US20220372392A1 - Use of a sterically hindered aromatic amine or phenol compound as an anti-corrosion additive in a lubricant composition for a propulsion system of an electric or hybrid vehicle - Google Patents

Use of a sterically hindered aromatic amine or phenol compound as an anti-corrosion additive in a lubricant composition for a propulsion system of an electric or hybrid vehicle Download PDF

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US20220372392A1
US20220372392A1 US17/619,863 US202017619863A US2022372392A1 US 20220372392 A1 US20220372392 A1 US 20220372392A1 US 202017619863 A US202017619863 A US 202017619863A US 2022372392 A1 US2022372392 A1 US 2022372392A1
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amine
sterically hindered
lubricant composition
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Shimin Zhang
Hakim EL-BAHI
Julien Guérin
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TotalEnergies Onetech SAS
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Total Marketing Services SA
TotalEnergies Onetech SAS
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/045Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32Heterocyclic sulfur, selenium or tellurium compounds
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    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/065Phenyl-Naphthyl amines
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/14Electric or magnetic purposes
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

Definitions

  • the present invention relates to the field of lubricant compositions for a propulsion system of an electric or hybrid vehicle.
  • the invention more particularly relates to the use of compounds bearing at least one sterically hindered amine or phenol function for improving the anticorrosion properties of a lubricant composition incorporating one or more amine-based and/or sulfur-based antiwear additives.
  • the term “electric vehicle” denotes a vehicle comprising an electric motor as sole means of propulsion, as opposed to a hybrid vehicle which comprises a combustion engine and an electric motor as combined means of propulsion.
  • propulsion system denotes a system comprising the mechanical parts required for propelling an electric vehicle.
  • the propulsion system thus more particularly encompasses an electric motor or the rotor-stator assembly of the power electronics (dedicated to regulating the speed), a transmission and a battery.
  • lubricant compositions also known as “lubricants”, for the main purposes of reducing the friction forces between the various parts of the propulsion system of the vehicle, notably between the metal parts in motion in the motors.
  • lubricant compositions are also effective for preventing premature wear or even damage of these parts, and in particular of their surface.
  • a lubricant composition is conventionally composed of one or more base oils which are generally combined with several additives intended for stimulating the lubricant performance of the base oil, for instance friction-modifying additives, but also for affording additional performance.
  • antiwear additives are considered in order to reduce the wear of the mechanical parts of the motor, and thus to prevent degradation of the durability of the motor.
  • antiwear additives exists, among which mention may be made, for example, of dimercaptothiadiazoles, polysulfides, notably sulfur-based olefins, amine phosphates, or else phospho-sulfur additives, for instance metal alkylthiophosphates, in particular zinc alkylthiophosphates and more specifically zinc dialkyldithiophosphates or ZnDTP.
  • antiwear additives the ones that are notably favored are amine-based and/or sulfur-based antiwear agents, such as dimercaptothiadiazoles, zinc dithiophosphate or polysulfides.
  • amine-based and/or sulfur-based antiwear additives such as dimercaptothiadiazoles
  • dimercaptothiadiazoles have the drawback of being corrosive.
  • the problem of corrosion is particularly critical in electric propulsion systems.
  • corrosion can lead to a risk of deterioration of the stator and rotor windings, the sensors in the propulsion system, the solenoid valves in the hydraulic system, but also of the rolling bearings between the rotor and stator of an electric motor, which are generally copper-based and thus particularly susceptible to corrosion, or to the seals or varnishes in the propulsion system.
  • the present invention is directed, specifically, towards overcoming this drawback.
  • the lubricant in order to be able to cool the propulsion systems of electric or hybrid vehicles, it is essential that the lubricant be insulating in order to avoid any failure in the electrical components.
  • a conductive lubricant can lead to a risk of electrical current leakage in the stator and rotor windings, which thus reduces the efficiency of the propulsion systems, and creates possible overheating of the electrical components, even to the point of damaging the system.
  • the present invention is specifically directed toward obtaining such properties
  • the present invention relates to the use of at least one compound bearing at least one sterically hindered amine or phenol function, as an anticorrosion additive in a lubricant composition intended for a propulsion system of an electric or hybrid vehicle and comprising one or more amine-based and/or sulfur-based antiwear additives.
  • the compounds bearing at least one sterically hindered amine or phenol function in particular bearing only one sterically hindered amine or phenol function, are referred to in the rest of the text as “compounds bearing a sterically hindered amine or phenol function”.
  • the compounds bearing a sterically hindered amine or phenol function for instance hindered aromatic amines or phenols, notably alkylphenols, are already described for their function as antioxidants, for example in engine lubricants, as described, for example, in patent application WO 2006/064 138.
  • These antioxidants generally make it possible to retard the degradation of the composition in service. This degradation may notably be reflected by the formation of deposits, the presence of sludges, or an increase in the viscosity of the composition.
