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WO2025158003A1 - Additive composition for hybrid vehicles - Google Patents

Additive composition for hybrid vehicles

Info

Publication number
WO2025158003A1
WO2025158003A1 PCT/EP2025/051812 EP2025051812W WO2025158003A1 WO 2025158003 A1 WO2025158003 A1 WO 2025158003A1 EP 2025051812 W EP2025051812 W EP 2025051812W WO 2025158003 A1 WO2025158003 A1 WO 2025158003A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfonate
additive composition
detergent
weight
total
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/051812
Other languages
French (fr)
Inventor
Isabelle DI SILVESTRO
Bénédicte Amblard
Paula USSA ALDANA
Jérôme OBIOLS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Onetech SAS
Original Assignee
TotalEnergies Onetech SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TotalEnergies Onetech SAS filed Critical TotalEnergies Onetech SAS
Publication of WO2025158003A1 publication Critical patent/WO2025158003A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • 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
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • the subject of the present invention is an additive composition, in particular for hybrid vehicles, as well as a lubricating composition comprising said additive composition and its use for lubricating in particular hybrid vehicle engines.
  • Hybrid vehicles consist of two engines: a combustion engine and an electric motor.
  • the combustion engine drives the wheels and is assisted by an electric motor.
  • a battery provides the electricity needed to operate the electric motor.
  • this battery is recharged during braking and deceleration by a kinetic energy recovery system (KERS) integrated into the vehicle.
  • KERS kinetic energy recovery system
  • hybrid vehicle technologies There are different hybrid vehicle technologies. These hybrid technologies include:
  • micro-hybrid vehicles also called mild hybridization
  • these vehicles equipped with the “stop&start” system, recover the energy generated by braking to charge a battery which can temporarily assist the thermal engine;
  • Plug-in hybrid vehicles include a combustion engine and an electric motor.
  • the battery can be recharged from the electricity network. These vehicles can therefore drive in 100% electric mode for a distance of several dozen kilometers, for example 50 kilometers.
  • range extender range extender also called a range extender in English
  • only the electric motor drives the wheels. This electric motor is powered by a battery for a few dozen kilometers.
  • the combustion engine starts and drives a current generator to produce the electricity needed to recharge the battery and keep the electric motor running.
  • the combustion engine is used less frequently and therefore operates at lower temperatures (around, or even below, 40°C) than the engines of other types of hybrid vehicles.
  • conventional lubricant compositions are more viscous and the additives are not as active as in a conventional application at higher temperatures.
  • Current lubricants have been optimized to achieve fuel consumption gains when hot.
  • the operation of the internal combustion engine in a hybrid vehicle involves changes in the stresses that the lubricant endures.
  • the temperature of the lubricant in hybrid engines is lower than that of conventional internal combustion vehicles, which results in greater dilution of the lubricant by the fuel as well as water accumulation.
  • the presence of water and gasoline induces the formation of water-oil emulsions in the field and raises the question of its impact on the corrosion performance of the lubricant in operation.
  • the present invention therefore aims to provide a composition exhibiting a reduction in corrosion in hybrid engines.
  • the present invention also aims to provide a lubricating composition improving corrosion performance for hybrid vehicles.
  • the present invention relates to a lubricant additive composition
  • a lubricant additive composition comprising a carboxylate detergent and one or more sulfonate detergent(s).
  • Detergent additives are generally used to reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products.
  • the present invention also relates to a lubricating composition comprising at least one base oil and the aforementioned additive composition.
  • additive composition means a composition before the addition of the base oil to form a lubricating composition.
  • the carboxylates according to the invention are, for example, aliphatic carboxylates (for example, stearates).
  • they can be prepared by reacting a carboxylic acid with a suitable metal compound such as an oxide or a hydroxide.
  • “Sulfonate detergent” means a sulfonate compound with an associated cation which may be a metal cation of an alkali or alkaline earth metal.
  • the sulfonates of the invention may be prepared from sulfonic acids which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from petroleum fractionation or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, diphenyl or their halogenated derivatives. This alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
  • Alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms (e.g., from 16 to 60 carbon atoms) per alkyl-substituted aromatic residue.
  • the alkali and alkaline earth metals of the above-mentioned carboxylates and sulfonates are preferably calcium, magnesium, sodium or barium.
  • the additive composition according to the invention comprises a carboxylate detergent and two sulfonate detergents.
  • the additive composition according to the invention comprises a carboxylate detergent, in particular MOB, a sulfonate detergent LOB and a sulfonate detergent HOB.
  • the carboxylate detergent is chosen from alkali metal or alkaline earth metal salts of carboxylate, and is preferably calcium carboxylate.
  • the carboxylate detergent of the additive composition according to the invention is calcium carboxylate.
  • the carboxylate detergent of the additive composition according to the invention is calcium carboxylate MOB.
  • the sulfonate detergents are chosen from alkali metal or alkaline earth metal sulfonate salts, preferably calcium sulfonate, magnesium sulfonate or their mixture.
  • the sulfonate detergents of the additive composition according to the invention are a mixture of calcium sulfonate and magnesium sulfonate.
  • the sulfonate detergents of the additive composition according to the invention are a mixture of calcium sulfonate LOB and magnesium sulfonate HOB.
  • the carboxylate detergent has a total base number TBN of 120 to 200 mg KOH/g, as measured according to ASTM D-2896, as noted above.
  • the additive composition of the invention comprises a mixture of two sulfonate detergents, the first sulfonate detergent, preferably calcium sulfonate, having a total TBN base number of less than 100 mg KOH/g, and the second sulfonate detergent, preferably magnesium sulfonate, having a total TBN base number of greater than 200 mg KOH/g, as measured according to ASTM D-2896.
  • the first sulfonate detergent preferably calcium sulfonate
  • the second sulfonate detergent preferably magnesium sulfonate
  • the additive composition according to the invention comprises calcium carboxylate, calcium sulfonate and magnesium sulfonate, preferably calcium carboxylate with a total number of TBN bases of from 120 to 200 mg KOH/g, calcium sulfonate with a total number of TBN bases of less than 100 mg KOH/g and magnesium sulfonate with a total number of TBN bases of greater than 200 mg KOH/g.
  • the additive composition according to the invention comprises calcium carboxylate, calcium sulfonate and magnesium sulfonate.
  • the additive composition according to the invention comprises calcium carboxylate with a TBN of 120 to 200 mg KOH/g, calcium sulfonate TBN strictly less than 200 mg KOH/g and magnesium sulfonate TBN strictly greater than 200 mg KOH/g, the TBNs being measured according to ASTM D-2896.
  • the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 20%, preferentially from 8% to 15%, by weight of carboxylate detergent, relative to the total weight of said additive composition.
  • the additive composition according to the invention comprises from 1% to 20%, preferably from 5% to 10%, by weight of sulfonate detergent(s), relative to the total weight of said additive composition.
  • the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 20%, preferentially from 8% to 15%, by weight of carboxylate detergent and from 1% to 20%, preferably from 5% to 10%, by weight of sulfonate detergent(s), relative to the total weight of said additive composition.
  • the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 15% by weight of calcium carboxylate and from 1% to 20%, preferably from 5% to 10%, by weight of calcium sulfonate, preferably LOB, and magnesium sulfonate, preferably HOB, relative to the total weight of said additive composition.
  • the total content of carboxylate detergent and sulfonate detergent(s) in the additive composition according to the invention is from 1% to 30%, in particular from 2% to 30%, preferably from 5% to 20%, by weight relative to the total weight of said additive composition.
  • the total content of calcium carboxylate and calcium sulfonate and magnesium sulfonate in the additive composition according to the invention is from 1% to 30%, preferably from 5% to 20%, by weight relative to the total weight of said additive composition.
  • the additive composition comprises one or more dispersant(s) in a content of 10% to 50% by weight, preferably 15% to 40%, and preferentially 20% to 30% by weight relative to the total weight of said additive composition.
  • a lubricating composition according to the invention may comprise from 0.2% to 10% by mass of dispersing agent(s), relative to the total weight of the composition.
  • the additive composition according to the invention may also comprise other usual additives, different from the aforementioned detergent additives.
  • the additive composition according to the invention further comprises one or more additional additive(s) chosen from the group consisting of anti-wear additives, antioxidant additives, viscosity index improving additives, pour point lowering additives, friction modifying additives, and mixtures thereof.
  • the additive composition according to the invention further comprises at least one anti-wear additive.
  • the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as alkylthiophosphate metals, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP.
  • the preferred compounds are of formula Zn((SP(S)(OR)(OR'))2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
  • Amine phosphates are also anti-wear additives that can be used in the additive compositions according to the invention.
  • the phosphorus atoms provided by these additives can act as a poison to the systems catalytic converters in automobiles since they generate ash.
  • additives that do not provide phosphorus such as polysulfides, particularly sulfur-containing olefins.
  • the additive compositions according to the invention comprise from 0.1% to 20% by weight, preferably from 1% to 15% by weight, more preferably from 5% to 12% by weight of anti-wear additives (or anti-wear compound), in particular ZnDTP, relative to the total weight of the additive composition according to the invention.
  • the additive compositions according to the invention comprise from 0.01% to 2% by weight, preferably from 0.05% to 1.5% by weight, more preferably from 0.1% to 1.2% by weight of anti-wear additives (or anti-wear compound), in particular ZnDTP, relative to the total weight of the lubricating composition.
  • composition of additives according to the invention may comprise at least one antioxidant additive.
  • Antioxidant additives generally delay the degradation of the lubricating composition. This degradation is most often expressed by the formation of deposits, by the presence of sludge or by an increase in the viscosity of the lubricating composition.
  • Antioxidant additives generally act as free radical inhibitors or hydroperoxide destructive inhibitors. Commonly used antioxidants include phenolic antioxidants, amine antioxidants, sulfur- and phosphorus-containing antioxidants. Some of these antioxidants, for example those comprising sulfur and phosphorus, may generate ash. Phenolic antioxidant additives may be ash-free or in the form of neutral or basic metal salts.
  • Antioxidant additives may include, but are not limited to, sterically hindered phenols, sterically hindered phenol esters, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1-C12 alkyl group, N,N'-dialkylaryldiamines, and mixtures thereof.
  • the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one C1 to C10 alkyl group, preferably a group C1-C6 alkyl, preferably a C4 alkyl group, preferably a tert-butyl group.
  • Amine compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives.
  • amine compounds are aromatic amines, for example aromatic amines of the formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula RdS(O)zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2.
  • Sulfur-containing alkylphenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
  • antioxidant additives are compounds containing copper, e.g. copper thio- or dithio-phosphate, copper salts of carboxylic acids, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.
  • additive compositions according to the invention may also comprise any type of antioxidant known to those skilled in the art.
  • the lubricating composition used according to the invention comprises at least one ash-free antioxidant additive.
  • the additive composition according to the invention comprises from 1% to 20% by weight of at least one antioxidant additive, relative to the total weight of said additive composition.
  • the lubricating composition according to the invention comprises from 0.1% to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.
  • the additive composition according to the invention may also comprise at least one viscosity index improving additive of the hydrogenated butylene and styrene polymer type, of the ethylene propylene copolymer type, or of the polymethacrylate polymer type, preferably a hydrogenated butylene and styrene polymer.
  • the additive composition according to the invention may therefore also comprise at least one viscosity index improving additive chosen from the group consisting of hydrogenated butylene and styrene polymers, ethylene propylene copolymers and polymethacrylate polymers, said viscosity index improving additive preferably being a hydrogenated butylene and styrene polymer.
  • the additive composition according to the invention may comprise from 20% to 60% by weight of viscosity index improving additive, relative to the total weight of said additive composition.
  • the lubricating composition according to the invention may comprise from 0.1% to 15% by weight of additive improving the viscosity index, relative to the total weight of lubricating composition.
  • the lubricating composition used according to the invention may also comprise a pour point lowering additive.
  • the pour point lowering additive By slowing the formation of paraffin crystals, the pour point lowering additive generally improves the cold behavior of the lubricating composition according to the invention.
  • pour point lowering additives examples include alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, and alkyl polystyrenes.
  • the additive composition according to the invention further comprises a friction modifying additive, preferably based on molybdenum.
  • the additive composition according to the invention comprises at least one friction-modifying additive.
  • the friction-modifying additives make it possible to limit friction by forming adsorbed monolayers on the surfaces of the metals in contact with them. They may be chosen from compounds providing metallic elements and ash-free compounds. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon 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 esters and polyols, distinct from the monoester required according to the invention, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides, fatty amines or fatty acid glycerol esters.
  • the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
  • the molybdenum-based compounds may be chosen from molybdenum dithiocarbamates (Mo-DTC), molybdenum dithiophosphates (Mo-DTP), and mixtures thereof.
  • the lubricating composition according to the invention may comprise from 0.01 to 10% by mass or from 0.01 to 5% by mass, preferably from 0.01 to 2% by mass, preferably from 0.1 to 1.5% by mass or from 0.1 to 2% by mass relative to the total mass of the lubricating composition, of friction modifying additive.
  • the Molybdenum (Mo) in the lubricating composition of the invention is provided by an organomolybdenum compound, in particular a compound chosen from a molybdenum dithiocarbamate derivative (MoDTC), a molybdenum dithiophosphate derivative (MoDTP) or a sulfur-free molybdenum complex, preferably a molybdenum dithiocarbamate derivative (MoDTC).
  • MoDTC molybdenum dithiocarbamate derivative
  • MoDTP molybdenum dithiophosphate derivative
  • sulfur-free molybdenum complex preferably a molybdenum dithiocarbamate derivative (MoDTC).
  • Molybdenum dithiocarbamate compounds are complexes formed of a metal core bound to one or more ligands independently selected from alkyl dithiocarbamate groups.
  • the MoDTC compound of the compositions used according to the invention may comprise from 0.01 to 5%, preferably from 0.1 to 1.5% by mass of molybdenum, relative to the total mass of the MoDTC compound.
  • the composition according to the invention comprises a molybdenum-based friction modifying additive and preferably comprises (in active content) from 1 to 1,000 ppm of Mo, preferably from 400 to 600 ppm relative to the weight of lubricating composition.
  • the present invention also relates to a lubricating composition comprising at least one base oil and an additive composition as defined above.
  • the base oils used in the lubricating compositions of the invention may be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1) or their mixtures. Table 1
  • the mineral base oils of the invention include any type of base oil obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing.
  • the base oils of the lubricating compositions according to the invention may also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins.
  • the polyalphaolefins used as base oils are, for example, obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100°C is between 1.5 and 15 mm 2 . s -1 according to standard ASTM D445.
  • base oil As base oil, according to the present invention, mention may also be made of re-refined oils, or even oils of biological origin.
  • the lubricating composition according to the invention comprises a base oil content of from 75% to 95%, preferably from 80% to 90%, by weight relative to the weight of said lubricating composition. According to one embodiment, the lubricating composition according to the invention comprises less than 2.5%, preferably from 1% to 2.5%, preferentially from 1.5% to 2%, by weight of carboxylate detergent relative to the total weight of said lubricating composition.
  • the lubricating composition according to the invention comprises from 0.02% to 2%, preferably from 0.8% to 1.5%, by weight of sulfonate detergent(s), relative to the total weight of said lubricating composition.
  • the lubricating composition according to the invention comprises less than 2.5%, preferably from 1% to 2.5%, preferentially from 1.5% to 2%, by weight of carboxylate detergent relative to the total weight of said lubricating composition and from 0.02% to 2%, preferably from 0.8% to 1.5%, by weight of sulfonate detergent(s), relative to the total weight of said lubricating composition.
  • the total content of carboxylate detergent and sulfonate detergent(s) is from 0.05% to 3%, preferably from 1.1% to 2%, by weight relative to the total weight of said lubricating composition.
  • the lubricating composition according to the invention comprises from 0.1% to 1%, preferably from 0.5% to 0.8%, by weight of a first sulfonate detergent having a total number of TBN bases of less than 100 mg KOH/g, and from 0.1% to 1%, preferably from 0.5% to 0.8%, by weight of a second sulfonate detergent having a total number of TBN bases of greater than 200 mg KOH/g, relative to the total weight of said lubricating composition.
  • the lubricating composition according to the invention further comprises one or more dispersant(s), preferably in a content of from 2% to 5% by weight, preferably from 3% to 4.5% by weight, and preferentially from 3.5% to 4% by weight, relative to the total weight of said lubricating composition.
  • the present invention also relates to a method for lubricating a plug-in hybrid vehicle engine or a hybrid vehicle engine comprising a range extender, comprising bringing at least one mechanical part of said engine into contact with a lubricating composition as defined above.
  • the present invention also relates to the use of the additive composition according to the invention in a lubricating composition for reducing corrosion in a plug-in hybrid vehicle engine or one comprising a range extender.
  • Example 1 Preparation of lubricating compositions
  • the lubricating compositions are prepared by mixing the compounds described in Table 2 below.
  • the percentages indicated correspond to percentages by mass relative to the total mass of the composition.
  • the additive package includes, among other things, an antioxidant, two anti-wear agents, a viscosity index improver and/or a friction modifier and/or a pour point depressant additive.
  • Example 2 Evaluation of lubricating compositions
  • the lubricating compositions are evaluated for their anti-corrosion performance in PEHV (“Plug-In Hybrid Electric Vehicle”) hybrid engines.
  • the evaluation method is adapted from ASTM D1748-22 and aims to evaluate the anti-corrosive properties of a lubricating composition.
  • This method evaluates the anti-corrosion properties of metal protection products in high humidity conditions.
  • the test consists of positioning steel plates previously immersed in oil in a humidity cabinet at 49°C, with air circulation, for 72 hours (Humidity cabinet Linetronic LT/HC- 250000M).
  • Sandblast a batch of plates under the following conditions: a pressure of 5 bars and the sandblaster nose positioned at a distance of 51 mm to 76 mm.
  • Oils are PASS or FAIL depending on the number and size of corrosion spots visible on the surface of the plate.
  • the result will be PASS: If the plate does not contain more than 3 rust spots, and the size does not exceed 1 mm.
  • additives according to the invention comprising both a carboxylate detergent and two sulfonate detergents, makes it possible to obtain good anti-corrosion properties for the lubricating composition, particularly in comparison with an additive composition comprising other types of detergents.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to an additive composition for lubricants comprising a carboxylate detergent and one or more sulphonate detergent(s), as well as to a lubricant composition containing the additive composition, in particular intended for hybrid vehicle engines.

