US20230220294A1 - Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound - Google Patents

Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound Download PDF

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US20230220294A1
US20230220294A1 US17/916,162 US202117916162A US2023220294A1 US 20230220294 A1 US20230220294 A1 US 20230220294A1 US 202117916162 A US202117916162 A US 202117916162A US 2023220294 A1 US2023220294 A1 US 2023220294A1
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alkyl
compound
moiety
carboxylate
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Chantal Boyer
Benoît THIEBAUT
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TotalEnergies Onetech SAS
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
    • 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
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2030/54—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
    • C10N2040/25—Internal-combustion engines

Definitions

  • the invention relates to the field of lubricant compositions, in particular to the fuel economy (FE or “fuel eco”) properties of lubricant compositions. More specifically, the invention concerns an additive composition which makes it possible to maintain the fuel economy properties of a lubricant composition (FE retention or “fuel eco retention”) over time. The invention also relates to the use in a lubricant composition of an additive composition according to the invention as well as the resulting lubricant composition.
  • the operating conditions for gasoline and diesel engines include both extremely short and long journeys. Indeed, 80% of car journeys in Western Europe are less than 12 kilometers, while some vehicles cover annual distances of up to 300,000 km.
  • Oil change intervals also vary widely, from 5,000 km for some small diesel engines to up to 100,000 km for modern commercial diesel engines.
  • Lubricant compositions for motor vehicles must be adaptable to all these conditions of use and thus must have improved properties and performance.
  • An essential requirement of engine lubricant compositions is the environmental aspects. It has become essential to reduce fuel consumption in order to reduce CO 2 emissions.
  • Fuel-saving automotive engine lubricant compositions are often referred to as “fuel eco” (FE).
  • the fuel eco performance should be maintained as much as possible. Indeed, a decrease in fuel eco performance reduces the benefits.
  • Friction modifiers such as organomolybdenum compounds are known to be added to lubricant compositions to lower the coefficient of friction. The addition of such compounds results in fuel savings and gives the lubricant FE properties.
  • MoDTC mobdenum dithiocarbamate
  • MoDTC mobdenum dithiocarbamate
  • the organomolybdenum compound such as MoDTC forms two compounds, MoS 2 (lamellar molybdenum disulphide), which reduces friction, and molybdenum trioxide (MoO 3 ) which tends to increase wear.
  • MoS 2 laamellar molybdenum disulphide
  • MoO 3 molybdenum trioxide
  • the Molybdenum forming part of the organomolybdenum compound oxidizes which is responsible for the loss of performance of the organomolybdenum compound over time and therefore a loss of performance of the Fuel Eco lubricant composition (and therefore fuel economy) over time.
  • organic friction modifiers can be used, but they are less effective.
  • An increase in the amount of organomolybdenum compound was also considered.
  • a high molybdenum content represents a considerable additional formulation cost.
  • the lubricant compositions are no longer stable, and these stability problems result in a high risk of engine fouling and/or engine corrosion, especially in copper engines.
  • a further objective of the present invention is to provide a lubricant composition that maintains a low coefficient of friction over time.
  • a further objective of the present invention is to provide a solution to the decrease in efficiency of the organomolybdenum compound over time.
  • a further objective of the present invention is to provide a compound that protects the organomolybdenum compound of a lubricant composition from degradation over time, particularly by oxidation.
  • the invention relates firstly to a lubricating oil additive composition
  • a lubricating oil additive composition comprising:
  • the invention also relates to a lubricant composition
  • a lubricant composition comprising:
  • the invention finally relates to the use of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound in a lubricant composition
  • a lubricant composition comprising at least one base oil and at least one organomolybdenum compound, preferably chosen from dinuclear organomolybdenum compounds.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound is used to maintain the fuel economy of an internal combustion engine over time.
  • the mass ratio between the organomolybdenum compound and the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound ranges from 1:100 to 100:1, preferably from 1:10 to 10:1, more preferably from 1:5 to 5:1.
  • the organomolybdenum compound is chosen from dinuclear organomolybdenum compounds, preferably from molybdenum dithiocarbamates.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound is selected from compounds of the following formula (IV):
  • R′ is a C 1 -C 34 alkyl moiety substituted with at least one C 1 -C 34 alkyl carboxylate moiety, preferably at least two C 1 -C 34 alkyl carboxylate moieties.