  • Antioxidants are capable of capturing the free radicals formed during the use of the lubricant, thus making it possible to interrupt the chain reactions liable to lead to the accumulation of acids.
  • the addition of at least one compound bearing a sterically hindered amine or phenol function, in particular of aromatic amine or alkylphenol type, can advantageously improve the anticorrosion properties of a lubricant composition comprising one or more amine-based and/or sulfur-based antiwear additives.
  • anticorrosion additive denotes an additive for preventing or reducing the corrosion of metal parts.
  • An anticorrosion additive used in a composition thus makes it possible to improve the “anticorrosion” properties of said composition.
  • a composition according to the invention thus simultaneously has good antiwear and anticorrosion properties.
  • the corrosive (or corroding) power of a compound may be evaluated by means of a test which studies the variation in the electrical resistance value of a copper w % ire of a preestablished diameter, as a function of the duration of immersion of this wire in a composition comprising said test compound in a noncorrosive medium, for example in one or more base oils.
  • the variation in this electrical resistance value is directly correlated with the variation in the diameter of the test wire.
  • a compound is termed “noncorrosive” when the loss of diameter of the copper wire studied is less than or equal to 2 ⁇ m after immersion for 80 hours, in particular less than or equal to 0.3 ⁇ m after immersion for 20 hours in the composition comprising said compound.
  • the dielectric properties of a lubricant are notably represented by the electrical resistivity and the dielectric loss (tan ⁇ ) and may be measured according to the standard IEC 60247.
  • the electrical resistivity represents the capacity of a material to oppose the circulation of an electric current. It is expressed in ohm-metres ( ⁇ .m). The resistivity must not be low to prevent electrical conduction.
  • the electric dissipation factor or the loss angle tangent also make it possible to measure the properties of a lubricant.
  • the loss angle ⁇ is the complementary angle ⁇ f the phase shift between the applied voltage and the alternating current. This factor reflects the Joule-effect energy losses. Heating is thus directly linked to the ⁇ value.
  • a transmission oil typically has a tan ⁇ value of the order of unity at ambient temperature.
  • a good insulating lubricant must maintain a low tan ⁇ level.
  • the compound bearing a sterically hindered amine or phenol function according to the invention used according to the invention is chosen from aromatic amines, in particular diarylamine compounds and more particularly diphenylamine compounds; sterically hindered phenols, in particular alkylphenols; and mixtures thereof.
  • the compound bearing a sterically hindered amine or phenol function is chosen from substituted diphenylamines, which are in particular substituted on at least one of the positions para to the amine function with at least one alkyl or alkenyl group comprising from 1 to 12 carbon atoms, preferably from 3 to 10 carbon atoms.
  • said compound may be p,p′-butyloctyldiphenylamine.
  • the compound bearing a sterically hindered amine or phenol function is chosen from compounds comprising a phenol group, of which at least one carbon vicinal to the carbon bearing the alcohol function is substituted with at least one group chosen from an optionally substituted C 1 -C 10 alkyl group and a hydroxyl function.
  • said compound may be octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or 2,6-di-tert-butylphenol.
  • a lubricant composition intended for a propulsion system of an electric or hybrid vehicle of one or more compounds bearing a sterically hindered amine or phenol function according to the invention thus advantageously permits the use, in the composition, of amine-based and/or sulfur-based antiwear additives, such as dimercaptothiadiazoles, without, however, entailing an adverse corrosive effect.
  • amine-based and/or sulfur-based antiwear additives such as dimercaptothiadiazoles
  • amine-based and/or sulfur-based antiwear additives used in a lubricant composition according to the invention are more particularly detailed in the text hereinbelow. They are preferably chosen from amine-based and sulfur-based antiwear additives. They may preferably be thia(di)azole compounds, in particular dimercaptothiadiazole derivatives.
  • composition that is suitable for use in the invention has the advantage of being easy to formulate. Besides good antiwear and anticorrosion performance, it has good stability, notably with respect to oxidation, and also good properties in terms of electrical insulation.
  • the present invention also relates to the use, for lubricating a propulsion system of an electric or hybrid vehicle, in particular for lubricating the electric motor and the power electronics of an electric or hybrid vehicle, of a lubricant composition
  • a lubricant composition comprising:
  • a subject of the present invention is also a process for lubricating a propulsion system of an electric or hybrid vehicle, comprising at least one step of placing at least one mechanical part of said system in contact with a lubricant composition comprising at least one compound bearing a sterically hindered amine or phenol function as defined in the invention, as anticorrosion additive and at least one amine-based and/or sulfur-based antiwear additive as defined in the invention.
  • a lubricant composition according to the invention is used for lubricating the electric motor itself, in particular the rolling bearings located between the rotor and the stator of an electric motor, and/or the transmission, in particular the reducer, in an electric or hybrid vehicle.
  • FIG. 1 schematically represents a propulsion system of an electric or hybrid vehicle.
