invention comprising at least one compound comprising a metal dithiocarbamate group, at least one compound comprising an amine dithiocarbamate group, at least one compound comprising a phosphite group and at least one compound comprising a dithiophosphate group, present simultaneously good properties in wear, extreme pressure, friction and anti-seizing.
  • this lubricant composition also has good properties in terms of oxidation and corrosion.
  • the invention relates to a lubricating composition
  • a lubricating composition comprising at least one base oil, at least one compound comprising a dithiocarbamate group, at least one compound comprising a phosphite group and at least one compound comprising a dithiophosphate group, the compound comprising a dithiocarbamate group being a mixed: at least one amine dithiocarbamate of general formula (Ic)
  • R 8 and R 9 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms,
  • Rio, Ru and R12 represent, independently of one another, a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the groups Rio, Ru and R12 is not a hydrogen atom, and
  • R 17 and R 8 independently of one another hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms, M represents a metal cation and n is the valence of the metal cation.
  • composition according to the invention may further comprise another compound comprising at least one dithiocarbamate group.
  • this other compound comprising a dithiocarbamate group is chosen from the group consisting of bisdithiocarbamates, ammonium dithiocarbamates and ester dithiocarbamates, taken alone or as a mixture.
  • the bisdithiocarbamate has the formula (la), in which R 1, R 2 , R 3 and R 4 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, R 5 represents a hydrocarbon group of 1 to 8 carbon atoms:
  • ammonium dithiocarbamate has the formula (Ib), in which R 6 and R 7 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms:
  • the dithiocarbamate ester has the formula (ld) wherein R 13 and R i4 represent independently of the other hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms, R i5 and Ri 6 represent, independently of one another, a hydrocarbon group of 1 to 18 carbon atoms:
  • the lubricating composition comprises from 0.1 to 5% by weight of compounds comprising a dithiocarbamate group, with respect to the total weight of lubricating composition, preferably from 0.2 to 4%, more preferably from 0.3 to 2%, even more preferably from 0.5 to 1%.
  • the lubricating composition comprises from 0.1 to 3% by weight of the mixture of compounds corresponding to formula (Ic) and (1-e), preferably from 0.1 to 2% by weight, advantageously from 0, 5 to 2% by weight.
  • the compound comprising a phosphite group is chosen from phosphite monoesters, phosphite diesters or phosphite triesters, taken alone or as a mixture.
  • the phosphite monoester has the general formula (II-a) in its alcohol and / or ketone form, in which R 19 represents an optionally substituted hydrocarbon group of 1 to 30 carbon atoms:
  • the phosphite diester has the general formula (II-b) in its alcohol and / or ketone form, in which R 20 and R 2 i represent, independently of each other, optionally substituted hydrocarbon groups of 1 to 30 carbon atoms:
  • the phosphite triester has the general formula (II-c) wherein R 22, 2 3 and R 24 each independently of the other hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms :
  • the lubricating composition comprises from 0.1 to 5% by weight of compound comprising a phosphite group, relative to the total weight of lubricating composition, preferably from 0.2 to 4%, more preferably from 0.3 to 2%, even more preferably from 0.5 to 1%.
  • the compound comprising a dithiophosphate group is selected from the group consisting of ammonium dithiophosphates, amine dithiophosphates, ester dithiophosphates and metal dithiophosphates, alone or in admixture.
  • ammonium dithiophosphate has the general formula (III-a), in which R 25 and R 26 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms:
  • the amine dithiophosphate has the general formula (III-b), in which R 27 and R 28 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, R 29 , R 30 and R 3i represent, independently of one another, a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the groups R 29 , R 30 and R 3i is not a hydrogen atom:
  • the ester dithiophosphate has the general formula (III-c), in which R 33 and R 34 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, R 35 and R 36 represent, independently of one another, hydrocarbon groups comprising from 1 to 18 carbon atoms:
  • the metal dithiophosphate has the general formula (III-d), in which R 37 and R 38 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, M represents a metal cation and n is the valence of this metal cation:
  • the lubricating composition comprises from 0.1 to 5% by weight of compound comprising a dithiophosphate group, relative to the total weight of lubricating composition, preferably from 0.2 to 4%, more preferably from 0.3 to 2%, even more preferably from 0.5 to 1%.