  • the moiety R′ is a C 1 -C 30 , preferably C 1 -C 20 , more preferably C 1 -C 10 , typically a C 1 -C 5 alkyl moiety, for example is an ethyl moiety.
  • the alkyl carboxylate moiety(-ies) are independently selected from C 1 -C 30 , preferably C 1 -C 20 , more preferably C 1 -C 10 , alkyl carboxylate moieties, for example is a 2-ethylhexyl moiety.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound has the following formula (V):
  • the lubricant composition comprises from 50% to 99.5% by weight of base oil(s) relative to the total weight of the lubricant composition.
  • the content of the element molybdenum in the lubricant composition ranges from 50 to 1,500 ppm by weight, preferably from 100 to 1,000 ppm by weight, compared to the total weight of the lubricant composition.
  • the lubricant composition comprises from 0.2% to 1.0% by weight of 2,5-dimercapto-1,3,4-thiadiazole, alkyl (poly)carboxylate compound, preferably from 0.2% to 0.9% by weight, e.g. 0.5% by weight, compared to the total weight of the lubricant composition.
  • the lubricant composition has a sulphur content ranging from 0.01% to 5% by weight, preferably from 0.1% to 2% by weight, more preferably from 0.1% to 0.5% by weight, compared to the total weight of the composition.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound is more thermally stable than other sulphur compounds used in lubricant compositions such as a polysulphide compound or a phospho-sulphur compound.
  • the presence of the compound 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate in a lubricant composition comprising an organomolybdenum compound, such as molybdenum dithiocarbamate, also called MoDTC, enables the oxidation of molybdenum to be reduced or even protected from oxidation and promotes the sulphurisation of the organomolybdenum compound and the sulphurised by-products of molybdenum and thus maintains the properties of the organomolybdenum compound, such as MoDTC, over time.
  • organomolybdenum compound such as molybdenum dithiocarbamate
  • FIG. 1 shows the evolution of the coefficient of friction of a composition according to the invention and a reference composition as a function of the engine operating time.
  • the invention relates to a lubricating oil additive composition
  • a lubricating oil additive composition comprising:
  • the invention also relates to a lubricant composition
  • a lubricant composition comprising:
  • An organomolybdenum compound according to the invention means any fat-soluble organomolybdenum compound.
  • the organomolybdenum compound according to the present invention may be selected from organic molybdenum complexes comprising at least one chemical element molybdenum (Mo), preferably at least two chemical elements molybdenum (Mo), and at least one ligand such as a carboxylate ligand, an ester ligand, an amide ligand, a dithiophosphate ligand, a dithiocarbamate ligand.
  • Mo chemical element molybdenum
  • Mo chemical elements molybdenum
  • ligand such as a carboxylate ligand, an ester ligand, an amide ligand, a dithiophosphate ligand, a dithiocarbamate ligand.
  • organic complexes of molybdenum with carboxylates, esters and amides can be obtained by reacting molybdenum oxide or ammonium molybdates with fats, glycerides, fatty acids or fatty acid derivatives (esters, amines, amides, etc.).
  • carboxylate ligands, ester ligands and amide ligands are free of sulphur and phosphorus.
  • the organomolybdenum compound of the invention is selected from complexes of molybdenum with amide ligands, mainly prepared by reacting a source of molybdenum, which can be for example molybdenum trioxide, and an amine derivative, and fatty acids comprising for example from 4 to 36 carbon atoms such as for example fatty acids contained in vegetable or animal oils.
  • a source of molybdenum which can be for example molybdenum trioxide, and an amine derivative
  • fatty acids comprising for example from 4 to 36 carbon atoms such as for example fatty acids contained in vegetable or animal oils.
  • the organomolybdenum compound is selected from dinuclear organomolybdenum compounds.
  • dinuclear organomolybdenum compound means organomolybdenum compounds with two molybdenum atoms in the nucleus. They are also known as dimeric organomolydbene compounds.
  • the organomolybdenum compound is selected from organic complexes of molybdenum with amide ligands obtained by the reaction of:
  • molybdenum source selected from molybdenum trioxide or molybdates, preferably ammonium molybdate.
  • the organomolybdenum compound may comprise from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, more preferably from 2 to 8.5% by weight of molybdenum compared to the total weight of the organomolybdenum complex.