  • the additive used as anticorrosion agent according to the invention, together with one or more amine-based and/or sulfur-based antiwear additives, in a lubricant composition for the powertrain system of an electric or hybrid vehicle is a compound bearing at least one sterically hindered amine or phenol function.
  • the compounds bearing a sterically hindered amine or phenol function are known to those skilled in the art, in the field of lubricants, for their antioxidant action. These compounds are capable of acting as radical inhibitors.
  • sterically hindered function means that the function is hindered by a steric effect or constraint. The effect of this hindrance is to make the amine or phenol function significantly less nucleophilic than the unhindered amine or phenol function, and thus to prevent nucleophilic addition reactions.
  • the compounds bearing a hindered amine function may be chosen more particularly from aromatic amines, in particular as defined in the text hereinbelow.
  • the compounds bearing a hindered phenol function are preferably chosen from sterically hindered phenols, in particular alkylphenols, in particular as defined in the text hereinbelow.
  • said compound(s) bearing a hindered amine or phenol function are chosen from aromatic amines, sterically hindered phenols, and mixtures thereof.
  • the compounds of aromatic amine type may have the formula:
  • R 3 and R 5 represent, independently of each other, a hydrogen atom, a C 1-20 and preferably C 4-16 aliphatic group, or an aromatic or heteroaromatic, monocyclic or fused polycyclic, substituted or unsubstituted group;
  • R 5 is an aromatic or heteroaromatic, monocyclic or fused polycyclic group, which is unsubstituted or bears at least one C 1-20 alkyl substituent;
  • R 3 and R 5 together form an aromatic or heteroaromatic, monocyclic or fused polycyclic group.
  • the aromatic amines may be chosen more particularly from substituted or unsubstituted diphenylamines, substituted or unsubstituted phenylnaphthylamines, substituted or unsubstituted phenothiazines, substituted or unsubstituted imidodibenzyls, substituted or unsubstituted N,N′-diphenyl(phenylenediamines), and mixtures thereof.
  • the compounds bearing a hindered amine function are chosen from secondary amines in which the nitrogen atom is linked to at least one aryl group, preferably to at least one phenyl group.
  • the compound bearing a hindered amine function is chosen from diarylamine compounds, in particular in which at least one of the aryl groups is a phenyl, and more particularly diphenylamine compounds.
  • the compound bearing a hindered amine function is a compound of aromatic amine type chosen from diarylamines, preferably corresponding to the formula.
  • R 6 , and R 7 are chosen, independently of each other, from:
  • the compound bearing a hindered amine or phenol function is chosen from diphenylamine compounds, which are preferably substituted, in particular substituted on at least one of the positions para to the amine function with at least one alkyl or alkenyl group comprising from 1 to 12 carbon atoms, preferably from 3 to 10 carbon atoms.
  • the compound bearing a hindered amine function may advantageously be of formula (I) below:
  • R 1 and R 2 are chosen, independently of each other, from a hydrogen atom, linear or branched alkyl or alkenyl groups, preferably alkyl groups, comprising from 1 to 12 carbon atoms, preferably from 3 to 10 carbon atoms.
  • the compound bearing a hindered amine function is of the abovementioned formula (I), in which at least one from among R 1 and R 2 is a linear or branched alkyl or alkenyl group, preferably an alkyl group, comprising from 1 to 12 carbon atoms, preferably from 3 to 10 carbon atoms.
  • said compound is of the abovementioned formula (I), in which R 1 and R 2 are chosen, independently of each other, from linear or branched alkyl or alkenyl groups, preferably alkyl groups, comprising from 1 to 12 carbon atoms, preferably from 3 to 10 carbon atoms.
  • R 1 and R 2 are in the para position relative to the amine function.
  • the compound bearing a hindered amine function may advantageously be of formula (I′):
  • R 1 and R 2 are as defined previously.
  • R 1 and R 2 which may be identical or different, represent linear or branched C 1 to C 12 and preferably C 3 to C 10 alkyl groups, for example chosen from linear or branched octyl and butyl groups.
  • the compounds bearing a hindered amine function may be commercially available or prepared according to synthetic methods known to those skilled in the art.
  • the compounds bearing a hindered amine or phenol function may also be compounds of sterically hindered phenol type.
  • the compounds of sterically hindered phenol type are preferably compounds including a phenol group, of which at least one carbon atom other than the one bearing the hydroxyl function and forming part of the phenyl group bears a hydroxyl radical, a linear or branched C 1-10 alkyl, a dialkylaminoalkyl group or a styryl group.
  • the sterically hindered phenols are chosen from compounds comprising a phenol group, in which at least one carbon vicinal to the carbon bearing the alcohol function is substituted with at least one group chosen from a C 1 -C 10 alkyl group and a hydroxyl function.