  • the lubricating composition further comprises an antioxidant selected from the group consisting of aromatic amines or phenol derivatives.
  • phenol derivatives within the meaning of the present invention is meant any compound comprising at least one phenol or phenoxy group.
  • the lubricating composition further comprising a dispersant derived from polyisobutene.
  • the lubricating composition further comprises a polymer of polymethacrylate type.
  • the lubricating composition has a kinematic viscosity at 100 ° C according to ASTM D445 of between 4 and 40 cSt, preferably between 4.1 and 32.5 cSt, preferably between 6 and 18.5 cSt.
  • the invention also relates to the use of a lubricant composition as defined above for the lubrication of transmissions such as gearboxes, bridges, preferably manual gearboxes of motor vehicles.
  • the lubricant composition is used to reduce the fuel consumption of vehicles, particularly motor vehicles.
  • the invention also relates to the use of at least one compound comprising a dithiocarbamate group, at least one compound comprising a phosphite group and at least one compound comprising a dithiophosphate group in a base oil to improve the properties of wear, extreme pressure, friction and anti-seizing of a lubricating composition, the compound comprising a dithiocarbamate group being a mixture:
  • R 8 and R 9 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms,
  • Rio, Ru and R12 represent, independently of one another, a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the groups Rio, Ru and R12 is not a hydrogen atom, and
  • R 17 and R 8 independently of one another hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms, M represents a metal cation and n is the valence of the metal cation.
  • the lubricating composition consists essentially of at least one base oil, at least one compound comprising a dithiocarbamate group, at least one compound comprising a phosphite group and at least one compound comprising a dithiophosphate group, the compound comprising a dithiocarbamate group being a mixture:
  • R 8 and R 9 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms,
  • Rio, Ru and R12 represent, independently of one another, a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the groups Rio, Ru and R12 is not a hydrogen atom, and
  • R 17 and R 8 independently of one another hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms, M represents a metal cation and n is the valence of the metallic cation.
  • the lubricating composition according to the invention comprises at least one compound comprising a metal dithiocarbamate group and at least one compound comprising an amine dithiocarbamate group.
  • the compound comprising a metal dithiocarbamate group is called “metal dithiocarbamate” and the compound comprising an amine dithiocarbamate is called “amine dithiocarbamate” in the following description.
  • the metal dithiocarbamate is a metal dithiocarbamate of the general formula (1-e) wherein R 17 and R 8 independently of u n of the other hydrocarbon groups, optionally substituted, containing 1 to 30 carbon atoms, M represents a metal cation and n is the valence of this metal cation:
  • the metal is selected from the group consisting of zinc, aluminum, copper, iron, mercury, silver, cadmium, tin, lead, antimony, bismuth, thallium, chromium, molybdenum, cobalt, nickel, tungsten, sodium, calcium, magnesium, manganese and arsenic.
  • the preferred metals are zinc, molybdenum and antimony, preferably zinc and molybdenum, preferably zinc. Mixtures of metals can be used.
  • Metallic dithiocarbamates are neutral as represented in the formula (1-e) or basic when a stoichiometric excess of metal is present.
  • R 17 and R 8 represent independently of the other hydrocarbon groups, optionally substituted, comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, more preferably from 5 to 12 carbon atoms.
  • R 17 and R 8 represent independently of the other hydrocarbon groups, unsubstituted, said hydrocarbon groups may be alkyl, alkenyl, alkynyl comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, more preferably 5 to 12 carbon atoms, phenyl or benzyl.
  • R 17 and R 8 independently of one another linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups comprising 2 to 24 carbon ca rbone, more preferably from 3 to 18 carbon atoms, more preferably from 5 to 12 carbon atoms.
  • R 17 and R 8 independently of one another hydrocarbon groups optionally substituted by one or more heteroatoms such as oxygen atom, nitrogen atom, sulfur atom, the phosphorus atom, preferably with one or more oxygen atoms.