Description

COMPOSITION D’ADDITIFS POUR VÉHICULES HYBRIDES COMPOSITION OF ADDITIVES FOR HYBRID VEHICLES

La présente invention a pour objet une composition d’additifs, notamment pour véhicules hybrides, ainsi qu’une composition lubrifiante comprenant ladite composition d’additifs et son utilisation pour lubrifier notamment les moteurs de véhicules hybrides. The subject of the present invention is an additive composition, in particular for hybrid vehicles, as well as a lubricating composition comprising said additive composition and its use for lubricating in particular hybrid vehicle engines.

Les véhicules hybrides comprennent deux moteurs, un moteur thermique et un moteur électrique. Dans la plus grande partie des véhicules hybrides, le moteur thermique entraîne les roues et est secondé par un moteur électrique. Une batterie fournit l’électricité nécessaire au fonctionnement du moteur électrique, cette batterie est, dans le cas des véhicules hybrides classiques, rechargée pendant les phases de freinage et de décélération, par un système de récupération de l’énergie cinétique (SREC) intégré au véhicule. Hybrid vehicles consist of two engines: a combustion engine and an electric motor. In most hybrid vehicles, the combustion engine drives the wheels and is assisted by an electric motor. A battery provides the electricity needed to operate the electric motor. In conventional hybrid vehicles, this battery is recharged during braking and deceleration by a kinetic energy recovery system (KERS) integrated into the vehicle.

Il existe différentes technologies de véhicules hybrides. Parmi ces technologies hybrides, on peut notamment citer : There are different hybrid vehicle technologies. These hybrid technologies include:

- les véhicules micro-hybrides (également appelé hybridation légère), ces véhicules, équipés du système « stop&start », récupèrent l’énergie générée par le freinage pour charger une batterie qui peut venir assister momentanément le moteur thermique ; - micro-hybrid vehicles (also called mild hybridization), these vehicles, equipped with the “stop&start” system, recover the energy generated by braking to charge a battery which can temporarily assist the thermal engine;

- les véhicules mild-hybrides qui comprennent une assistance électrique lors des accélérations ; et - mild-hybrid vehicles which include electric assistance during acceleration; and

- les véhicules full-hybrides sont des véhicules dont l’hybridation est totale. A faible vitesse, lorsque la batterie est chargée, le moteur électrique se charge du démarrage et de la locomotion. A grande vitesse, ou quand la batterie est déchargée, le moteur thermique prend le relais, lorsqu’il y a besoin d’une puissance accrue (par exemple accélération) les deux moteurs fonctionnent ensemble. Il est ainsi possible de rouler avec le moteur thermique coupé pendant quelques kilomètres. - Full hybrid vehicles are vehicles with total hybridization. At low speeds, when the battery is charged, the electric motor takes care of starting and locomotion. At high speeds, or when the battery is discharged, the combustion engine takes over; when increased power is needed (for example, acceleration), the two engines work together. It is thus possible to drive with the combustion engine switched off for a few kilometers.