  • the compound bearing a hindered phenol function may be a sterically hindered phenol of formula (II) below:
  • R 1 and R 2 represents a C 1 -C 10 alkyl group, preferably a C 1 -C 6 alkyl group, preferably a C 4 alkyl group, for example tert-butyl; or a hydroxyl group;
  • the compound bearing a hindered phenol function may be of formula (II′) below:
  • R 1 and R 2 represents a C 1 -C 10 alkyl group, preferably a C 1 -C 6 alkyl group, preferably a C 4 alkyl group, for example tert-butyl; or a hydroxyl group;
  • n an integer between 0 and 3:
  • R being chosen, independently of each other, from C 1 -C 10 alkyl groups, optionally substituted with one or more C 2 to C 10 alkoxycarbonyl groups such as an octyloxycarbonyl group and/or with one or more aryl groups, the aryl group(s) themselves being optionally substituted with one or more alkyl groups; and a hydroxyl group.
  • BHT 2,6-di-t-butyl-4-methylphenol
  • TBHQ t-butylhydroquinone
  • 2,6- and 2,4-di-t-butylphenol 2,6-dimethyl-6-t-butylphenol
  • pyrogallol and octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate alone or as a mixture.
  • the compound of sterically hindered phenol type is chosen from “alkylphenol” compounds, comprising a phenol group bearing on at least one of the positions ortho to the hydroxyl function, preferably on both the ortho positions, a sterically hindered alkyl group, preferably of C 1 to C 10 , in particular C 1 -C 6 , in particular a C 4 alkyl group, preferably tert-butyl.
  • it may be a compound of the abovementioned formula (II), in particular of the abovementioned formula (II′), in which at least one from among R 1 and R 2 , or even both the groups R 1 and R 2 , are chosen from C 1 -C 10 alkyl groups, preferably C 1 -C 6 alkyl groups, preferably a C 4 alkyl group, preferably tert-butyl.
  • the compounds bearing a hindered phenol function may be commercially available or prepared according to synthetic methods known to those skilled in the art.
  • octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or 2,6-di-tert-butylphenol examples of preferred compounds of sterically hindered phenol type.
  • An example of an even more preferred compound of sterically hindered phenol type that may be mentioned is octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate.
  • the compound of sterically hindered aromatic amine or phenol type is chosen from p,p′-butyloctyldiphenylamine, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 2,6-di-tert-butylphenol, and mixtures thereof.
  • the compound of sterically hindered aromatic amine or phenol type is chosen from p,p′-butyloctyldiphenylamine, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and mixtures thereof.
  • the invention is not limited to the compounds of hindered aromatic amine or phenol type described above.
  • Other compound bearing a sterically hindered amine or phenol function notably known as antioxidants, may be used as anticorrosion additives according to the invention.
  • said compound(s) bearing a sterically hindered amine or phenol function used according to the invention are chosen from:
  • a compound bearing a sterically hindered amine or phenol function may be in the form of a mixture of at least two compounds bearing a sterically hindered amine or phenol function, for example a mixture of at least one compound bearing a sterically hindered amine function and of at least one compound bearing a sterically hindered phenol function.
  • the compound(s) bearing a sterically hindered amine or phenol function in particular as defined previously, may be used in a lubricant composition according to the invention in a proportion of from 0.01% to 5% by mass, in particular from 0.1% to 3% by mass and more particularly from 0.1% to 1% by mass relative to the total mass of the lubricant composition.
  • a lubricant composition under consideration according to the invention does not comprise any anticorrosion additives other than the compounds bearing a sterically hindered amine or phenol function.
  • a lubricant composition used according to the invention is free of anticorrosion additives of triazole type or of succinimide type.
  • a lubricant composition under consideration according to the invention comprises one or more amine-based and/or sulfur-based antiwear additives.
  • amine-based and/or sulfur-based antiwear additive denotes an additive chosen from amine-based antiwear additives, sulfur-based antiwear additives and amine-based and sulfur-based antiwear additives.
  • antiwear additive denotes a compound which, when used in a lubricant composition, notably a lubricant composition for a propulsion system of an electric or hybrid vehicle, makes it possible to improve the antiwear properties of the composition.
  • the amine-based and/or sulfur-based antiwear additive may be chosen, for example, from additives of thia(di)azole type, in particular dimercaptothiadiazole derivatives; polysulfide additives, notably sulfur-based olefins, amine phosphates, phospho-sulfur additives such as alkylthiophosphates, and mixtures thereof.
  • a lubricant composition under consideration according to the invention comprises at least one thia(di)azole antiwear additive.
  • Thia(di)azole compounds are compounds which contain both a sulfur atom and at least one nitrogen atom in a five-atom ring. Benzothiazoles are a particular type of thia(di)azoles. This term “thia(di)azole” includes, besides cyclic compounds containing one sulfur atom and one nitrogen atom per five-atom ring, also thiadiazoles which contain sulfur and two nitrogen atoms in such a ring.
  • thia(di)azole compounds may be chosen from benzothiazole derivatives, thiazole derivatives and thiadiazole derivatives.
  • the antiwear additive may be a thiadiazole derivative.