  • Useful metal dithiocarbamates are compounds well known to those skilled in the art. One of the processes for preparing these compounds is described in US Patent 2492314. Suppliers of such additives are, for example, Vanderbilt, Rhein Chemie, Adeka, King Industries.
  • Vanlube ® AZ Vanlube ® EZ
  • Vanlube ® 73 Vanlube ® 73 Super Plus
  • Molyvan ® A Molyvan ® 807, Molyvan ® 822
  • Additin ® RC 6301 Additin ® RC 6320
  • Sakura-Lube ® 200 Sakura-Lube ® 165, Sakura-Lube ® 525, Sakura-Lube ® 600, Na-Lube ® ADTC.
  • the metal dithiocarbamate is a molybdenum dithiocarbamate of formula (Ic-1), in which R 17 and R 8 have the same meaning as in formula (1-e):
  • the metal dithiocarbamate is a zinc dithiocarbamate of formula (le-2), in which R 17 and R 8 have the same meaning as in formula (1-e):
  • Particularly preferred compounds of formula (Ic-2) are such that R 17 and R 8 independently of one another the groups linear alkyl hydrocarbon compounds comprising from 5 to 12 carbon atoms and are, for example, zinc diamyldithiocarbamate and zinc dibutyldithiocarbamate.
  • the amine dithiocarbamate is an amine dithiocarbamate of the general formula (Ic), in which R 8 and R 9 represent, independently of one another, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, Rio, Ru and R 12 independently of one another represent a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the groups Rio, Ru and R 12 is not a hydrogen atom:
  • R 8 and R 9 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 12 carbon atoms.
  • R 8 and R 9 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl or alkynyl groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 24 carbon atoms. 18 carbon atoms, even more preferably 5 to 12 carbon atoms, phenyls or benzyls.
  • R 8 and R 9 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms. more preferably 5 to 12 carbon atoms.
  • R 8 and R 9 represent, independently of one another, hydrocarbon groups optionally substituted with one or more heteroatoms such as the oxygen atom, the nitrogen atom, the sulfur atom, the phosphorus atom, preferably by one or more oxygen atoms.
  • R 10, R 11 and R 12 independently of one another represent a hydrocarbon group 2 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, even more preferably 5 to 12 carbon atoms.
  • Particularly preferred compounds are diamyl amine diamyldithiocarbamate and diamyl amine dibutyldithiocarbamate.
  • the dithiocarbamate is a mixture of the dithiocarbamates of formula (I-c) and (I-e-2) described above.
  • the dithiocarbamate is a mixture of zinc dithiocarbamate and diamylammonium diamyldithiocarbamate.
  • the composition according to the invention may further comprise another compound comprising a dithiocarbamate group.
  • this other dithiocarbamate compound is a bisdithiocarbamate of general formula (Ia), in which R 1, R 2 , R 3 and R 4 represent, independently of each other, optionally substituted hydrocarbon groups comprising 1 to 30 carbon atoms, R 5 represents a hydrocarbon group of 1 to 8 carbon atoms:
  • R 1, R 2 , R 3 and R 4 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferentially from 5 to 12 carbon atoms.
  • R 1, R 2 , R 3 and R 4 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 1, R 2 , R 3 and R 4 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 1, R 2 , R 3 and R 4 independently of one another represent hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably atoms. oxygen.
  • R 5 represents a hydrocarbon group of 2 to 6 carbon atoms.
  • this other dithiocarbamate compound is an ammonium dithiocarbamate of general formula (Ib), in which R 6 and R 7 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to at 30 carbon atoms:
  • R 6 and R 7 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 12 carbon atoms. carbon atoms.
  • R 6 and R 7 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 6 and R 7 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 6 and R 7 represent, independently of each other, hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably with oxygen atoms.
  • another dithiocarbamate compound is a dithiocarbamate ester of general formula (ld) wherein R da ns i3 i4 and R independently of one another hydrocarbon groups, optionally substituted, comprising 1 to 30 carbon atoms, R 15 and R 16 represent, independently of one another, hydrocarbon groups comprising from 1 to 18 carbon atoms:
  • R and R i3 i4 represent independently of the other hydrocarbon groups, optionally substituted, comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, more preferably from 5 to 12 carbon atoms.