D’autres technologies complémentaires ont été récemment développées : les véhicules hybrides rechargeables et les véhicules hybrides comprenant un prolongateur d’autonomie. Les véhicules hybrides rechargeables (appelés également plug-in en anglais) comprennent un moteur thermique et un moteur électrique, la batterie peut être rechargée sur le réseau électrique, ces véhicules peuvent ainsi rouler en mode 100% électrique sur une distance de plusieurs dizaines de kilomètres, par exemple 50 kilomètres. Dans les véhicules hybrides comprenant un prolongateur d’autonomie (appelé également range extender en anglais), seul le moteur électrique entraine les roues. Ce moteur électrique est alimenté par une batterie pendant quelques dizaines de kilomètres. Lorsque la batterie atteint un certain seuil de charge (par exemple de l’ordre de 30%) le moteur thermique démarre et entraîne un générateur de courant permettant de produire l’électricité nécessaire pour recharger la batterie et maintenir le fonctionnement du moteur électrique. Other complementary technologies have recently been developed: plug-in hybrid vehicles and hybrid vehicles with a range extender. Plug-in hybrid vehicles include a combustion engine and an electric motor. The battery can be recharged from the electricity network. These vehicles can therefore drive in 100% electric mode for a distance of several dozen kilometers, for example 50 kilometers. In hybrid vehicles with a range extender range extender (also called a range extender in English), only the electric motor drives the wheels. This electric motor is powered by a battery for a few dozen kilometers. When the battery reaches a certain charge threshold (for example, around 30%), the combustion engine starts and drives a current generator to produce the electricity needed to recharge the battery and keep the electric motor running.

Dans ces deux types de véhicules hybrides, le moteur thermique est utilisé moins souvent et fonctionne donc à des températures plus basses (aux alentours, voire même inférieures à 40°C) notamment que les moteurs des autres types de véhicules hybrides. Or, à faible température, les compositions lubrifiantes classiques sont plus visqueuses et les additifs ne sont pas actifs comme dans une application conventionnelle à plus haute température. Les lubrifiants actuels ont été optimisés pour permettre un gain de consommation de carburant à chaud. In both types of hybrid vehicles, the combustion engine is used less frequently and therefore operates at lower temperatures (around, or even below, 40°C) than the engines of other types of hybrid vehicles. However, at low temperatures, conventional lubricant compositions are more viscous and the additives are not as active as in a conventional application at higher temperatures. Current lubricants have been optimized to achieve fuel consumption gains when hot.

Le fonctionnement du moteur thermique dans un véhicule hybride implique des changements dans les contraintes que le lubrifiant endure. La température du lubrifiant des moteurs hybrides est plus faible que celle des véhicules thermiques classiques, ce qui engendre une dilution plus importante du lubrifiant par le carburant ainsi qu’une accumulation d’eau. La présence d’eau et d’essence induit la formation d’émulsions eau-huile sur le terrain et pose la question de son impact sur les performances en corrosion du lubrifiant en fonctionnement. The operation of the internal combustion engine in a hybrid vehicle involves changes in the stresses that the lubricant endures. The temperature of the lubricant in hybrid engines is lower than that of conventional internal combustion vehicles, which results in greater dilution of the lubricant by the fuel as well as water accumulation. The presence of water and gasoline induces the formation of water-oil emulsions in the field and raises the question of its impact on the corrosion performance of the lubricant in operation.

A ce jour, pour réduire la corrosion en présence d’eau et d’essence, on utilise des additifs anti-corrosion ajoutés dans la composition lubrifiante. Cette solution présente cependant un certain nombre d’inconvénients, notamment en termes de coûts et d’efficacité. Currently, to reduce corrosion in the presence of water and gasoline, anti-corrosion additives are used in the lubricant composition. However, this solution has several disadvantages, particularly in terms of cost and effectiveness.

Il existe donc un besoin pour réduire la corrosion dans les moteurs hybrides. There is therefore a need to reduce corrosion in hybrid engines.

La présente invention a donc pour but de fournir une composition présentant une réduction de la corrosion dans les moteurs hybrides. The present invention therefore aims to provide a composition exhibiting a reduction in corrosion in hybrid engines.

La présente invention a également pour but de fournir une composition lubrifiante améliorant les performances en corrosion pour les véhicules hybrides. The present invention also aims to provide a lubricating composition improving corrosion performance for hybrid vehicles.

Ainsi, la présente invention concerne une composition d’additifs pour lubrifiants comprenant un détergent carboxylate et un ou plusieurs détergent(s) sulfonate(s). Thus, the present invention relates to a lubricant additive composition comprising a carboxylate detergent and one or more sulfonate detergent(s).

Les additifs détergents sont utilisés généralement pour réduire la formation de dépôts à la surface des pièces métalliques par dissolution des produits secondaires d’oxydation et de combustion. La présente invention concerne également une composition lubrifiante comprenant au moins une huile de base et la composition d’additifs susmentionnée. Detergent additives are generally used to reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products. The present invention also relates to a lubricating composition comprising at least one base oil and the aforementioned additive composition.

Selon l’invention, on entend par « composition d’additifs » une composition avant l’addition de l’huile de base pour former une composition lubrifiante. According to the invention, the term "additive composition" means a composition before the addition of the base oil to form a lubricating composition.

La composition d’additifs selon l’invention est un mélange binaire comprenant un détergent carboxylate et un détergent sulfonate ou un mélange au moins ternaire comprenant un détergent carboxylate et plusieurs détergents sulfonates. The additive composition according to the invention is a binary mixture comprising a carboxylate detergent and a sulfonate detergent or an at least ternary mixture comprising a carboxylate detergent and several sulfonate detergents.

Par « détergent carboxylate », on désigne un composé carboxylate avec un cation associé qui peut être un cation métallique d’un métal alcalin ou alcalino-terreux. "Carboxylate detergent" means a carboxylate compound with an associated cation which may be a metal cation of an alkali or alkaline earth metal.

Les carboxylates selon l’invention sont par exemple des carboxylates aliphatiques (par exemple stéarates). En particulier, ils peuvent être préparés par réaction d’un acide carboxylique avec un composé métallique approprié comme un oxyde ou un hydroxyde. The carboxylates according to the invention are, for example, aliphatic carboxylates (for example, stearates). In particular, they can be prepared by reacting a carboxylic acid with a suitable metal compound such as an oxide or a hydroxide.

Par « détergent sulfonate », on désigne un composé sulfonate avec un cation associé qui peut être un cation métallique d’un métal alcalin ou alcalino-terreux. “Sulfonate detergent” means a sulfonate compound with an associated cation which may be a metal cation of an alkali or alkaline earth metal.

Les sulfonates selon l’invention peuvent être préparés à partir d’acides sulfoniques qui sont typiquement obtenus par sulfonation d’hydrocarbures aromatiques substitués par un groupe alkyle comme ceux obtenus à partir du fractionnement du pétrole ou par alkylation d’hydrocarbures aromatiques. Comme exemples, on peut citer ceux obtenus par alkylation du benzène, toluène, xylène, naphthalène, le diphényle ou leurs dérivés halogénés. Cette alkylation peut être effectuée en présence d’un catalyseur avec des agents alkylants ayant de 3 à plus de 70 atomes de carbone. Les alkaryl sulfonates contiennent usuellement de 9 à 80 ou plus atomes de carbone (par exemple de 16 à 60 atomes de carbone) par résidu aromatique alkyle-substitué. The sulfonates of the invention may be prepared from sulfonic acids which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from petroleum fractionation or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, diphenyl or their halogenated derivatives. This alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms. Alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms (e.g., from 16 to 60 carbon atoms) per alkyl-substituted aromatic residue.

Les métaux alcalins et alcalino-terreux des carboxylates et sulfonates susmentionnés sont préférentiellement le calcium, le magnésium, le sodium ou le baryum. The alkali and alkaline earth metals of the above-mentioned carboxylates and sulfonates are preferably calcium, magnesium, sodium or barium.

Ces sels métalliques comprennent généralement le métal en quantité stoechiométrique ou bien en excès, donc en quantité supérieure à la quantité stoechiométrique. Il s’agit alors d’additifs détergents surbasés ; le métal en excès apportant le caractère surbasé à l’additif détergent est alors généralement sous la forme d’un sel métallique insoluble dans l’huile. These metal salts generally contain the metal in stoichiometric quantity or in excess, i.e. in a quantity greater than the stoichiometric quantity. These are then overbased detergent additives; the excess metal providing the overbased character to the detergent additive is then generally in the form of an oil-insoluble metal salt.

Parmi les additifs détergents, on peut citer les additifs détergents surbasés, et en particulier les additifs détergents faiblement surbasés (« LOB » ou « low overbased »), moyennement surbasés (« MOB » ou « medium overbased ») ou fortement surbasés (« HOB » ou « high overbased »). Ces additifs détergents surbasés sont notamment définis par leur nombre total de bases ou TBN. Detergent additives include overbased detergent additives, and in particular low overbased (LOB), medium overbased (MOB) or high overbased (HOB). These overbased detergent additives are defined in particular by their total base number or TBN.

Le terme « nombre total de bases » (ou TBN) désigne la quantité de bases, équivalente à des milligrammes de KOH dans un gramme d’un échantillon dudit détergent. Ainsi, les valeurs élevées de TBN correspondent à des produits plus alcalins, et donc à une alcalinité plus importante. La valeur du TBN est déterminée selon la norme ASTM D2896. The term "total base number" (or TBN) refers to the amount of bases, equivalent to milligrams of KOH in one gram of a sample of said detergent. Thus, higher TBN values correspond to more alkaline products, and therefore to greater alkalinity. The TBN value is determined according to ASTM D2896.

Selon l’invention, un détergent LOB présente généralement un TBN inférieur à 100 mg KOH/g et un détergent HOB présente généralement un TBN supérieur à 200 mg KOH/g. According to the invention, a LOB detergent generally has a TBN of less than 100 mg KOH/g and a HOB detergent generally has a TBN of greater than 200 mg KOH/g.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend un détergent carboxylate et deux détergents sulfonates. Selon un mode de réalisation, la composition d’additifs selon l’invention comprend un détergent carboxylate, notamment MOB, un détergent sulfonate LOB et un détergent sulfonate HOB. According to one embodiment, the additive composition according to the invention comprises a carboxylate detergent and two sulfonate detergents. According to one embodiment, the additive composition according to the invention comprises a carboxylate detergent, in particular MOB, a sulfonate detergent LOB and a sulfonate detergent HOB.