  • the organomolybdenum compound comprises at least one organic molybdenum complex of formula (I) or (II), alone or in mixture:
  • organic molybdenum complex of formula (I) or (II) is prepared by the reaction of:
  • the organic molybdenum complex of formula (I) consists of at least one compound of formula (I-a) or (I-b), alone or as a mixture:
  • Molyvan 855® marketed by the company Vanderbilt.
  • the organomolybdenum compound is selected from organic complexes of molybdenum with dithiophosphate ligands or organic complexes of molybdenum with dithiocarbamate ligands.
  • organic complexes of molybdenum with dithiophosphate ligands are also referred to as molybdenum dithiophosphates or Mo-DTP compounds and organic complexes of molybdenum with dithiocarbamate ligands are also referred to as molybdenum dithiocarbamates or Mo-DTC compounds.
  • the organomolybdenum compound is selected from molybdenum dithiocarbamate.
  • Mo-DTC compounds are complexes formed by a molybdenum metal core bound to one or more ligands, the ligand being an alkyl dithiocarbamate moiety. These compounds are well-known to the skilled person.
  • the Mo-DTC compound may comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of molybdenum, compared to the total weight of the Mo-DTC compound.
  • the Mo-DTC compound may comprise from 1 to 40%, preferably from 2 to 30%, more preferably from 3 to 28%, advantageously from 4 to 15% by weight of sulphur, compared to the total weight of the Mo-DTC compound.
  • the Mo-DTC compound is a dimeric Mo-DTC compound.
  • dimeric Mo-DTC compounds are the compounds and their preparation methods as described in EP 0757093, EP 0719851, EP 0743354 or EP 1013749.
  • Dimeric Mo-DTC compounds generally correspond to compounds of formula (III):
  • Alkyl moiety within the meaning of the invention means a linear or branched, saturated or unsaturated hydrocarbon moiety comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms.
  • the alkyl moiety is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl tert-butyl, n-pentyl, iso-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-ethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-oct
  • Alkenyl moiety in the sense of the present invention means a linear or branched hydrocarbon moiety comprising at least one double bond and comprising from 2 to 24 carbon atoms.
  • the alkenyl moiety may be selected from vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleic.
  • Aryl moiety in the sense of the present invention means a polycyclic aromatic hydrocarbon or an aromatic moiety, whether or not substituted by an alkyl moiety.
  • the aryl moiety may comprise from 6 to 24 carbon atoms.
  • the aryl moiety may be selected from the group consisting of phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, phenylstyrene, p-cumylphenyl and naphthyl.
  • Cycloalkyl moiety in the sense of the present invention means a polycyclic or cyclic hydrocarbon, whether or not substituted by an alkyl moiety.
  • “Cycloalkenyl moiety” in the sense of the present invention means a polycyclic or cyclic hydrocarbon, whether or not substituted by an alkyl moiety, and comprises at least one double bond.
  • Cycloalkyl moieties and cycloalkenyl moieties may comprise from 3 to 24 carbon atoms.
  • cycloalkyl moieties and cycloalkenyl moieties may be selected, without limitation, from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl.
  • R 3 , R 4 , R 5 and R 6 which may be the same or different, independently represent an alkyl moiety comprising from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, or an alkenyl moiety comprising from 2 to 24 carbon atoms.
  • X 3 , X 4 , X 5 and X 6 may be identical and may represent a sulphur atom.
  • X 3 , X 4 , X 5 and X 6 may be identical and may be an oxygen atom.
  • X 3 and X 4 may represent a sulphur atom and X 5 and X 6 may represent an oxygen atom.
  • X 3 and X 4 may represent an oxygen atom and X 5 and X 6 may represent a sulphur atom.
  • the ratio of the number of sulphur atoms to the number of oxygen atoms (S/O) of the Mo-DTC compound may vary from (1/3) to (3/1).
  • the Mo-DTC compound of formula (III) may be selected from a symmetrical Mo-DTC compound, an asymmetrical Mo-DTC compound and a combination thereof.
  • “Symmetric Mo-DTC compound” means a Mo-DTC compound of formula (V) in which the moieties R 3 , R 4 , R 5 and R 6 are identical.
  • Asymmetric Mo-DTC compound according to the invention means an Mo-DTC compound of formula (V) in which the moieties R 3 and R 4 are identical, the moieties R 5 and R 6 are identical and the moieties R 3 and R 4 are different from the moieties R 5 and R 6 .