  • R and R i3 i4 represent independently of the other hydrocarbon groups, unsubstituted, said hydrocarbon groups may be alkyl, alkenyl, alkynyl, phenyl or benzyl.
  • R and R i3 i4 represent independently of the other hydrocarbon groups linear or branched alkyls, more preferably hydrocarbon groups linear alkyls.
  • R and R i3 i4 represent independently of the other hydrocarbon groups optionally substituted by oxygen, nitrogen, sulfur and / or phosphorus, preferably oxygen atoms.
  • R 15 and R 16 represent, independently of one another, hydrocarbon groups of 2 to 6 carbon atoms.
  • the lubricant composition according to the invention comprises at least one compound comprising a phosphite group.
  • the compound comprising a phosphite group is called "phosphite" in the following description.
  • phosphite is meant a phosphite ester, whether it is a phosphite monoester, a phosphite diester or a phosphite triester, taken alone or in mixture.
  • Phosphite monoesters are found in two equilibrium forms, a "ketone” form and an “alcohol” form. It is the same for the phosphite diesters.
  • a phosphite which may be used may be a phosphite monoester of general formula (IIa) in its alcohol and / or ketone form, in which R 19 represents an optionally substituted hydrocarbon group of 1 to 30 carbon atoms:
  • R i9 represents an optionally substituted hydrocarbon-based group comprising from 2 to 24 carbon atoms, more preferably from 3 to 20 carbon atoms, even more preferentially from 4 to 18 carbon atoms, even more preferably from 6 to 16 carbon atoms. carbon atoms, more preferably 8 to 12 carbon atoms.
  • R 19 represents an unsubstituted hydrocarbon group, said hydrocarbon group possibly being an alkyl, alkenyl, alkynyl, phenyl or benzyl group.
  • R i9 represents a linear or branched alkyl hydrocarbon group, more preferably a linear alkyl hydrocarbon group.
  • R 19 represents a hydrocarbon group substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably oxygen atoms.
  • phosphite monoesters there may be mentioned a I ky I (Ci 0) bisphenol A phosphite, have ky I (C 2 -C 5) bisphenol A phosphite.
  • a phosphite which may be used may also be a phosphite diester of general formula (II-b) in its alcohol and / or ketone form, in which R 2 o and R 2i represent, independently of each other, optionally substituted hydrocarbon groups , from 1 to 30 carbon atoms:
  • R 20 and R 2i represent hydrocarbon groups, optionally substituted, comprising from 2 to 24 carbon atoms, more preferably from 3 to 20 carbon atoms, even more preferably from 4 to 18 carbon atoms, even more preferably from 6 to 16 carbon atoms, more preferably 8 to 12 carbon atoms.
  • R 20 and R 2i represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 20 and R 2i are independently from each other linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 20 and R 2i represent hydrocarbon groups substituted with oxygen, nitrogen, sulfur and / or phosphorus, preferably oxygen atoms.
  • phosphite diesters that may be mentioned include dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, dihexyl phosphite, dicylohexyl phosphite, diisodecyl phosphite, di-n-octyl phosphite, dibenzyl phosphite, diphenyl phosphite, dioleyl phosphite.
  • a usable phosphite triester may also be a phosphite of general formula (II-c) wherein R 22, 2 3 and R 24 each independently of the other hydrocarbon groups, optionally substituted, containing 1 to 30 carbon of carbon:
  • R 22 , R 23 and R 24 preferably represent optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 4 to 18 carbon atoms, and even more preferably preferably from 6 to 16 carbon atoms, more preferably from 8 to 12 carbon atoms.
  • R 22 , R 23 and R 24 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 22 , R 23 and R 24 represent independently of each other linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 22 , R 23 and R 24 represent hydrocarbon groups substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably oxygen atoms.
  • phosphite triesters mention may be made of diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, tridimethylphenyl phosphite, diphenyl ethylhexyl phosphite, phenyl diisodecyl phosphite, triisodecyl phosphite, trilauryl phosphite, triphenyl phosphite, tris (dipropylene glycol).