  • Thiadiazoles are heterocyclic compounds comprising two nitrogen atoms, one sulfur atom, two carbon atoms and two double bonds, of general formula C 2 N 2 SH 2 , which may exist in the following forms, respectively: 1,2,3-thiadiazole; 1,2,4-thiadiazole; 1,2,5-thiadiazole; 1,3,4-thiadiazole:
  • the thiadiazole derivative is a dimercaptothiadiazole derivative.
  • a lubricant composition according to the invention comprises at least one antiwear additive chosen from dimercaptothiazole derivatives.
  • dimercaptothiadiazole derivative means chemical compounds derived from the following four dimercaptothiadiazole molecules below: 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, taken alone or as a mixture:
  • the dimercaptothiadiazole derivatives are more particularly molecules or a mixture of molecules based on 4,5-dimercapto-1,2,3-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4-dimercapto-1,2,5-thiadiazole or 2,5-dimercapto-1,3,4-thiadiazole, as represented above, in which at least one of the substitutions ⁇ S, or even both substitutions ⁇ S on the thiadiazole ring is replaced with a substituent:
  • R 1 is chosen from a hydrogen atom, a linear or branched, saturated or unsaturated alkyl group comprising from 1 to 24, preferably from 2 to 18, more preferentially from 4 to 16 and even more preferentially from 8 to 12 carbon atoms or an aromatic substituent.
  • 2,5-dimercapto-1,3,4-thiadiazole as example, the 2,5-dimercapto-1,3,4-thiadiazole derivatives are molecules having the following formulae, taken alone or as a mixture:
  • group(s) R 1 represent, independently of each other, hydrogen atoms, linear or branched alkyl or alkenyl groups comprising from 1 to 24, preferably from 2 to 18, more preferentially from 4 to 16 and even more preferentially from 8 to 12 carbon atoms or aromatic substituents, n being, independently of each other, integers equal to 1, 2, 3 or 4, n preferably being equal to 1.
  • R 1 represent, independently of each other, linear C 1 to C 24 , preferably C 2 to C 18 , notably C 4 to C 16 , more particularly C 8 to C 12 and preferably C 12 alkyl groups.
  • dimercaptothiadiazole derivatives used in the present invention may be commercially available, for example from the suppliers Vanderbilt, Rhein Chemie or Afton.
  • the amine-based and/or sulfur-based antiwear additive(s) used in a lubricant composition according to the invention may also be chosen from sulfur-based antiwear additives of polysulfide type, in particular sulfur-based olefins.
  • the sulfur-based olefins used in a lubricant composition according to the invention may notably be dialkyl sulfides represented by the general formula R a —S x —R b , in which R a and R b are alkyl groups including from 3 to 15 carbon atoms, preferentially from 1 to 5 carbon atoms, preferentially 3 carbon atoms, and x is an integer between 2 and 6.
  • the polysulfide additive is chosen from dialkyl trisulfides.
  • the antiwear additive present in a composition used according to the invention is chosen from amine-based and sulfur-based antiwear additives, and advantageously from thia(di)azole compounds as described above and more preferentially from dimercaptothiadiazole derivatives.
  • a lubricant composition under consideration according to the invention may comprise from 0.01% to 5% by mass, in particular from 0.1% to 3% by mass and more particularly from 0.1% to 1% by mass of amine-based and/or sulfur-based antiwear additive(s), preferably of thia(di)azole type and more preferentially chosen from dimercaptothiadiazole derivatives.
  • antiwear additives notably known for lubricants for propulsion systems, other than amine-based and/or sulfur-based additives, is envisageable, provided that they do not affect the properties imparted by the combination of said compound(s) bearing a sterically hindered amine or phenol function and of said amine-based and/or sulfur-based antiwear additive(s) according to the invention.
  • a lubricant composition required according to the invention is free of antiwear additives other than said amine-based and/or sulfur-based antiwear additive(s) used according to the invention.
  • a lubricant composition under consideration according to the invention combines:
  • a composition used according to the invention may comprise, besides one or more additives bearing a sterically hindered amine or phenol function and one or more amine-based and/or sulfur-based antiwear additives, in particular as defined previously, one or more base oils, and also other additives, conventionally considered in lubricant compositions.
  • a lubricant composition under consideration according to the invention may thus comprise one or more base oils.
  • base oils may be chosen from the base oils conventionally used in the field of lubricant oils, such as mineral, synthetic or natural, animal or plant oils or mixtures thereof.
  • It may be a mixture of several base oils, for example a mixture of two, three or four base oils.
  • the base oils of the lubricant compositions under consideration according to the invention may in particular be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined in the API classification (or equivalents thereof according to the ATIEL classification) and presented in Table 1 below or mixtures thereof.
  • the mineral base oils include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent deparaffinning, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing.
  • Mixtures of synthetic and mineral oils, which may be biobased, may also be used.