Selon un mode de réalisation, dans la composition d’additifs selon l’invention, le détergent carboxylate est choisi parmi les sels de métaux alcalins ou de métaux alcalino-terreux de carboxylate, et est de préférence du carboxylate de calcium. According to one embodiment, in the additive composition according to the invention, the carboxylate detergent is chosen from alkali metal or alkaline earth metal salts of carboxylate, and is preferably calcium carboxylate.

Selon un mode de réalisation, le détergent carboxylate de la composition d’additifs selon l’invention est du carboxylate de calcium. De préférence, le détergent carboxylate de la composition d’additifs selon l’invention est du carboxylate de calcium MOB. According to one embodiment, the carboxylate detergent of the additive composition according to the invention is calcium carboxylate. Preferably, the carboxylate detergent of the additive composition according to the invention is calcium carboxylate MOB.

Selon un mode de réalisation, dans la composition d’additifs selon l’invention, les détergents sulfonates sont choisis parmi les sels de métaux alcalins ou de métaux alcalino-terreux de sulfonate, de préférence du sulfonate de calcium, du sulfonate de magnésium ou leur mélange. Selon un mode de réalisation, les détergents sulfonates de la composition d’additifs selon l’invention sont un mélange de sulfonate de calcium et de sulfonate de magnésium. De préférence, les détergents sulfonates de la composition d’additifs selon l’invention sont un mélange de sulfonate de calcium LOB et de sulfonate de magnésium HOB. According to one embodiment, in the additive composition according to the invention, the sulfonate detergents are chosen from alkali metal or alkaline earth metal sulfonate salts, preferably calcium sulfonate, magnesium sulfonate or their mixture. According to one embodiment, the sulfonate detergents of the additive composition according to the invention are a mixture of calcium sulfonate and magnesium sulfonate. Preferably, the sulfonate detergents of the additive composition according to the invention are a mixture of calcium sulfonate LOB and magnesium sulfonate HOB.

Selon un mode de réalisation, le détergent carboxylate présente un nombre total de bases TBN compris de 120 à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896, comme indiqué plus haut. In one embodiment, the carboxylate detergent has a total base number TBN of 120 to 200 mg KOH/g, as measured according to ASTM D-2896, as noted above.

De préférence, le détergent carboxylate de la composition d’additifs selon l’invention est du carboxylate de calcium présentant un nombre total de bases TBN compris de 120 à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896. Preferably, the carboxylate detergent of the additive composition according to the invention is calcium carboxylate having a total base number TBN of from 120 to 200 mg KOH/g, as measured according to ASTM D-2896.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend un mélange de deux détergents sulfonates, le premier détergent sulfonate, de préférence du sulfonate de calcium, présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et le deuxième détergent sulfonate, de préférence du sulfonate de magnésium, présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896. In one embodiment, the additive composition of the invention comprises a mixture of two sulfonate detergents, the first sulfonate detergent, preferably calcium sulfonate, having a total TBN base number of less than 100 mg KOH/g, and the second sulfonate detergent, preferably magnesium sulfonate, having a total TBN base number of greater than 200 mg KOH/g, as measured according to ASTM D-2896.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend du carboxylate de calcium, du sulfonate de calcium et du sulfonate de magnésium, de préférence du carboxylate de calcium avec un nombre total de bases TBN compris de 120 à 200 mg KOH/g, du sulfonate de calcium avec un nombre total de bases TBN inférieur à 100 mg KOH/g et du sulfonate de magnésium avec un nombre total de bases TBN supérieur à 200 mg KOH/g. According to one embodiment, the additive composition according to the invention comprises calcium carboxylate, calcium sulfonate and magnesium sulfonate, preferably calcium carboxylate with a total number of TBN bases of from 120 to 200 mg KOH/g, calcium sulfonate with a total number of TBN bases of less than 100 mg KOH/g and magnesium sulfonate with a total number of TBN bases of greater than 200 mg KOH/g.

Selon un mode de réalisation préféré, la composition d’additifs selon l’invention comprend du carboxylate de calcium, du sulfonate de calcium et du sulfonate de magnésium. De préférence, la composition d’additifs selon l’invention comprend du carboxylate de calcium avec un TBN compris de 120 à 200 mg KOH/g, du sulfonate de calcium TBN strictement inférieur à 200 mg KOH/g et du sulfonate de magnésium TBN strictement supérieur à 200 mg KOH/g, les TBN étant mesurés selon la norme ASTM D-2896. Selon un mode de réalisation, la composition d’additifs selon l’invention comprend de 1% à 30%, de préférence de 5% à 20%, préférentiellement de 8% à 15%, en poids de détergent carboxylate, par rapport au poids total de ladite composition d’additifs. According to a preferred embodiment, the additive composition according to the invention comprises calcium carboxylate, calcium sulfonate and magnesium sulfonate. Preferably, the additive composition according to the invention comprises calcium carboxylate with a TBN of 120 to 200 mg KOH/g, calcium sulfonate TBN strictly less than 200 mg KOH/g and magnesium sulfonate TBN strictly greater than 200 mg KOH/g, the TBNs being measured according to ASTM D-2896. According to one embodiment, the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 20%, preferentially from 8% to 15%, by weight of carboxylate detergent, relative to the total weight of said additive composition.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend de 1% à 20%, de préférence de 5% à 10%, en poids de détergent(s) sulfonate(s), par rapport au poids total de ladite composition d’additifs. According to one embodiment, the additive composition according to the invention comprises from 1% to 20%, preferably from 5% to 10%, by weight of sulfonate detergent(s), relative to the total weight of said additive composition.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend de 1% à 30%, de préférence de 5% à 20%, préférentiellement de 8% à 15%, en poids de détergent carboxylate et de 1% à 20%, de préférence de 5% à 10%, en poids de détergent(s) sulfonate(s), par rapport au poids total de ladite composition d’additifs. According to one embodiment, the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 20%, preferentially from 8% to 15%, by weight of carboxylate detergent and from 1% to 20%, preferably from 5% to 10%, by weight of sulfonate detergent(s), relative to the total weight of said additive composition.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend de 1% à 30%, de préférence de 5% à 15% en poids de carboxylate de calcium et de 1% à 20%, de préférence de 5% à 10%, en poids de sulfonate de calcium, de préférence LOB, et de sulfonate de magnésium, de préférence HOB, par rapport au poids total de ladite composition d’additifs. According to one embodiment, the additive composition according to the invention comprises from 1% to 30%, preferably from 5% to 15% by weight of calcium carboxylate and from 1% to 20%, preferably from 5% to 10%, by weight of calcium sulfonate, preferably LOB, and magnesium sulfonate, preferably HOB, relative to the total weight of said additive composition.

Selon un mode de réalisation, la teneur totale en détergent carboxylate et en détergent(s) sulfonate(s) dans la composition d’additifs selon l’invention est comprise de 1 % à 30%, notamment de 2% à 30%, de préférence de 5% à 20%, en poids par rapport au poids total de ladite composition d’additifs. According to one embodiment, the total content of carboxylate detergent and sulfonate detergent(s) in the additive composition according to the invention is from 1% to 30%, in particular from 2% to 30%, preferably from 5% to 20%, by weight relative to the total weight of said additive composition.

Selon un mode de réalisation, la teneur totale en carboxylate de calcium et en sulfonate de calcium et sulfonate de magnésium dans la composition d’additifs selon l’invention est comprise de 1 % à 30%, de préférence de 5% à 20%, en poids par rapport au poids total de ladite composition d’additifs. According to one embodiment, the total content of calcium carboxylate and calcium sulfonate and magnesium sulfonate in the additive composition according to the invention is from 1% to 30%, preferably from 5% to 20%, by weight relative to the total weight of said additive composition.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend de 1% à 10%, de préférence de 2% à 5%, en poids d’un premier détergent sulfonate présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et de 1% à 10%, de préférence de 2% à 5%, en poids d’un deuxième détergent sulfonate présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, par rapport au poids total de ladite composition d’additifs. Une composition d’additifs selon l’invention peut également comprendre au moins un agent dispersant, boré ou non. De tels agents dispersants assurent le maintien en suspension et l’évacuation des contaminants solides insolubles constitués par les produits secondaires d’oxydation qui se forment lorsque la composition lubrifiante est en service. Ils peuvent être choisis parmi les bases de Mannich, les succinimides et leurs dérivés, tels que les dérivés de polyisobutylène anhydride succinique. According to one embodiment, the additive composition according to the invention comprises from 1% to 10%, preferably from 2% to 5%, by weight of a first sulfonate detergent having a total number of TBN bases of less than 100 mg KOH/g, and from 1% to 10%, preferably from 2% to 5%, by weight of a second sulfonate detergent having a total number of TBN bases of greater than 200 mg KOH/g, relative to the total weight of said additive composition. An additive composition according to the invention may also comprise at least one dispersing agent, whether borated or not. Such dispersing agents ensure the maintenance in suspension and the removal of insoluble solid contaminants consisting of secondary oxidation products which form when the lubricating composition is in service. They may be chosen from Mannich bases, succinimides and their derivatives, such as polyisobutylene succinic anhydride derivatives.

Selon un mode de réalisation, la composition d’additifs comprend un ou plusieurs dispersant(s) en une teneur de 10% à 50% en poids, de préférence de 15% à 40%, et préférentiellement de 20% à 30% en poids par rapport au poids total de ladite composition d’additifs. According to one embodiment, the additive composition comprises one or more dispersant(s) in a content of 10% to 50% by weight, preferably 15% to 40%, and preferentially 20% to 30% by weight relative to the total weight of said additive composition.

En particulier, une composition lubrifiante selon l’invention peut comprendre de 0,2% à 10% massique d’agent(s) dispersant(s), par rapport au poids total de la composition. In particular, a lubricating composition according to the invention may comprise from 0.2% to 10% by mass of dispersing agent(s), relative to the total weight of the composition.

La composition d’additifs selon l’invention peut également comprendre d’autres additifs usuels, différents des additifs détergents susmentionnés. The additive composition according to the invention may also comprise other usual additives, different from the aforementioned detergent additives.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend en outre un ou plusieurs additif(s) additionnel(s) choisi(s) dans le groupe constitué des additifs anti-usure, des additifs antioxydants, des additifs améliorant l’indice de viscosité, des additifs abaisseurs de point d’écoulement, des additifs modificateurs de frottement, et de leurs mélanges. According to one embodiment, the additive composition according to the invention further comprises one or more additional additive(s) chosen from the group consisting of anti-wear additives, antioxidant additives, viscosity index improving additives, pour point lowering additives, friction modifying additives, and mixtures thereof.