  • phosphite tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (5-norbornene-2-methyl) phosphite, tris (tridecyl) phosphite, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, triisoctyl phosphite, tribenzyl phosphite, triphenyl phosphite, poly (dipropylene glycol) phenyl phosphite, tris (dipropylene glycol) phosphite.
  • the lubricant composition according to the invention comprises from 0.1 to 5% by weight of phosphite, relative to the total weight of the lubricating composition, preferably from 0.2 to 4%, more preferably from 0.3 to 2%. more preferably from 0.5 to 1%.
  • the lubricating composition according to the invention comprises at least one compound comprising a dithiophosphate group.
  • the compound comprising a dithiophosphate group is called "dithiophosphate" in the following description.
  • a suitable dithiophosphate is a dithiophosphate selected from the group consisting of ammonium dithiophosphates, amine dithiophosphates, ester dithiophosphates and metal dithiophosphates, alone or in admixture.
  • Ammonium dithiophosphates, amine dithiophosphates and ester dithiophosphates have the advantage of being dithiophosphate without ash and in particular without zinc.
  • the dithiophosphate is an ammonium dithiophosphate of general formula (III-a), wherein R 25 and R 2 6 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms:
  • R 25 and R 2 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 18 carbon atoms. 12 carbon atoms.
  • R 25 and R 26 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkenyl, alkynyl, phenyl or benzyl groups.
  • R 25 and R 26 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 25 and R 26 represent, independently of one another, hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably oxygen atoms.
  • Examples of commercial products are ammonium dimethyl dithiophosphates, ammonium diethyl dithiophosphates, ammonium dibutyl dithiophosphates.
  • the dithiophosphate is an amine dithiophosphate of the general formula (III-b), in which R 27 and R 28 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to at 30 carbon atoms, R 29 , R 30 and R 3i represent, independently of one another, a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms, it being understood that at least one of the R groups 29 , R 30 and R 3i is not a hydrogen atom:
  • R 27 and R 28 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 12 carbon atoms. carbon atoms.
  • R 27 and R 28 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 27 and R 28 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 27 and R 28 represent, independently of one another, hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably with oxygen atoms.
  • R 29 , R 30 and R 3i independently of one another represent a hydrocarbon group 2 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, even more preferably 5 to 12 carbon atoms. .
  • the dithiophosphate is an ester dithiophosphate of the general formula (III-c), in which R 33 and R 34 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to at 30 carbon atoms, R 35 and R 36 represent, independently of one another, hydrocarbon groups comprising from 1 to 18 carbon atoms:
  • R 33 and R 34 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 12 carbon atoms. carbon atoms.
  • R 33 and R 34 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 33 and R 34 represent independently of each other linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 33 and R 34 represent, independently of one another, hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably oxygen atoms.
  • R 33 and R 34 represent, independently of one another, a hydrocarbon group of 2 to 6 carbon atoms.
  • R 35 and R 36 represent independently of each other hydrocarbon groups of 2 to 6 carbon atoms.
  • the dithiophosphate is a metal dithiophosphate of general formula (III-d), in which R 37 and R 38 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 1 to 30 carbon atoms, M represents a metal cation and n is the valence of this metal cation:
  • the metal is selected from the group consisting of zinc, aluminum, copper, iron, mercury, silver, cadmium, tin, lead, antimony, bismuth, thallium, chromium, molybdenum, cobalt, nickel, tungsten, sodium, calcium, magnesium, manganese and arsenic.
  • the preferred metals are zinc, molybdenum, antimony, preferably zinc and molybdenum, preferably zinc. Mixtures of metals can be used.
  • Metal dithiophosphates are neutral as exemplified in formula (III-d) or basic when a stoichiometric excess of metal is present.
  • R 37 and R 38 represent, independently of each other, optionally substituted hydrocarbon groups comprising from 2 to 24 carbon atoms, more preferably from 3 to 18 carbon atoms, even more preferably from 5 to 12 carbon atoms. carbon atoms.
  • R 37 and R 38 represent, independently of each other, unsubstituted hydrocarbon groups, said hydrocarbon groups possibly being alkyl, alkenyl, alkynyl, phenyl or benzyl groups.