  • the base oils of the compositions used according to the invention may also be chosen from synthetic oils, such as certain esters of carboxylic acids and of alcohols, poly- ⁇ -olefins (PAO) and polyalkylene glycols (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
  • the PAOs used as base oils are obtained, for example, from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene.
  • the weight-average molecular mass of the PAO may vary quite broadly. Preferably, the weight-average molecular mass of the PAO is less than 600 Da.
  • the weight-average molecular mass of the PAO may also range from 100 to 600 Da, from 150 to 600 Da or from 200 to 600 Da.
  • the base oil(s) of the composition used according to the invention are chosen from poly- ⁇ -olefins (PAO), polyalkylene glycols (PAG) and esters of carboxylic acids and of alcohols.
  • PAO poly- ⁇ -olefins
  • PAG polyalkylene glycols
  • esters of carboxylic acids and of alcohols are chosen from poly- ⁇ -olefins (PAO), polyalkylene glycols (PAG) and esters of carboxylic acids and of alcohols.
  • the base oil(s) of the composition used according to the invention may be chosen from group II or III base oils.
  • a lubricant composition under consideration according to the invention may comprise at least 50% by mass of base oil(s) relative to its total mass, in particular from 60% to 99% by mass of base oil(s), relative to its total mass.
  • a lubricant composition that is suitable for use in the invention may also comprise any type of additive, different from the additives bearing a sterically hindered amine or phenol function and from the amine-based and/or sulfur-based antiwear additives defined in the context of the present invention, that are suitable for use in a lubricant for a propulsion system of an electric or hybrid vehicle.
  • Such additives which are known to a person skilled in the art in the field of the lubrication and/or cooling of the propulsion systems of electric or hybrid vehicles, may be chosen from friction modifiers, detergents, extreme-pressure additives, antifoams, pour-point depressant additives, dispersants, antioxidants other than the compounds bearing a sterically hindered amine or phenol function according to the invention, pour-point depressants, antifoams and mixtures thereof.
  • a composition that is suitable for use in the invention comprises at least one additional additive chosen from friction modifiers, detergents, extreme-pressure additives, antifoams, pour-point depressant additives, dispersants, antioxidants other than the compounds bearing a sterically hindered amine or phenol function according to the invention, and mixtures thereof.
  • additives may be introduced individually and/or in the form of a mixture such as those already available for sale for commercial lubricant formulations for vehicle engines, with a performance level as defined by the ACEA (Association des Constructeurs Eurofugs d'Automobiles) and/or the API (American Petroleum Institute), which are well known to those skilled in the art.
  • ACEA Association des Constructeurs Eurofugs d'Automobiles
  • API American Petroleum Institute
  • a lubricant composition that is suitable for use in the invention may comprise at least one friction-modifying additive.
  • the friction-modifying additive may be chosen from a compound providing metal elements and an ash-free compound.
  • the compounds providing metal elements mention may be made of complexes of transition metals such as Mo, Sb, Sn, Fe, Cu or Zn, the ligands of which may be hydrocarbon-based compounds comprising oxygen, nitrogen, sulfur or phosphorus atoms.
  • the ash-free friction-modifying additives are generally of organic origin and may be chosen from fatty acid monoesters of polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides, fatty amines or fatty acid esters of glycerol.
  • the fatty compounds comprise at least one hydrocarbon-based group comprising 10 to 24 carbon atoms.
  • a lubricant composition that is suitable for use according to the invention may comprise from 0.01% to 2% by weight or from 0.01% to 5% by weight, preferentially from 0.1% to 1.5% by weight or from 0.1% to 2% by weight of friction-modifying additive, relative to the total weight of the composition.
  • a lubricant composition used according to the invention may comprise at least one antioxidant additive different from the compounds bearing a sterically hindered amine or phenol function as defined according to the invention.
  • the antioxidant additive generally makes it possible to retard the degradation of the composition in service. This degradation may notably be reflected by the formation of deposits, the presence of sludges, or by an increase in the viscosity of the composition.
  • the antioxidant additives notably act as free-radical inhibitors or hydroperoxide destroyers.
  • Antioxidant additives different from the compounds bearing a sterically hindered amine or phenol function may be, for example, copper compounds, for example copper thio- or dithio-phosphates, copper salts of carboxylic acids, and copper dithiocarbamates, sulfonates, phenates and acetylacetonates. Copper I and II salts and succinic acid or anhydride salts may also be used.
  • a lubricant composition used according to the invention may contain any type of antioxidant additive known to those skilled in the art.
  • a lubricant composition used according to the invention may comprise from 0.5% to 2% by weight of at least one antioxidant additive, relative to the total weight of the composition.
  • the lubricant composition used according to the present invention does not comprise any antioxidant different from the compounds bearing a sterically hindered amine or phenol function as defined according to the invention.
  • the detergent additives generally make it possible to reduce the formation of deposits on the surface of metal parts by dissolving the oxidation and combustion byproducts.