De préférence, la composition d’additifs selon l’invention comprend en outre au moins un additif anti-usure. Preferably, the additive composition according to the invention further comprises at least one anti-wear additive.

Il existe une grande variété d’additifs anti-usure. De préférence, pour les compositions lubrifiantes utilisées selon l’invention, les additifs anti-usure sont choisis parmi les additifs comprenant du phosphore et du soufre tels que les métaux alkylthiophosphate, en particulier zinc alkylthiophosphate, et plus précisément le zinc dialkyldithiophosphate ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR)(OR'))2, dans laquelle R et R', identique ou différent, représente indépendamment un groupe alkyle, de préférence un groupe alkyle comprenant de 1 à 18 atomes de carbone. There is a wide variety of anti-wear additives. Preferably, for the lubricating compositions used according to the invention, the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as alkylthiophosphate metals, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP. The preferred compounds are of formula Zn((SP(S)(OR)(OR'))2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.

Les phosphates d’amine sont également des additifs anti-usure qui peuvent être utilisés dans les compositions d’additifs selon l’invention. Cependant, les atomes de phosphore apportés par ces additifs peuvent agir comme poison des systèmes catalytiques des automobiles puisqu’ils génèrent des cendres. Il est possible de minimiser ces effets en substituant une partie des phosphates d’amine avec des additifs n’apportant pas de phosphore, tels que par exemple les polysulfures, notamment les oléfines contenant du soufre. Amine phosphates are also anti-wear additives that can be used in the additive compositions according to the invention. However, the phosphorus atoms provided by these additives can act as a poison to the systems catalytic converters in automobiles since they generate ash. These effects can be minimized by substituting some of the amine phosphates with additives that do not provide phosphorus, such as polysulfides, particularly sulfur-containing olefins.

Avantageusement, les compositions d’additifs selon l’invention comprennent de 0,1 % à 20% en poids, de préférence de 1 % à 15% en poids, plus préférentiellement de 5% à 12% en poids d’additifs anti-usure (ou composé anti-usure), notamment de ZnDTP, par rapport au poids total de composition d’additifs selon l’invention. Advantageously, the additive compositions according to the invention comprise from 0.1% to 20% by weight, preferably from 1% to 15% by weight, more preferably from 5% to 12% by weight of anti-wear additives (or anti-wear compound), in particular ZnDTP, relative to the total weight of the additive composition according to the invention.

Avantageusement, les compositions d’additifs selon l’invention comprennent de 0,01% à 2% en poids, de préférence de 0,05% à 1 ,5% en poids, plus préférentiellement de 0,1 % à 1 ,2% en poids d’additifs anti-usure (ou composé antiusure), notamment de ZnDTP, par rapport au poids total de la composition lubrifiante. Advantageously, the additive compositions according to the invention comprise from 0.01% to 2% by weight, preferably from 0.05% to 1.5% by weight, more preferably from 0.1% to 1.2% by weight of anti-wear additives (or anti-wear compound), in particular ZnDTP, relative to the total weight of the lubricating composition.

Avantageusement, la composition d’additifs selon l’invention peut comprendre au moins un additif antioxydant. Advantageously, the composition of additives according to the invention may comprise at least one antioxidant additive.

Les additifs antioxydants généralement retardant la dégradation de la composition lubrifiante. Cette dégradation s’exprime le plus souvent par la formation de dépôt, par la présence de boues ou par une augmentation de la viscosité de la composition lubrifiante. Antioxidant additives generally delay the degradation of the lubricating composition. This degradation is most often expressed by the formation of deposits, by the presence of sludge or by an increase in the viscosity of the lubricating composition.

Les additifs antioxydants agissent généralement comme inhibiteurs radicalaires ou inhibiteurs destructeurs de l'hydroperoxyde. Parmi les antioxydants couramment utilisés on peut citer les antioxydants de type phénolique, les antioxydants de type amine, les antioxydants contenant du soufre et du phosphore. Certains de ces antioxydants, par exemple ceux comprenant du soufre et du phosphore peuvent générer des cendres. Les additifs antioxydants phénoliques peuvent être exempt de cendres ou bien être sous la forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, des esters de phénols stériquement encombrés, des phénols stériquement encombrés comprenant un pont thioéther, des diphénylamines, des diphénylamines substituées avec au moins un groupe alkyl en C1 à C12, des N,N’- dialkyl-aryl-diamines et leurs mélanges. Antioxidant additives generally act as free radical inhibitors or hydroperoxide destructive inhibitors. Commonly used antioxidants include phenolic antioxidants, amine antioxidants, sulfur- and phosphorus-containing antioxidants. Some of these antioxidants, for example those comprising sulfur and phosphorus, may generate ash. Phenolic antioxidant additives may be ash-free or in the form of neutral or basic metal salts. Antioxidant additives may include, but are not limited to, sterically hindered phenols, sterically hindered phenol esters, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1-C12 alkyl group, N,N'-dialkylaryldiamines, and mixtures thereof.

De préférence selon l’invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupe phénol pour lequel au moins un des atomes de carbone au voisinage de l’atome de carbone portant la fonction alcool est substitué par au moins un groupe alkyle en C1 à C10, de préférence un groupe alkyle en C1 à C6, de préférence un groupe alkyle en C4, de préférence un groupe ter-butyle. Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one C1 to C10 alkyl group, preferably a group C1-C6 alkyl, preferably a C4 alkyl group, preferably a tert-butyl group.

Les composés amines sont une autre classe d’additifs antioxydants qui peuvent être utilises, optionnellement en combinaison avec des additifs antioxydants phénoliques. Des exemples de composés amines sont les amines aromatiques, par exemple les amines aromatiques de formule NRaRbRc dans laquelle Ra représente un groupe aliphatique ou un groupe aromatique, optionnellement substitué, Rb représente un groupe aromatique, optionnellement substitué, Rc représente un atome d’hydrogène, un groupe alkyle, un groupe aryle group ou un groupe de groupe de formule RdS(O)zRe dans lequel Rd représente un groupe alkylène ou alkénylène, Re représente un groupe alkyle, un groupe alkényle ou un groupe aryle et z représente 0, 1 ou 2. Amine compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, for example aromatic amines of the formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula RdS(O)zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2.

Les alkyl-phénols contenant du soufre ou leurs sels de métaux alcalins ou alcalino-terreux peuvent aussi être utilisés comme additifs antioxydants. Sulfur-containing alkylphenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.

D’autres classes d’additifs antioxydants sont les composés comprenant du cuivre, par exemple thio- ou dithio-phosphate de cuivre, des sels de cuivre et d’acides carboxylique, des dithiocarbamates, des sulfonates, des phénates, des acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d’acide ou d’anhydride succinique peuvent également être utilisés. Other classes of antioxidant additives are compounds containing copper, e.g. copper thio- or dithio-phosphate, copper salts of carboxylic acids, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.

Les compositions d’additifs selon l’invention peuvent également comprendre tout type d’antioxydant connu de l’homme du métier. The additive compositions according to the invention may also comprise any type of antioxidant known to those skilled in the art.

Avantageusement, la composition lubrifiante utilisée selon l’invention comprend au moins un additif antioxydant exempt de cendres. Advantageously, the lubricating composition used according to the invention comprises at least one ash-free antioxidant additive.

Egalement avantageusement la composition d’additifs selon l’invention comprend de 1% à 20% en poids d’au moins un additif antioxydant, par rapport au poids total de ladite composition d’additifs. Also advantageously, the additive composition according to the invention comprises from 1% to 20% by weight of at least one antioxidant additive, relative to the total weight of said additive composition.

Egalement avantageusement la composition lubrifiante selon l’invention comprend de 0,1 % à 2% en poids par rapport au poids total de la composition, d’au moins un additif antioxydant. Also advantageously, the lubricating composition according to the invention comprises from 0.1% to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.

La composition d’additifs selon l’invention peut également comprendre au moins un additif améliorant l’indice de viscosité de type polymère de butylène et de styrène hydrogéné, de type copolymère d’éthylène propylène, ou encore de type polymère polyméthacrylate, de préférence un polymère de butylène et de styrène hydrogéné. La composition d’additifs selon l’invention peut donc comprendre également au moins un additif améliorant l’indice de viscosité choisi dans le groupe constitué des polymères de butylène et de styrène hydrogénés, des copolymères éthylène propylène et des polymères polyméthacrylate, ledit additif améliorant l’indice de viscosité étant de préférence un polymère de butylène et de styrène hydrogéné. La composition d’additifs selon l’invention peut comprendre de 20% à 60% en poids d’additif améliorant l’indice de viscosité, par rapport au poids total de ladite composition d’additifs. The additive composition according to the invention may also comprise at least one viscosity index improving additive of the hydrogenated butylene and styrene polymer type, of the ethylene propylene copolymer type, or of the polymethacrylate polymer type, preferably a hydrogenated butylene and styrene polymer. The additive composition according to the invention may therefore also comprise at least one viscosity index improving additive chosen from the group consisting of hydrogenated butylene and styrene polymers, ethylene propylene copolymers and polymethacrylate polymers, said viscosity index improving additive preferably being a hydrogenated butylene and styrene polymer. The additive composition according to the invention may comprise from 20% to 60% by weight of viscosity index improving additive, relative to the total weight of said additive composition.

La composition lubrifiante selon l’invention peut comprendre de 0,1% à 15% en poids d’additif améliorant l’indice de viscosité, par rapport au poids total de composition lubrifiante. The lubricating composition according to the invention may comprise from 0.1% to 15% by weight of additive improving the viscosity index, relative to the total weight of lubricating composition.

Egalement de manière avantageuse, la composition lubrifiante utilisée selon l’invention peut aussi comprendre un additif abaisseur du point d’écoulement. Also advantageously, the lubricating composition used according to the invention may also comprise a pour point lowering additive.

En ralentissant la formation de cristaux de paraffine, l’additif abaisseur du point d’écoulement améliore généralement le comportement à froid de la composition lubrifiante selon l’invention. By slowing the formation of paraffin crystals, the pour point lowering additive generally improves the cold behavior of the lubricating composition according to the invention.

Comme exemple d’additif abaisseurs du point d’écoulement on peut mentionner, les alkyles polyméthacrylates, polyacrylates, polyarylamides, polyalkylphénols, polyalkylnaphtalène, les alkyls polystyrènes. Examples of pour point lowering additives include alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, and alkyl polystyrenes.