  • R 37 and R 38 represent, independently of one another, linear or branched alkyl hydrocarbon groups, more preferably linear alkyl hydrocarbon groups.
  • R 37 and R 38 represent, independently of one another, hydrocarbon groups optionally substituted with oxygen, nitrogen, sulfur and / or phosphorus atoms, preferably with oxygen atoms.
  • Useful metal dithiophosphates are compounds well known to those skilled in the art.
  • Additin 3038 RC the RC Additin 3045, the Additin ® RC 3048, the Additin ® RC 3058, the Additin ® RC 3080, the Additin ® RC 3180, Additin ® RC 3212, Additin ® RC 3580, Kikulube ® Z112, Lubrizol ® 1371, Lub zol ® 1375, Lub zol ® 1395, Lub zol ® 5179, Oloa ® 260, Oloa ® 267.
  • the metal dithiophosphate is a molybdenum dithiophosphate of formula (III-d-1), in which R 37 and R 38 have the same meaning as in formula (III-d):
  • the metal dithiophosphate is a zinc dithiophosphate of formula (III-d-2), wherein R 37 and R 38 have the same meaning as in formula (III-d):
  • the lubricating composition according to the invention comprises from 0.1 to 5% by weight of dithiophosphate, relative to the total weight of the lubricating composition, preferably from 0.2 to 4%, more preferably from 0.3 to 2%. more preferably from 0.5 to 1%.
  • the lubricant 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 lubricant 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. 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 polyalphaolefins used as base oils are, for example, obtained from monomers containing from 4 to 32 carbon atoms (for example octene, decene) and a viscosity at 100 ° C. of between 1.5 and 15 cSt according to the standard. ASTM D445. Their weight average molecular weight is typically between 250 and 3000 according to ASTM D5296. Mixtures of synthetic and mineral oils can also be used.
  • a particular lubricating base for producing the lubricating compositions according to the invention must have properties, in particular viscosity, viscosity index, sulfur, oxidation resistance, adapted for use in a gearbox, in particular in a gearbox of motor vehicles, particularly in a manual gearbox.
  • the lubricating bases represent at least 50% by weight, relative to the total mass of the lubricating composition, preferably at least 60%, or at least 70%. Typically, they represent between 75 and 90% by weight, relative to the total mass of the lubricating 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 have a kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard of between 4 and 41 cSt, according to classification SAE J 306, preferably between 4.1 and 32.5 cSt.
  • Preferred grades are all grades from 75W to
  • the lubricant compositions according to the invention have a viscosity index (VI) greater than 120 (ASTM 2270 standard).
  • the lubricating compositions according to the invention may also contain any type of additive suitable for use in transmission oil formulations, for example one or more additives chosen from polymers, antioxidants, corrosion inhibitors, dispersants, present at the usual contents required for the application.
  • the polymers are selected from the group of shear-stable polymers, preferably from the group consisting of copolymers of ethylene and alpha-olefin, polyacrylates such as polymethacrylates, copolymer olefins (OCP), ethylene propylene diene Monomers (EPDM), polybutenes, copolymers of styrene and olefin, hydrogenated or not, copolymers of styrene and acrylate.
  • the preferred polymers are polymethacrylates (PMA).
  • the preferred dispersants are polyisobutylenes (PIB), polyisobutylene succinic anhydride, amino derivatives of polyisobutylene succinic anhydride (PIB succinimides).
  • Preferred antioxidants are, for example, amino antioxidants, preferably diphenylamines, in particular dialkylphenylamines, such as octadiphenylamines, phenyl-alpha-naphthyl amines, or phenolic antioxidants (dibutylhydroxytoluene BHT and derivatives) or sulfur-containing antioxidants
  • the preferred anti-corrosion additives are phenolic derivatives, in particular ethoxylated phenol derivatives substituted with ortho-position alkyl groups.
  • the corrosion inhibitors may be derivatives of dimercaptothiadiazole.
  • the lubricant composition comprises:
  • the lubricant composition comprises:
  • the lubricant composition comprises:
  • the additional additive may be selected from the other additives described above.