  • the Mo-DTC compound is a mixture of at least one symmetric Mo-DTC compound and at least one asymmetric Mo-DTC compound.
  • R 3 and R 4 which are identical, represent an alkyl moiety comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms
  • R 5 and R 6 which are identical, represent an alkyl moiety comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms
  • the moieties R 3 and R 4 are identical or different from the moieties R 5 and R 6 .
  • R 3 and R 4 which are identical, represent an alkyl moiety comprising from 6 to 10 carbon atoms and R 5 and R 6 , which are identical, represent an alkyl moiety comprising from 10 to 15 carbon atoms, and the moieties R 3 and R 4 are different from the moieties R 5 and R 6 .
  • R 3 and R 4 which are identical, represent an alkyl moiety comprising from 10 to 15 carbon atoms and R 5 and R 6 , which are identical, represent an alkyl moiety comprising from 6 to 10 carbon atoms, and the moieties R 3 and R 4 are different from the moieties R 5 and R 6 .
  • R 3 , R 4 , R 5 and R 6 which are identical, represent an alkyl moiety comprising from 5 to 15 carbon atoms, preferably from 8 to 13 carbon atoms.
  • the Mo-DTC compound is selected from compounds of formula (III) in which:
  • the Mo-DTC compound is selected from the compounds of formula (III-a)
  • the Mo-DTC compound is a mixture:
  • Mo-DTC compounds are Molyvan L®, Molyvan 807® or Molyvan 822® marketed by the R.T. Vanderbilt Company® or the products Sakura-lube 200®, Sakura-lube 165®, Sakura-lube 525® or Sakura-lube 600® marketed by the company Adeka.
  • the lubricant composition according to the invention comprises from 50 ppm to 1,500 ppm by weight of elemental molybdenum, preferably from 100 ppm to 1,000 ppm by weight, compared to the total weight of the lubricant composition.
  • 2,5-dimercapto-1,3,4 thiadiazole alkyl (poly)carboxylate compound is meant, within the meaning of the invention, a compound derived from 2,5-dimercapto-1,3,4 thiadiazole, of which at least one of the thiol moieties is substituted by an alkyl (poly)carboxylate moiety.
  • alkyl (poly)carboxylate moiety is meant, in the sense of the invention, an alkyl moiety substituted by one or more carboxylate moieties. When substituted with a single carboxylate moiety, it is called an “alkyl carboxylate moiety”. When substituted with at least two carboxylate moieties, it is called an “alkyl polycarboxylate moiety”.
  • only one of the thiol moieties is substituted with an alkyl (poly)carboxylate moiety.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound is selected from compounds of the following formula (IV):
  • the moiety R′ is chosen from C 1 -C 30 , more preferably C 1 -C 20 , even more preferably C 1 -C 10 , and advantageously C 1 -C 5 alkyl moieties, substituted by at least one C 1 -C 34 alkyl carboxylate moiety.
  • the moiety R′ is selected from methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl and neopentyl moieties, substituted by at least one C 1 -C 34 alkyl carboxylate moiety.
  • the moiety R′ is an ethyl moiety substituted by at least one C 1 -C 34 alkyl carboxylate moiety.
  • the alkyl carboxylate moiety is selected from C 1 -C 30 , more preferably C 1 -C 20 , even more preferably C 5 -C 10 alkyl carboxylate moieties.
  • the alkyl moiety of the alkyl carboxylate moiety may be linear, branched or cyclic.
  • the alkyl moiety of the alkyl carboxylate moiety is selected from branched alkyl moieties.
  • the alkyl moiety of the alkyl carboxylate moiety may be saturated or unsaturated.
  • the alkyl moiety of the alkyl carboxylate moiety is saturated.
  • the alkyl carboxylate moiety is a 2-ethylhexyl carboxylate moiety.
  • the moiety R′ is substituted with at least two C 1 -C 34 alkyl carboxylate moieties.
  • the alkyl carboxylate moieties may be the same or different.
  • the alkyl carboxylate moieties are identical.
  • alkyl carboxylate moieties are all 2-ethylhexyl carboxylate moieties.
  • the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound has the following formula (V):
  • Vanlube® 871 CAS no. 12610453-53-8.