  • the detergent additives that may be used in a lubricant composition used according to the invention are generally known to those skilled in the art.
  • the detergent additives may be anionic compounds comprising a long lipophilic hydrocarbon-based chain and a hydrophilic head.
  • the associated cation may be a metal cation of an alkali metal or an alkaline-earth metal.
  • the detergent additives are preferentially chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulfonates, salicylates and naphthenates, and also phenate salts.
  • the alkali metals and alkaline-earth metals are preferentially calcium, magnesium, sodium or barium.
  • metal salts generally comprise the metal in a stoichiometric amount or in excess, thus in an amount greater than the stoichiometric amount. They are then overbased detergent additives; the excess metal giving the overbased nature to the detergent additive is then generally in the form of a metal salt that is insoluble in the oil, for example a carbonate, a hydroxide, an oxalate, an acetate or a glutamate, preferentially a carbonate.
  • a lubricant composition that is suitable for use in the invention may comprise, for example, from 2% to 4% by weight of detergent additive relative to the total weight of the composition.
  • a lubricant composition used according to the invention may comprise at least one dispersant.
  • the dispersant may be chosen from Mannich bases, succinimides and derivatives thereof.
  • a lubricant composition used according to the invention may comprise, for example, from 0.2% to 10% by weight of dispersant(s) relative to the total weight of the composition.
  • a lubricant composition used according to the invention is free of dispersant additive of succinimide type.
  • a lubricant composition that is suitable for use in the invention may also comprise at least one antifoam.
  • the antifoam may be chosen from silicones.
  • a lubricant composition that is suitable for use in the invention may comprise from 0.01% to 2% by mass or from 0.01% to 5% by mass, preferentially from 0.1% to 1.5% by mass or from 0.1% to 2% by mass of antifoam, relative to the total weight of the composition.
  • a lubricant composition that is suitable for use in the invention may also comprise at least one pour-point depressant (PPD).
  • PPD pour-point depressant
  • pour-point depressant additives By slowing down the formation of paraffin crystals, the pour-point depressant additives generally improve the cold-temperature behavior of the composition.
  • pour-point depressant additives include polyalkyl methacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and polyalkylstyrenes.
  • a lubricant composition used according to the invention may be free of anticorrosion additive of triazole type and of dispersant additive of succinimide type.
  • said compound(s) bearing a sterically hindered amine or phenol function may be added to a base oil or mixture of base oils, and the other additional additives, including the amine-based and/or sulfur-based antiwear additive(s), are then added.
  • said compound(s) bearing a sterically hindered amine or phenol function may be added to a pre-existing conventional lubricant formulation, notably comprising one or more base oils, one or more amine-based and/or sulfur-based antiwear additives, and optionally additional additives.
  • said additive(s) bearing a sterically hindered amine or phenol function according to the invention may be combined with one or more additional additives, and the additive “pack” thus formed is added to a base oil or mixture of base oils.
  • a lubricant composition used according to the invention has a kinematic viscosity, measured at 100° C. according to the standard ASTM D445, ranging from 1 to 15 mm 2 /s, in particular ranging from 3 to 10 mm 2 /s.
  • a lubricant composition used according to the invention has a kinematic viscosity, measured at 40° C. according to the standard ASTM D445, ranging from 3 to 80 mm 2 /s, in particular from 15 to 70 mm 2 /s.
  • the electrical resistivity values measured at 90° C. for the lubricant compositions used according to the invention are between 5 and 10 000 Mohm.m, more preferably between 6 and 5000 Mohm.m.
  • the dielectric loss values measured at 90° C. for the lubricant compositions used according to the invention are between 0.01 and 30, more preferably between 0.02 and 25 and more preferentially between 0.02 and 10.
  • a lubricant composition used according to the invention may be of a grade according to the SAEJ300 classification defined by the formula (X)W(Y), in which X represents 0 or 5, and Y represents an integer ranging from 4 to 20, in particular ranging from 4 to 16 or from 4 to 12.
  • a lubricant composition used according to the invention comprises, or even consists of.
  • a lubricant composition used according to the invention comprises, or even consists of:
  • a lubricant composition that is suitable for use in the invention as described previously is used as lubricant for a propulsion system of an electric or hybrid vehicle, and more particularly for the motor and the power electronics.
  • the present invention relates to the use of a lubricant composition as defined previously, combining one or more compounds bearing a sterically hindered amine or phenol function, in particular as defined previously, and one or more amine-based and/or sulfur-based antiwear additives, preferably dimercaptothiazole derivatives, for lubricating a propulsion system of an electric or hybrid vehicle, in particular for lubricating the electric motor and the power electronics of an electric or hybrid vehicle.
  • the electric motor typically comprises power electronics ( 11 ) connected to a stator ( 13 ) and a rotor ( 14 ).
  • the stator comprises coils, in particular copper coils, which are powered by an alternating electric current. This makes it possible to generate a rotating magnetic field.