  • the other additive may be selected from the group consisting of polymers, antioxidants, corrosion inhibitors, dispersants and mixtures thereof.
  • the other additive is a mixture of at least one antioxidant and at least one dispersant.
  • the other additive is a mixture of at least one polysiobutylene succinimide and at least one dialkylphenylamine.
  • the lubricant composition essentially consists of:
  • the lubricant composition essentially consists of:
  • the lubricant composition consists essentially of:
  • the additional additive may be selected from the other additives described above.
  • the other additive may be selected from the group consisting of polymers, antioxidants, corrosion inhibitors, dispersants and mixtures thereof.
  • the other additive is a mixture of at least one antioxidant and at least one dispersant.
  • the other additive is a mixture of at least one polysiobutylene succinimide and at least one dialkylphenylamine.
  • the invention also relates to a method of lubricating transmissions such as gearboxes, bridges, preferably manual gearboxes of motor vehicles, said method comprising a step of contacting the lubricating composition as defined above with transmissions such as gearboxes.
  • this method simultaneously makes it possible to reduce the wear, to improve the extreme-pressure properties, to reduce the friction and to improve the anti-seizing properties of the lubricant composition.
  • this method makes it possible to reduce the fuel consumption of vehicles, in particular of motor vehicles.
  • the lubricating composition comprises at least one base oil, at least one compound comprising a metal dithiocarbamate group of formula (1-e), at least one compound comprising an amine dithiocarbamate group of formula (lc ), at least one compound comprising a phosphite group, at least one compound comprising a dithiophosphate group, at least one antioxidant and at least one dispersant.
  • a metal dithiocarbamate group of formula (1-e) at least one compound comprising an amine dithiocarbamate group of formula (lc )
  • at least one compound comprising a phosphite group at least one compound comprising a dithiophosphate group
  • at least one antioxidant and at least one dispersant does not impair the extreme-pressure, wear, friction and anti-seize properties, which are always very good and at the same time ensures excellent resistance to oxidation. It is surprising to note that the use of the dispersant makes it possible to significantly improve the resistance to oxidation.
  • Lubricating compositions 1 to 7 are prepared from:
  • a PAO group IV base oil having a viscosity at 100 ° C. of 6 cSt according to the ASTDM D445 standard and a viscosity index equal to 125 according to the ASTM 2270 standard,
  • a phosphite Pi which is di-n-octyl phosphite
  • the roller stroke on the plane that is to say the reciprocating back and forth movement, is set at 7 mm.
  • the duration of the test is 10 min.
  • the reduction of the friction under these test conditions makes it possible to indicate a reduction in shifting forces and friction losses in the gears of the gearbox operating with the type of lubricant studied.
  • the value of the measured coefficient of friction ⁇ , taken at different temperatures, corresponds to the minimum value of the coefficient of friction taken on the average of the 4 charges for the last minute of test.
  • Lubricating compositions 1 to 6 are control lubricating compositions comprising only one or two of the three essential additives to the invention. Lubricating compositions 1 to 6 do not simultaneously have good properties in anti-wear, extreme pressure and friction. Only the composition lubricant 7, which is a lubricant composition according to the invention, has simultaneously good properties in anti-wear, extreme pressure and friction.
  • Example 2
  • Lubricating compositions 8 to 9 according to the invention are then prepared from:
  • a PAO group IV base oil having a viscosity at 100 ° C. of 6 cSt according to the ASTDM D445 standard and a viscosity index equal to 125 according to the ASTM 2270 standard,
  • a dithiocarbamate (Vanlube EZ) which is a mixture of zinc diamyldithiocarbamate and diamylamino dithiocarbamate,
  • a phosphite Pi which is di-n-octyl phosphite
  • compositions 7 to 9 have a very satisfactory extreme-pressure level.
  • the compositions 7 and 8 give a deterioration stage of 12, the composition 9 gives a deterioration stage of 10.
  • This reference oil H comprises 72% by weight of Group I base oil, relative to the weight of oil, 11% by weight of polymer of polymethacrylate type, 8% by weight of PAO , 8% by weight of a package comprising a zinc dialkyldithiophosphate, a dibutyl phosphite, an aryl phosphite and a diphenylamine as an antioxidant.