  • the organomolybdenum compound and the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound are present in the additive composition according to the invention in a weight ratio ranging from 1:100 to 100:1, preferably from 1:10 to 10:1, more preferably from 1:5 to 5:1.
  • the lubricant oil composition according to the invention comprises from 0.2% to 1.0% by weight of 2,5-dimercapto-1,3,4-thiadiazole, alkyl (poly)carboxylate compound, preferably from 0.2% to 0.9% by weight, e.g. 0.5% by weight, compared to the total weight of the lubricant composition.
  • the base oil used in the lubricant compositions according to the invention may be oils of mineral or synthetic origin belonging to groupings I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) (table 1) or mixtures thereof.
  • Mineral base oils according to the invention include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, de-alkalization, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofining.
  • Mixtures of synthetic and mineral oils can also be used.
  • the base oils of the lubricant compositions according to the invention may also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and from polyalphaolefins.
  • Polyalphaolefins used as base oils are for example obtained from monomers with 4 to 32 carbon atoms, for example from octene or decene, and whose viscosity at 100° C. is between 1.5 and 15 mm2 ⁇ s-1 according to ASTM D445.
  • Their average molar weight is generally between 250 and 3,000 according to ASTM D5296.
  • the lubricant composition according to the invention comprises at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, compared to the total weight of the composition.
  • the lubricant composition according to the invention comprises from 50% to 99.5% by weight of base oils, preferably from 70% to 99.5% by weight of base oils, relative to the total weight of the composition.
  • Preferred additives for the lubricant composition according to the invention are selected from detergent additives, friction modifying additives other than the molybdenum compounds defined above, extreme pressure additives, dispersants, pour point depressants, anti-foaming agents, thickeners and mixtures thereof.
  • the lubricant compositions according to the invention comprise at least one extreme pressure additive, or a mixture.
  • Anti-wear additives and extreme pressure additives protect surface friction by forming a protective film adsorbed on its surfaces.
  • the anti-wear additives are chosen from additives comprising phosphorus and sulphur such as alkylthiophosphate metals, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP.
  • Preferred compounds are of the formula Zn((SP(S)(OR)(OR′)) 2 , wherein R and R′, the same or different, independently represent an alkyl moiety, preferably an alkyl moiety comprising from 1 to 18 carbon atoms.
  • Amine phosphates are also anti-wear additives which can be used in the lubricant compositions according to the invention.
  • the phosphorus atoms provided by these additives can act as a poison for automotive catalytic systems as these additives are ash generators.
  • These effects can be minimized by partially substituting amine phosphates with non-phosphorous additives, such as polysulphides, especially sulphur-containing olefins.
  • the lubricant compositions according to the invention may comprise from 0.01 to 6% by weight, preferably from 0.05 to 4% by weight, more preferably from 0.1 to 2% by weight compared to the total weight of lubricant composition, anti-wear additives and extreme pressure additives.
  • the lubricant compositions according to the invention comprise from 0.01 to 6% by weight, preferably from 0.05 to 4% by weight, more preferably from 0.1 to 2% by weight compared to the total weight of lubricant composition, of anti-wear additives (or anti-wear compounds).
  • compositions according to the invention may comprise at least one friction modifier additive different from the molybdenum compounds of the invention.
  • the friction modifier additives may be selected from compounds providing metallic elements and ash-free compounds.
  • compounds providing metallic elements we can mention transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, whose ligands can be hydrocarbon compounds comprising oxygen, nitrogen, sulphur or phosphorus atoms.
  • Ash-free friction modifier additives are generally of organic origin or may be selected from fatty acid monoesters of polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty epoxide borates, fatty amines or glycerol acid esters.
  • the fatty compounds comprise at least one hydrocarbon moiety comprising 10 to 24 carbon atoms.
  • the lubricant composition according to the invention may comprise anti-wear additives and extreme pressure additives in an amount ranging from 0.01 to 2% by weight or 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight, or from 0.1 to 2% by weight compared to the total weight of lubricant composition.
  • the lubricant composition according to the invention may comprise at least one antioxidant additive.
  • Antioxidant additives generally delay the degradation of the lubricant composition. This degradation may result in the formation of deposits, the presence of sludge or an increase in the viscosity of the lubricant composition.