Selon un mode de réalisation, la composition d’additifs selon l’invention comprend en outre un additif modificateur de frottement, de préférence à base de molybdène. According to one embodiment, the additive composition according to the invention further comprises a friction modifying additive, preferably based on molybdenum.

De préférence, la composition d’additifs selon l’invention comprend au moins un additif modificateur de frottement. Les additifs modificateurs de frottement permettent de limiter les frottements en formant des monocouches adsorbées sur les surfaces des métaux à leur contact. Ils peuvent être choisis parmi des composés apportant des éléments métalliques et des composés exempts de cendres. Parmi les composés apportant des éléments métalliques, on peut citer les complexes de métaux de transition tels que Mo, Sb. Sn, Fe, Cu, Zn dont les ligands peuvent être des composés hydrocarbonés comprenant des atomes d’oxygène, d’azote, de soufre ou de phosphore. Les additifs modificateurs de frottement exempts de cendres sont généralement d’origine organique et peuvent être choisis parmi les esters d’acides gras et de polyols, distincts du monoester requis selon l’invention, les amines alcoxylées, les amines grasses alcoxylées, les époxydes gras, les époxydes gras de borate, les amines grasses ou les esters de glycérol d’acide gras. Selon l’invention, les composés gras comprennent au moins un groupement hydrocarboné comprenant de 10 à 24 atomes de carbone. En particulier, les composés à base de molybdène peuvent être choisis parmi les dithiocarbamates de molybdène (Mo-DTC), les dithiophosphates de molybdène (Mo-DTP), et leurs mélanges. De manière avantageuse, la composition lubrifiante selon l’invention peut comprendre de 0,01 à 10 % en masse ou de 0,01 à 5 % en masse, préférentiellement de 0,01 à 2% en masse, de préférence de 0,1 à 1 ,5 % en masse ou de 0,1 à 2 % en masse par rapport à la masse totale de la composition lubrifiante, d’additif modificateur de frottement. Preferably, the additive composition according to the invention comprises at least one friction-modifying additive. The friction-modifying additives make it possible to limit friction by forming adsorbed monolayers on the surfaces of the metals in contact with them. They may be chosen from compounds providing metallic elements and ash-free compounds. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon 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 esters and polyols, distinct from the monoester required according to the invention, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides, fatty amines or fatty acid glycerol esters. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms. In particular, the molybdenum-based compounds may be chosen from molybdenum dithiocarbamates (Mo-DTC), molybdenum dithiophosphates (Mo-DTP), and mixtures thereof. Advantageously, the lubricating composition according to the invention may comprise from 0.01 to 10% by mass or from 0.01 to 5% by mass, preferably from 0.01 to 2% by mass, preferably from 0.1 to 1.5% by mass or from 0.1 to 2% by mass relative to the total mass of the lubricating composition, of friction modifying additive.

Le Molybdène (Mo) dans la composition lubrifiante de l’invention est apporté par un composé organomolybdène, notamment un composé choisi parmi un dérivé dithiocarbamate de molybdène (MoDTC), un dérivé dithiophosphate de molybdène (MoDTP) ou un complexe de molybdène exempt de soufre, de préférence un dérivé dithiocarbamate de molybdène (MoDTC). The Molybdenum (Mo) in the lubricating composition of the invention is provided by an organomolybdenum compound, in particular a compound chosen from a molybdenum dithiocarbamate derivative (MoDTC), a molybdenum dithiophosphate derivative (MoDTP) or a sulfur-free molybdenum complex, preferably a molybdenum dithiocarbamate derivative (MoDTC).

Les composés dithiocarbamate de molybdène (composé MoDTC) sont des complexes formés d'un noyau métallique lié à un ou plusieurs ligands indépendamment choisis parmi les groupements dithiocarbamates d'alkyles. Le composé MoDTC des compositions utilisées selon l'invention peut comprendre de 0,01 à 5%, de préférence de 0,1 à 1 ,5% en masse de molybdène, par rapport à la masse totale du composé MoDTC. Molybdenum dithiocarbamate compounds (MoDTC compound) are complexes formed of a metal core bound to one or more ligands independently selected from alkyl dithiocarbamate groups. The MoDTC compound of the compositions used according to the invention may comprise from 0.01 to 5%, preferably from 0.1 to 1.5% by mass of molybdenum, relative to the total mass of the MoDTC compound.

De préférence, la composition selon l’invention comprend un additif modificateur de frottement à base de molybdène et de préférence comprend (en teneur active) de 1 à 1 000 ppm de Mo, de préférence de 400 à 600 ppm par rapport au poids de composition lubrifiante. Preferably, the composition according to the invention comprises a molybdenum-based friction modifying additive and preferably comprises (in active content) from 1 to 1,000 ppm of Mo, preferably from 400 to 600 ppm relative to the weight of lubricating composition.

La présente invention concerne également une composition lubrifiante comprenant au moins une huile de base et une composition d’additifs telle que définie ci-dessus. The present invention also relates to a lubricating composition comprising at least one base oil and an additive composition as defined above.

Les huiles de base utilisées dans les compositions lubrifiantes de l’invention peuvent être des huiles d’origine minérale ou synthétique appartenant aux groupes I à V selon les classes définies par la classification API (ou leurs équivalents selon la classification ATIEL (Tableau 1) ou leurs mélanges. Tableau 1 The base oils used in the lubricating compositions of the invention may be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1) or their mixtures. Table 1

Les huiles de base minérales de l’invention incluent tout type d’huile de base obtenue par distillation atmosphérique et sous vide de pétrole brut, suivi par des opérations de raffinage telle que l’extraction par solvant, désasphaltage, déparaffinage au solvant, hydrotraitement, hydrocraquage, hydroisomérisation et hydrofinition. The mineral base oils of the invention include any type of base oil obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing.

Les huiles de base des compositions lubrifiantes selon l’invention peuvent aussi être choisies parmi les huiles synthétiques, tels que certains esters d’acides carboxyliques et d’alcools, et les polyalphaoléfines. Les polyalphaoléfines utilisées en tant qu’huile de base sont par exemple obtenues à partir de monomères comprenant de 4 à 32 atomes de carbone, par exemple à partir d’octène ou décène, et pour lesquels la viscosité à 100°C est comprise entre 1 ,5 et 15 mm2. s-1 selon la norme ASTM D445. The base oils of the lubricating compositions according to the invention may also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins. The polyalphaolefins used as base oils are, for example, obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100°C is between 1.5 and 15 mm 2 . s -1 according to standard ASTM D445.

A titre d’huile de base, selon la présente invention, on peut également citer les huiles re-raffinées, ou encore les huiles d’origine biologique. As base oil, according to the present invention, mention may also be made of re-refined oils, or even oils of biological origin.

Selon un mode de réalisation, la composition lubrifiante selon l’invention comprend une teneur en huile de base comprise de 75% à 95%, de préférence de 80% à 90%, en poids par rapport au poids de ladite composition lubrifiante. Selon un mode de réalisation, la composition lubrifiante selon l’invention comprend moins de 2,5%, de préférence de 1% à 2,5%, préférentiellement de 1 ,5% à 2%, en poids de détergent carboxylate par rapport au poids total de ladite composition lubrifiante. According to one embodiment, the lubricating composition according to the invention comprises a base oil content of from 75% to 95%, preferably from 80% to 90%, by weight relative to the weight of said lubricating composition. According to one embodiment, the lubricating composition according to the invention comprises less than 2.5%, preferably from 1% to 2.5%, preferentially from 1.5% to 2%, by weight of carboxylate detergent relative to the total weight of said lubricating composition.

Selon un mode de réalisation, la composition lubrifiante selon l’invention comprend de 0,02% à 2%, de préférence de 0,8% à 1 ,5%, en poids de détergent(s) sulfonate(s), par rapport au poids total de ladite composition lubrifiante. According to one embodiment, the lubricating composition according to the invention comprises from 0.02% to 2%, preferably from 0.8% to 1.5%, by weight of sulfonate detergent(s), relative to the total weight of said lubricating composition.

Selon un mode de réalisation, la composition lubrifiante selon l’invention comprend moins de 2,5%, de préférence de 1% à 2,5%, préférentiellement de 1 ,5% à 2%, en poids de détergent carboxylate par rapport au poids total de ladite composition lubrifiante et de 0,02% à 2%, de préférence de 0,8% à 1 ,5%, en poids de détergent(s) sulfonate(s), par rapport au poids total de ladite composition lubrifiante. According to one embodiment, the lubricating composition according to the invention comprises less than 2.5%, preferably from 1% to 2.5%, preferentially from 1.5% to 2%, by weight of carboxylate detergent relative to the total weight of said lubricating composition and from 0.02% to 2%, preferably from 0.8% to 1.5%, by weight of sulfonate detergent(s), relative to the total weight of said lubricating composition.

Selon un mode de réalisation, dans la composition lubrifiante selon l’invention, la teneur totale en détergent carboxylate et en détergent(s) sulfonate(s) est comprise de 0,05% à 3%, de préférence de 1 ,1 % à 2%, en poids par rapport au poids total de ladite composition lubrifiante. According to one embodiment, in the lubricating composition according to the invention, the total content of carboxylate detergent and sulfonate detergent(s) is from 0.05% to 3%, preferably from 1.1% to 2%, by weight relative to the total weight of said lubricating composition.

Selon un mode de réalisation, la composition lubrifiante selon l’invention comprend de 0,1% à 1%, de préférence de 0,5% à 0,8%, en poids d’un premier détergent sulfonate présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et de 0,1 % à 1%, de préférence de 0,5% à 0,8%, en poids d’un deuxième détergent sulfonate présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, par rapport au poids total de ladite composition lubrifiante. According to one embodiment, the lubricating composition according to the invention comprises from 0.1% to 1%, preferably from 0.5% to 0.8%, by weight of a first sulfonate detergent having a total number of TBN bases of less than 100 mg KOH/g, and from 0.1% to 1%, preferably from 0.5% to 0.8%, by weight of a second sulfonate detergent having a total number of TBN bases of greater than 200 mg KOH/g, relative to the total weight of said lubricating composition.