  • Lubricating compositions 7 to 9 therefore have a better extreme-pressure behavior than this reference oil H since their failure occurs at higher loads.
  • the lubricant compositions 7 to 9 and especially the composition 9 are insensitive to corrosion (copper or steel) and oxidation.
  • Lubricant control compositions 10 to 15 are then prepared from a PAO type IV group base oil having a viscosity at 100 ° C. of 6 cSt according to ASTDM D445 and a viscosity number of 125. according to ASTM 2270,
  • dithiocarbamate which is a mixture of zinc diamyldithiocarbamate and diamylamino diamyldithiocarbamate. This mixture is identical to that used in Example 1,
  • phosphite P 2 which is triphenyl phosphite
  • Additin ® RC 2545 is an extreme-pressure additive, it has the same function as the compound comprising a dithiophosphate group used in the compositions according to the invention.
  • the comparative lubricating composition 16 is prepared on the basis of the composition according to the invention 7 above in which the mixture of metallic dithiocarbamate and amine dithiocarbamate (Vanlube EZ) is replaced by a zinc diamyl dithiocarbamate (Vanlube AZ). .

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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP13703847.7A 2012-02-15 2013-02-14 Compositions lubrifiantes pour transmissions Withdrawn EP2814918A1 (fr)

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FR1251393A FR2986801B1 (fr) 2012-02-15 2012-02-15 Compositions lubrifiantes pour transmissions
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EP3241883B1 (en) 2012-12-28 2018-07-18 Afton Chemical Corporation Lubricant compositions
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
CN109135871B (zh) * 2017-06-27 2021-11-02 中国石油化工股份有限公司 一种重负荷车辆齿轮油组合物及其制备方法
JP7296711B2 (ja) * 2018-10-23 2023-06-23 出光興産株式会社 潤滑油組成物、潤滑油組成物を備える機械装置および潤滑油組成物の製造方法
FR3097870B1 (fr) * 2019-06-28 2022-01-14 Total Marketing Services Utilisation d’un composé de type amine aromatique ou phénol stériquement encombré à titre d’additif anticorrosion dans une composition lubrifiante
FR3097875B1 (fr) * 2019-06-28 2022-03-04 Total Marketing Services Composition lubrifiante pour prévenir la corrosion et/ou la tribocorrosion des pièces métalliques dans un moteur

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US2805996A (en) * 1954-09-20 1957-09-10 Pennsalt Chemicals Corp Process for the production of oil soluble amine complexes and compositions containing such complexes
US5872085A (en) * 1987-04-10 1999-02-16 Froeschmann; Erasmus Lubricant or lubricant concentrate
DE3712132A1 (de) * 1987-04-10 1988-10-20 Grill Max Gmbh Schmiermittel bzw. schmiermittelkonzentrat
JPH0539495A (ja) * 1991-08-05 1993-02-19 Tonen Corp 潤滑油組成物
US5354485A (en) * 1993-03-26 1994-10-11 The Lubrizol Corporation Lubricating compositions, greases, aqueous fluids containing organic ammonium thiosulfates
JPH07197058A (ja) * 1993-12-30 1995-08-01 Tonen Corp 潤滑油組成物
JPH07196603A (ja) * 1993-12-30 1995-08-01 Tonen Corp 塩基性ジチオカルバミン酸金属塩、及び該塩を含有する潤滑油組成物
US5674820A (en) * 1995-09-19 1997-10-07 The Lubrizol Corporation Additive compositions for lubricants and functional fluids
SG64414A1 (en) * 1996-01-16 1999-04-27 Lubrizol Corp Lubricating compositions
JP4246963B2 (ja) * 2002-05-22 2009-04-02 シェブロンジャパン株式会社 潤滑油組成物
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CN104284968B (zh) 2017-03-22
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FR2986801A1 (fr) 2013-08-16
JP6240618B2 (ja) 2017-11-29
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FR2986801B1 (fr) 2014-09-05
CN104284968A (zh) 2015-01-14

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