  • Antioxidant additives act as radical inhibitors or hydroperoxide destroyer inhibitors. Commonly used antioxidants include phenolic antioxidants, amine antioxidants, and sulphur- and phosphorus-containing antioxidants. Some of these antioxidants, for example those containing sulphur and phosphorus, can generate ash. Phenolic antioxidant additives can be ash-free or in the form of neutral or basic metal salts.
  • the antioxidant additives may in particular be selected from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C1-C12 alkyl moiety, N,N′-dialkyl-aryl-diamines and mixtures thereof.
  • the sterically hindered phenols are chosen from compounds comprising a phenol moiety in which at least one of the carbon atoms in the vicinity of the carbon atom bearing the alcohol function is substituted by at least one C1-C10 alkyl moiety, preferably a C1-C6 alkyl moiety, preferably a C4 alkyl moiety, preferably by a ter-butyl moiety.
  • Amino compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives.
  • Examples of amino compounds are aromatic amines, for example aromatic amines of the formula NRaRbRc where Ra represents an aliphatic moiety or an aromatic moiety, optionally substituted, Rb represents an aromatic moiety, optionally substituted, Rc represents a hydrogen atom, an alkyl moiety, an aryl moiety or a moiety of formula RdS(O)zRe in which Rd represents an alkylene moiety or an alkenylene moiety, Re represents an alkyl moiety, an alkenyl moiety or an aryl moiety and z represents 0, 1 or 2.
  • Alkyl phenols containing sulphur or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
  • antioxidant additives are compounds comprising copper, e.g. copper thio- or dithio-phosphates, copper salts of carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.
  • the lubricant compositions according to the invention may also comprise any type of antioxidant known to the person skilled in the art.
  • the lubricant composition comprises at least one ash-free antioxidant additive.
  • the lubricant composition according to the invention comprises from 0.1 to 2% by weight, compared to the total weight of the composition, of at least one antioxidant additive.
  • the lubricant composition according to the invention may also comprise at least one detergent additive.
  • Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving oxidation and combustion by-products.
  • detergent additives that can be used in the lubricant compositions according to the invention are generally known to the person skilled in the art.
  • Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophobic head.
  • the associated cation may be a metal cation of an alkali or alkaline earth metal.
  • the detergent additives are preferably selected from alkali or alkaline earth metals of carboxylic acids, sulphonates, salicylates, naphthenates, and phenate salts.
  • the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
  • metal salts generally contain the metal in a stoichiometric amount or in excess, i.e. in an amount greater than the stoichiometric amount.
  • overbased detergent additives the excess metal giving the overbased character to the detergent is generally in the form of oil-insoluble metal salts, e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • the lubricant composition according to the invention may comprise from 0.5% to 8% or from 2% to 4% by weight of overbased detergent additives relative to the total weight of the lubricant composition.
  • the lubricant composition according to the invention may also comprise at least one pour point depressant additive.
  • the pour point depressant additive By slowing down the formation of paraffin crystals, the pour point depressant additive generally improves the cold behavior of the lubricant composition according to the invention.
  • pour point depressants are alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalene, alkyl polystyrenes.
  • the lubricant composition according to the invention may also comprise a dispersing agent.
  • the dispersing agents may be selected from Mannich bases, succinimides and derivatives thereof.
  • the lubricant composition according to the invention may comprise from 0.2% to 10% by weight of dispersant(s) compared to the total weight of the lubricant composition.
  • the lubricant composition of the present invention may also comprise at least one additional polymer that can improve the viscosity index.
  • additional viscosity index improving polymers are polymeric esters, hydrogenated or non-hydrogenated homopolymers or copolymers of styrene, butadiene and isoprene, polymethacrylates (PMA).
  • PMA polymethacrylates
  • the lubricant composition according to the invention may comprise from 1 to 15% by weight, compared to the total weight of the lubricant composition, of an additive improving the viscosity index.
  • the lubricant composition according to the invention may also comprise at least one thickening agent.
  • the lubricant composition according to the invention may also comprise an anti-foaming agent and a demulsifier.
  • the lubricant composition according to the invention comprises:
  • the lubricant composition according to the invention comprises:
  • the lubricant composition has a sulphur content ranging from 0.01% to 5% by weight, preferably from 0.1% to 2% by weight, more preferably from 0.1% to 0.5% by weight, compared to the total weight of the lubricant composition.
  • the invention also relates to the use of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound to protect an organomolybdenum compound, e.g. MoDTC, from degradation, preferably to protect the organomolybdenum compound, e.g. MoDTC, from oxidation.