De préférence, la composition lubrifiante selon l’invention comprend en outre un ou plusieurs dispersant(s), de préférence en une teneur comprise de 2% à 5% en poids, de préférence de 3% à 4,5% en poids, et préférentiellement de 3,5% à 4% en poids, par rapport au poids total de ladite composition lubrifiante. La présente invention concerne également un procédé de lubrification d’un moteur de véhicule hybride rechargeable ou d’un moteur de véhicule hybride comprenant un prolongateur d’autonomie, comprenant la mise en contact d’au moins une pièce mécanique dudit moteur avec une composition lubrifiante telle que définie ci-dessus. Preferably, the lubricating composition according to the invention further comprises one or more dispersant(s), preferably in a content of from 2% to 5% by weight, preferably from 3% to 4.5% by weight, and preferentially from 3.5% to 4% by weight, relative to the total weight of said lubricating composition. The present invention also relates to a method for lubricating a plug-in hybrid vehicle engine or a hybrid vehicle engine comprising a range extender, comprising bringing at least one mechanical part of said engine into contact with a lubricating composition as defined above.

La présente invention concerne également l’utilisation de la composition d’additifs selon l’invention dans une composition lubrifiante pour réduire la corrosion dans un moteur de véhicule hybride rechargeable ou comprenant un prolongateur d’autonomie. The present invention also relates to the use of the additive composition according to the invention in a lubricating composition for reducing corrosion in a plug-in hybrid vehicle engine or one comprising a range extender.

EXEMPLES EXAMPLES

Exemple 1 : Préparation des compositions lubrifiantes Example 1: Preparation of lubricating compositions

Les compositions lubrifiantes sont préparées par mélange des composés décrits dans le tableau 2 ci-dessous. The lubricating compositions are prepared by mixing the compounds described in Table 2 below.

Les pourcentages indiqués correspondent à des pourcentages en masse par rapport à la masse totale de la composition. The percentages indicated correspond to percentages by mass relative to the total mass of the composition.

Tableau 2 Table 2

Le paquet d’additifs comprend notamment un antioxydant, deux anti-usure, un améliorant de l’indice de viscosité et/ou une modification de frottement et/ou un additif abaisseur du point d’écoulement. Exemple 2 : Evaluation des compositions lubrifiantes The additive package includes, among other things, an antioxidant, two anti-wear agents, a viscosity index improver and/or a friction modifier and/or a pour point depressant additive. Example 2: Evaluation of lubricating compositions

Les compositions lubrifiantes sont évaluées pour leur performance anticorrosion dans des moteurs hybrides PEHV (« Plug-In Hybrid Electric Vehicle »). The lubricating compositions are evaluated for their anti-corrosion performance in PEHV (“Plug-In Hybrid Electric Vehicle”) hybrid engines.

La méthode d’évaluation est adaptée de la norme ASTM D1748-22 et a pour but d’évaluer les propriétés anti-corrosives d’une composition lubrifiante. The evaluation method is adapted from ASTM D1748-22 and aims to evaluate the anti-corrosive properties of a lubricating composition.

Cette méthode évalue les propriétés anti-corrosion des produits de protection des métaux dans des conditions d'humidité élevée. Le test consiste à positionner des plaques d’acier préalablement immergées dans l’huile dans un cabinet humide à 49°C, avec circulation air, pendant 72h (Humidity cabinet Linetronic LT/HC- 250000M). This method evaluates the anti-corrosion properties of metal protection products in high humidity conditions. The test consists of positioning steel plates previously immersed in oil in a humidity cabinet at 49°C, with air circulation, for 72 hours (Humidity cabinet Linetronic LT/HC- 250000M).

Matériel utilisé Materials used

• Plaques de dimension 102x51x3.2mm, acier selon ASTM A109 • Plates measuring 102x51x3.2mm, steel according to ASTM A109

• Plaques de dimension 102x51x3mm en PMMA • • Plates measuring 102x51x3mm in PMMA •

• Solvants : heptane, éthanol • Solvents: heptane, ethanol

Préparation des plaques a) Face sablée. Preparation of the plates a) Sandblasted face.

• Sabler un lot de plaques selon les conditions suivantes : une pression de 5 bars et le nez de la sableuse positionné à une distance de 51 mm à 76 mm. • Sandblast a batch of plates under the following conditions: a pressure of 5 bars and the sandblaster nose positioned at a distance of 51 mm to 76 mm.

• Pour chaque série de sablage, contrôler la rugosité obtenue par profilométrie. b) Face poncée. • For each sandblasting series, check the roughness obtained by profilometry. b) Sanded face.

• Polir, à l’aide du papier abrasif (240 grit (nb de grains / unité de surface)), la plaque dans le sens de la longueur. • Polish the plate lengthwise using sandpaper (240 grit (number of grains / unit of surface area)).

• Toujours garder la plaque propre et sèche. • Always keep the plate clean and dry.

• En respectant les précautions d'usage, polir les quatre bords arrondis avec des coups réguliers dans la direction de chaque bord. Aléser les deux trous utilisés pour la suspension et les nettoyer à l'aide de mouchoir mouillé de solvant sélectionné. • Following the usual precautions, polish the four rounded edges with regular strokes in the direction of each edge. Ream the two holes used for suspension and clean them using a tissue moistened with the selected solvent.

• Ne jamais bouger la plaque pendant le ponçage. Continuer de polir la plaque jusqu’à obtention d’une surface uniforme. Examiner la plaque et s’il y a des rayures ou des imperfections, continuer de polir jusqu’à leur disparition. • On peut utiliser un profilomètre pour vérifier que la plaque est bien polie (Ra=0.25 à 0.51 pm). c) Plaques sablées et poncées • Never move the plate while sanding. Continue polishing the plate until a uniform surface is obtained. Examine the plate and if there are any scratches or imperfections, continue polishing until they disappear. • A profilometer can be used to check that the plate is well polished (Ra=0.25 to 0.51 pm). c) Sanded and sanded plates

• Laisser tremper les plaques dans l’heptane environ 30 min, vider le solvant et sécher à l’étuve pendant environ 30 minutes. • Leave the plates to soak in heptane for approximately 30 minutes, empty the solvent and dry in an oven for approximately 30 minutes.

• Enlever la saleté présente sur la plaque en utilisant un mouchoir humidifié par le solvant choisi. • Remove any dirt from the plate using a tissue moistened with the chosen solvent.

• Nettoyer jusqu’à ce qu’il n’y ait plus de traces noires sur le mouchoir. • Clean until there are no more black marks on the tissue.

• Utiliser les plaques préparées le jour même. • Use the prepared plates the same day.

Préparation de l’enceinte Preparing the enclosure

• Mettre en route l’appareil, ouvrir la vanne d’arrivée d’air située en haut derrière l’appareil et laisser l’enceinte se stabiliser selon les conditions d’utilisation suivantes : • Start the device, open the air inlet valve located at the top behind the device and allow the enclosure to stabilize according to the following operating conditions:

- Température de l’air - Air temperature

■ Dans la cabine : 48,9 ± 1 ,1°C ■ In the cabin: 48.9 ± 1.1°C

■ En dehors de la cabine : 24,1 ± 5,5°C ■ Outside the cabin: 24.1 ± 5.5°C

■ Ratio d’air dans la cabine 0,878 ± 0,028 m3/h ■ Cabin air ratio 0.878 ± 0.028 m 3 /h

- Eau dans la cabine - Water in the cabin

■ Niveau : 203 mm ± 6,4 mm ■ Level: 203 mm ± 6.4 mm

■ pH : 5,5 à 7,5 ■ pH: 5.5 to 7.5

■ Vitesse de rotation : 0,33 r/min ± 0,03 r/min ■ Rotation speed: 0.33 r/min ± 0.03 r/min

Déroulé de l’essai Course of the test

• Placer la plaque dans l’huile à 23,3 ± 0,5°C (submerger entièrement la plaque) et agiter pendant 10set égoutter pendant 10s. • Place the plate in the oil at 23.3 ± 0.5°C (completely submerge the plate) and shake for 10s and drain for 10s.

• Replacer la plaque dans l’huile pendant 1 minute avec une légère agitation. • Place the plate back in the oil for 1 minute with gentle stirring.

• Suspendre la plaque sur le support et laisser égoutter à température ambiante pendant 2h ± 20 min. • Hang the plate on the support and leave to drain at room temperature for 2 hours ± 20 minutes.

Il est aussi possible de suspendre les plaques sur le support adéquat et de les imbiber d’huile par arrosage avec une pipette, ensuite les laisser s’égoutter. It is also possible to hang the plates on the appropriate support and soak them with oil by sprinkling with a pipette, then let them drain.

• A la fin de la période d’égouttage, suspendre les plaques dans la cabine d’humidité et ouvrir la cabine 2 fois par jour à 7 à 8h d’intervalle entre les deux, pendant 15 minutes, pour la première inspection, et pour 5 minutes pour la deuxième inspection. • Retirer les plaques, les rincer à l’éthanol ensuite à l’heptane et les laisser sécher sur le support. • At the end of the draining period, hang the plates in the humidity cabin and open the cabin twice a day at 7 to 8 hour intervals between the two, for 15 minutes for the first inspection, and for 5 minutes for the second inspection. • Remove the plates, rinse them with ethanol then with heptane and leave them to dry on the support.

Expression des résultats Expression of results

• Evaluer visuellement le pourcentage de corrosion sur chaque face des plaques. • Visually assess the percentage of corrosion on each side of the plates.

• Les huiles (ou compositions lubrifiantes) sont PASS ou FAIL selon le nombre et la taille des points de corrosion visibles sur la surface de la plaque. • Oils (or lubricating compositions) are PASS or FAIL depending on the number and size of corrosion spots visible on the surface of the plate.

• Le résultat sera PASS : Si la plaque ne contient pas plus de 3 points de rouille, et dont la taille ne dépasse pas 1 mm. • The result will be PASS: If the plate does not contain more than 3 rust spots, and the size does not exceed 1 mm.

• Le résultat sera FAIL : Si la plaque contient un ou plusieurs points de rouille de plus de 1 mm ou plus de 3 points de n'importe quelle taille. • The result will be FAIL: If the plate contains one or more rust spots larger than 1 mm or more than 3 spots of any size.

Les résultats obtenus pour la composition CL1 selon l’invention et la composition comparative CC1 sont indiqués dans le tableau 3 ci-dessous. The results obtained for the composition CL1 according to the invention and the comparative composition CC1 are indicated in table 3 below.

Tableau 3 Table 3

En conclusion, il apparait que la combinaison d’additifs selon l’invention, comprenant à la fois un détergent carboxylate et deux détergents sulfonates, permet d’obtenir de bonnes propriétés anti-corrosion pour la composition lubrifiante, notamment en comparaison avec une composition d’additifs comprenant d’autres types de détergents. In conclusion, it appears that the combination of additives according to the invention, comprising both a carboxylate detergent and two sulfonate detergents, makes it possible to obtain good anti-corrosion properties for the lubricating composition, particularly in comparison with an additive composition comprising other types of detergents.