  • the rotor comprises coils, permanent magnets or other magnetic materials, and is placed in rotation by the rotating magnetic field.
  • a rolling bearing ( 12 ) is generally incorporated between the stator ( 13 ) and the rotor ( 14 ).
  • a transmission, and in particular a speed reducer ( 3 ) makes it possible to reduce the rotation speed at the outlet of the electric motor and to adapt the speed transmitted to the wheels, making it possible simultaneously to control the speed of the vehicle.
  • the invention relates in particular to the use of a composition as described previously for lubricating an electric motor of an electric or hybrid vehicle, in particular for lubricating the rolling bearings located between the rotor and the stator of an electric motor.
  • the invention also relates to the use of a composition as described previously for lubricating the transmission, in particular the reducer, in an electric or hybrid vehicle.
  • composition according to the invention may thus be used for lubricating the various parts of a propulsion system of an electric or hybrid vehicle, in particular the rolling bearings located between the rotor and the stator of an electric motor, and/or the transmission, in particular the reducer, in an electric or hybrid vehicle.
  • a lubricant composition according to the invention has excellent antiwear and anticorrosion performance.
  • the invention also relates to a process for lubricating at least one part of a propulsion system of an electric or hybrid vehicle, in particular the rolling bearings located between the rotor and the stator of an electric motor; and/or the transmission, notably the reducer, comprising at least one step of placing at least said part in contact with a composition as described previously.
  • a composition according to the invention may simultaneously be used for lubricating one or more parts of a propulsion system of an electric or hybrid vehicle, in particular for lubricating the sensors and the solenoid valves of the motor, the rolling bearings, but also the windings located in the rotor and the stator of an electric motor, or else for lubricating the transmission, in particular the gears, the sensors, the solenoid valves or the reducer which are found in an electric or hybrid vehicle, and for electrically insulating at least one part of said propulsion system, notably the battery.
  • a lubricant composition under consideration according to the invention advantageously has a kinematic viscosity, measured at 100° C. according to the standard ASTM D445, of between 2 and 8 mm 2 /s, preferably between 3 and 7 mm 2 /s.
  • composition according to the invention make it possible to define uses according to the invention that are also particular, advantageous or preferred.
  • Compositions C1 to C3 comprise, besides the abovementioned compounds, a group V base oil.
  • compositions and the amounts are indicated in Table 2 below.
  • the corrosive (or corroding) power of a composition may be evaluated by means of a test involving study of the variation in the electrical resistance value of a copper wire of a preestablished diameter, as a function of the duration of immersion of this wire in the composition.
  • the variation in this electrical resistance value is directly correlated with the variation in the diameter of the test wire.
  • the diameter of the wire chosen is 70 ⁇ m.
  • compositions C2 and C3 being compositions according to the invention and composition C1 being a composition serving as a comparative).
  • the resistance of the wire is measured using an ohmmeter.
  • the measuring current is 1 mA.
  • the temperature of the test composition is brought to 150° C.
  • the resistance of the copper wire is calculated by this equation (1):
  • R is the resistance
  • is the resistivity of copper
  • L is the length of the wire
  • S is the cross-sectional area
  • the diameter of the wire is calculated from the cross-sectional area (equation (2)):
  • D is the diameter of the wire.
  • Equation (2) is inserted into equation (1) to obtain the relationship between the resistance and the diameter (equation (3)):
  • the diameter of the wire decreases, thus bringing about an increase in the resistance value.
  • the loss of diameter of the wire is thus calculated directly from the measured resistance.
  • a composition is considered to be “noncorrosive” when the loss of diameter of the copper wire studied is less than or equal to 2 ⁇ m after immersion for 80 hours, in particular less than or equal to 0.3 ⁇ m after immersion for 20 hours in the composition.

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US17/619,863 2019-06-28 2020-06-25 Use of a sterically hindered aromatic amine or phenol compound as an anti-corrosion additive in a lubricant composition for a propulsion system of an electric or hybrid vehicle Pending US20220372392A1 (en)

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FR1907146A FR3097870B1 (fr) 2019-06-28 2019-06-28 Utilisation d’un composé de type amine aromatique ou phénol stériquement encombré à titre d’additif anticorrosion dans une composition lubrifiante
PCT/EP2020/067822 WO2020260460A1 (fr) 2019-06-28 2020-06-25 Utilisation d'un composé de type amine aromatique ou phénol stériquement encombré à titre d'additif anticorrosion dans une composition lubrifiante destinée à un système de propulsion d'un véhicule électrique ou hybride

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EP3990588A1 (fr) 2022-05-04
ES2980465T3 (es) 2024-10-01
FR3097870A1 (fr) 2021-01-01
CN114096647A (zh) 2022-02-25
MX2021015550A (es) 2022-02-16
KR20220032058A (ko) 2022-03-15
FR3097870B1 (fr) 2022-01-14
WO2020260460A1 (fr) 2020-12-30
JP2022538640A (ja) 2022-09-05

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