  • an organomolybdenum compound e.g. MoDTC
  • the present invention also relates to the use of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound in a lubricant composition comprising at least one base oil and at least one organomolybdenum compound, e.g. an organic complex of molybdenum with dithiocarbamate ligands, to maintain the fuel economy properties of the lubricant composition over time.
  • organomolybdenum compound e.g. an organic complex of molybdenum with dithiocarbamate ligands
  • the present invention also relates to a method for protecting from degradation, in particular by oxidation, the organomolybdenum compound, for example MoDTC, of a lubricating composition comprising at least one base oil and an organomolybdenum compound, for example MoDTC, comprising the addition, to said lubricating composition, of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound.
  • the organomolybdenum compound for example MoDTC
  • the present invention also relates to a method of maintaining over time the fuel economy properties of a lubricating composition comprising at least one base oil and an organomolybdenum compound, e.g. MoDTC, comprising the addition to said lubricating composition of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound.
  • a lubricating composition comprising at least one base oil and an organomolybdenum compound, e.g. MoDTC, comprising the addition to said lubricating composition of a 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound.
  • organomolybdenum compound and for the 2,5-dimercapto-1,3,4-thiadiazole alkyl (poly)carboxylate compound also apply to the different uses defined above.
  • the maintenance of the fuel economy properties of a lubricant composition can typically be assessed by determining the change in the coefficient of friction of the composition during the operation of an engine lubricated with the composition being tested.
  • a sample of the lubricant composition is taken.
  • the coefficient of friction of the composition is then measured by any method known to the skilled person. This can be done, for example, by means of a reciprocating ball-on-flat tribometer. It is understood that the lower the coefficient of friction over time, the more the effects on the fuel economy properties of the lubricant composition are maintained over time.
  • This base oil comprises:
  • the C0 and C1 compositions are prepared by mixing the different components in the amounts shown in Table 2 below.
  • Composition C0 is a reference composition (non-additivated base oil).
  • Composition C1 is a composition according to the invention.
  • the coefficients of friction of the C0 and C1 lubricant compositions are measured under engine test conditions according to the following method.
  • Each lubricant composition (10 Kg) is evaluated in a cleanliness test of a turbocharged petrol engine.
  • the engine has a displacement of 1.6 L for 4 cylinders. Its power is 115 kW.
  • the test cycle time is 30 hours, alternating between idle speed (between 500 and 750 rpm) and heavy traffic speed (between 2,500 and 5,800 rpm).
  • the temperature of the lubricant composition shall be between 50 and 150° C. and the temperature of the water in the cooling system shall be between 50 and 97° C. No draining or topping up of the lubricant composition is carried out during the test. E10 fuel is used.

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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US17/916,162 2020-04-01 2021-03-29 Lubricant composition comprising a 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate compound Pending US20230220294A1 (en)

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FR2003253A FR3108914B1 (fr) 2020-04-01 2020-04-01 Composition lubrifiante comprenant un composé 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate
FR2003253 2020-04-01
PCT/EP2021/058073 WO2021198131A1 (fr) 2020-04-01 2021-03-29 Composition lubrifiante comprenant un composé 2,5-dimercapto-1,3,4-thiadiazole alkyl polycarboxylate

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JP2018062951A (ja) * 2016-10-11 2018-04-19 株式会社Adeka 摩擦低減方法及び摺動機構

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US6017858A (en) * 1993-01-19 2000-01-25 R.T. Vanderbilt Co., Inc. Synergistic organomolybdenum compositions and lubricating compositions containing same
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JP3454593B2 (ja) 1994-12-27 2003-10-06 旭電化工業株式会社 潤滑油組成物
JPH0931483A (ja) 1995-07-20 1997-02-04 Tonen Corp 潤滑油組成物
JP4201902B2 (ja) 1998-12-24 2008-12-24 株式会社Ａｄｅｋａ 潤滑性組成物
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JP2018062951A (ja) * 2016-10-11 2018-04-19 株式会社Adeka 摩擦低減方法及び摺動機構

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FR3108914A1 (fr) 2021-10-08
JP2023519736A (ja) 2023-05-12
KR20220157501A (ko) 2022-11-29
FR3108914B1 (fr) 2022-07-01

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