Claims

REVENDICATIONS 1. Utilisation d’une composition d’additifs pour lubrifiants dans une composition lubrifiante, pour réduire la corrosion dans un moteur de véhicule hybride rechargeable ou comprenant un prolongateur d’autonomie, ladite composition comprenant un détergent carboxylate et un ou plusieurs détergent(s) sulfonate(s). 1. Use of a lubricant additive composition in a lubricating composition, for reducing corrosion in a plug-in hybrid vehicle engine or one comprising a range extender, said composition comprising a carboxylate detergent and one or more sulfonate detergent(s). 2. Utilisation selon la revendication 1 , dans laquelle la composition d’additifs comprend un détergent carboxylate et deux détergents sulfonates. 2. Use according to claim 1, wherein the additive composition comprises a carboxylate detergent and two sulfonate detergents. 3. Utilisation selon la revendication 1 ou 2, dans laquelle le détergent carboxylate est choisi parmi les sels de métaux alcalins ou de métaux alcalino-terreux de carboxylate, et est de préférence du carboxylate de calcium. 3. Use according to claim 1 or 2, wherein the carboxylate detergent is selected from alkali metal or alkaline earth metal salts of carboxylate, and is preferably calcium carboxylate. 4. Utilisation selon l’une quelconque des revendications 1 à 3, dans laquelle les détergents sulfonates sont choisis parmi les sels de métaux alcalins ou de métaux alcalino-terreux de sulfonate, de préférence du sulfonate de calcium, du sulfonate de magnésium ou leur mélange. 4. Use according to any one of claims 1 to 3, in which the sulfonate detergents are chosen from alkali metal or alkaline earth metal sulfonate salts, preferably calcium sulfonate, magnesium sulfonate or their mixture. 5. Utilisation selon l’une quelconque des revendications 1 à 4, dans laquelle le détergent carboxylate présente un nombre total de bases TBN compris de 120 à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896. 5. Use according to any one of claims 1 to 4, wherein the carboxylate detergent has a total base number TBN of from 120 to 200 mg KOH/g, as measured according to ASTM D-2896. 6. Utilisation selon l’une quelconque des revendications 1 à 5, dans laquelle la composition d’additifs comprend un mélange de deux détergents sulfonates, le premier détergent sulfonate, de préférence du sulfonate de calcium, présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et le deuxième détergent sulfonate, de préférence du sulfonate de magnésium, présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896. 6. Use according to any one of claims 1 to 5, wherein the additive composition comprises a mixture of two sulfonate detergents, the first sulfonate detergent, preferably calcium sulfonate, having a total base number TBN of less than 100 mg KOH/g, and the second sulfonate detergent, preferably magnesium sulfonate, having a total base number TBN of greater than 200 mg KOH/g, as measured according to ASTM D-2896. 7. Utilisation selon l’une quelconque des revendications 1 à 6, dans laquelle la composition d’additifs comprend du carboxylate de calcium, du sulfonate de calcium et du sulfonate de magnésium, de préférence du carboxylate de calcium avec un nombre total de bases TBN compris de 120 à 200 mg KOH/g, du sulfonate de calcium avec un nombre total de bases TBN inférieur à 100 mg KOH/g et du sulfonate de magnésium avec un nombre total de bases TBN supérieur à 200 mg KOH/g. 7. Use according to any one of claims 1 to 6, wherein the additive composition comprises calcium carboxylate, calcium sulfonate and magnesium sulfonate, preferably calcium carboxylate with a total base number TBN of 120 to 200 mg KOH/g, calcium sulfonate calcium with a total base number TBN less than 100 mg KOH/g and magnesium sulfonate with a total base number TBN greater than 200 mg KOH/g. 8. Utilisation selon l’une quelconque des revendications 1 à 7, dans laquelle la composition d’additifs comprend de 1% à 30%, de préférence de 5% à 20%, préférentiellement de 8% à 15%, en poids de détergent carboxylate par rapport au poids total de ladite composition d’additifs. 8. Use according to any one of claims 1 to 7, in which the additive composition comprises from 1% to 30%, preferably from 5% to 20%, preferentially from 8% to 15%, by weight of carboxylate detergent relative to the total weight of said additive composition. 9. Utilisation selon l’une quelconque des revendications 1 à 8, dans laquelle la composition d’additifs comprend de 1% à 20%, de préférence de 5% à 10%, en poids de détergent(s) sulfonate(s), par rapport au poids total de ladite composition d’additifs. 9. Use according to any one of claims 1 to 8, in which the additive composition comprises from 1% to 20%, preferably from 5% to 10%, by weight of sulfonate detergent(s), relative to the total weight of said additive composition. 10. Utilisation selon l’une quelconque des revendications 1 à 9, dans laquelle la composition d’additifs comprend de 1 % à 10%, de préférence de 2% à 5%, en poids d’un premier détergent sulfonate présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et de 1% à 10%, de préférence de 2% à 5%, en poids d’un deuxième détergent sulfonate présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, par rapport au poids total de ladite composition d’additifs. 10. Use according to any one of claims 1 to 9, wherein the additive composition comprises from 1% to 10%, preferably from 2% to 5%, by weight of a first sulfonate detergent having a total TBN base number of less than 100 mg KOH/g, and from 1% to 10%, preferably from 2% to 5%, by weight of a second sulfonate detergent having a total TBN base number of greater than 200 mg KOH/g, relative to the total weight of said additive composition. 11. Utilisation selon l’une quelconque des revendications 1 à 10, dans laquelle la teneur totale en détergent carboxylate et en détergent(s) sulfonate(s) est comprise de 2% à 30%, de préférence de 5% à 20%, en poids par rapport au poids total de ladite composition d’additifs. 11. Use according to any one of claims 1 to 10, in which the total content of carboxylate detergent and sulfonate detergent(s) is from 2% to 30%, preferably from 5% to 20%, by weight relative to the total weight of said additive composition. 12. Utilisation selon l’une quelconque des revendications 1 à 11 , dans laquelle la composition d’additifs comprend en outre un ou plusieurs dispersant(s), de préférence en une teneur comprise de 10% à 50% en poids, de préférence de 15% à 40% en poids, et préférentiellement de 20% à 30% en poids, par rapport au poids total de ladite composition d’additifs. 12. Use according to any one of claims 1 to 11, in which the additive composition further comprises one or more dispersant(s), preferably in a content of 10% to 50% by weight, preferably 15% to 40% by weight, and preferentially 20% to 30% by weight, relative to the total weight of said additive composition. 13. Utilisation selon l’une quelconque des revendications 1 à 12, dans laquelle la composition d’additifs comprend en outre un ou plusieurs additif(s) additionnel(s) choisi(s) dans le groupe constitué des additifs anti-usure, des additifs antioxydants, des additifs améliorant l’indice de viscosité, des additifs abaisseurs de point d’écoulement, des additifs modificateurs de frottement, et de leurs mélanges. 13. Use according to any one of claims 1 to 12, wherein the additive composition further comprises one or more additional additive(s) selected from the group consisting of anti-wear additives, antioxidant additives, viscosity index improving additives, pour point depressant additives, friction modifying additives, and mixtures thereof. 14. Composition d’additifs pour lubrifiants, comprenant un détergent carboxylate et deux détergents sulfonates, le premier détergent sulfonate, de préférence du sulfonate de calcium, présentant un nombre total de bases TBN inférieur à 100 mg KOH/g, et le deuxième détergent sulfonate, de préférence du sulfonate de magnésium, présentant un nombre total de bases TBN supérieur à 200 mg KOH/g, tel que mesuré selon la norme ASTM D-2896. 14. A lubricant additive composition comprising a carboxylate detergent and two sulfonate detergents, the first sulfonate detergent, preferably calcium sulfonate, having a total base number (TBN) of less than 100 mg KOH/g, and the second sulfonate detergent, preferably magnesium sulfonate, having a total base number (TBN) of greater than 200 mg KOH/g, as measured according to ASTM D-2896. 15. Composition lubrifiante comprenant au moins une huile de base et une composition d’additifs selon la revendication 14. 15. Lubricating composition comprising at least one base oil and an additive composition according to claim 14. 16. Composition lubrifiante selon la revendication 15, dans laquelle la teneur en huile de base est comprise de 75% à 95%, de préférence de 80% à 90%, en poids par rapport au poids de ladite composition lubrifiante. 16. Lubricating composition according to claim 15, wherein the base oil content is from 75% to 95%, preferably from 80% to 90%, by weight relative to the weight of said lubricating composition. 17. Procédé de lubrification d’un moteur de véhicule hybride rechargeable ou d’un moteur de véhicule hybride comprenant un prolongateur d’autonomie, comprenant la mise en contact d’au moins une pièce mécanique dudit moteur avec une composition lubrifiante selon la revendication 15 ou 16. 17. Method for lubricating a plug-in hybrid vehicle engine or a hybrid vehicle engine comprising a range extender, comprising bringing at least one mechanical part of said engine into contact with a lubricating composition according to claim 15 or 16.
PCT/EP2025/051812 2024-01-25 2025-01-24 Additive composition for hybrid vehicles Pending WO2025158003A1 (en)

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Citations (6)

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US20050137098A1 (en) * 2003-12-22 2005-06-23 Chevron Oronite S.A. Overbased detergents for lubricating oil applications
US20070123437A1 (en) * 2005-11-30 2007-05-31 Chevron Oronite Company Llc Lubricating oil composition with improved emission compatibility
US20070142239A1 (en) * 2005-12-20 2007-06-21 Chevron Oronite Company Llc Lubricating oil composition
US20160130521A1 (en) * 2012-11-16 2016-05-12 Total Marketing Services Lubricant composition
US20190002795A1 (en) * 2017-06-30 2019-01-03 Chevron Oronite Company Llc Marine diesel lubricant oil compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995034619A1 (en) * 1994-06-16 1995-12-21 Exxon Chemical Limited Lubricating oils containing alkali metal additives
US20050137098A1 (en) * 2003-12-22 2005-06-23 Chevron Oronite S.A. Overbased detergents for lubricating oil applications
US20070123437A1 (en) * 2005-11-30 2007-05-31 Chevron Oronite Company Llc Lubricating oil composition with improved emission compatibility
US20070142239A1 (en) * 2005-12-20 2007-06-21 Chevron Oronite Company Llc Lubricating oil composition
US20160130521A1 (en) * 2012-11-16 2016-05-12 Total Marketing Services Lubricant composition
US20190002795A1 (en) * 2017-06-30 2019-01-03 Chevron Oronite Company Llc Marine diesel lubricant oil compositions

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