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
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • 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
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines

Definitions

• the present invention relates to the lubrication of hybrid motor vehicle engines and micro-hybrid powered vehicles, in particular micro-hybrid powered vehicles equipped with the "Stop-and-Start" system.
• Hybrid drive systems overcome these disadvantages by implementing an electric motor and a conventional thermal internal combustion engine, in series, in parallel or in combination.
• a hybrid vehicle starting is provided by the electric motor. Up to a speed of the order of 50 km / h, it is the electric motor that ensures the traction of the vehicle. As soon as a higher speed is reached or a strong acceleration is required, the internal combustion engine takes over. When the speed decreases or when the vehicle stops, the internal combustion engine stops and the electric motor takes over. Thus, the internal combustion engine of hybrid vehicles undergoes a significant number of stops and restarts compared to a conventional combustion engine thermal vehicles.
• certain vehicles are equipped with the "Stop-and-Start” system, also known as automatic stops and restarts. These vehicles are generally considered “micro-hybrid” vehicles. Indeed these vehicles are equipped with a thermal internal combustion engine and an alternator-starter or a reinforced starter that ensure the stopping and restarting of the internal combustion engine thermal when the vehicle comes to a stop.
• the thermal internal combustion engines of microhybrid vehicles equipped with the "stop-and-start” system such as the internal combustion engines of hybrid vehicles, undergo a significant number of shutdowns and restarts compared to a thermal internal combustion engine. conventional vehicles.
• the internal combustion engine of hybrid vehicles or micro-hybrid vehicles undergoes, during its lifetime, a number of stops and start-ups much larger than that of a conventional vehicle.
• the applicant company has therefore developed new lubricating compositions comprising at least one polyalkylene glycol obtained by polymerization or copolymerization of alkylene oxides, of which at least one butylene oxide, and also comprising at least one polymer improving the viscosity.
• the amount of polyalkylene glycol in the lubricant compositions according to the invention is between 1 to 28% by weight, relative to the total weight of lubricating composition.
• the Applicant Company has surprisingly found that the combination of these polyalkylene glycols and certain inorganic friction modifiers, in particular organomolybdenum compounds, advantageously makes it possible to further reduce the wear of the motor bearings.
• EP0438709 discloses an engine oil comprising at least one base oil, at least one viscosity index improving polymer and at least one product resulting from the reaction of alkylphenols or bisphenol A with at least one butylene oxide or an oxide of butylene / propylene to improve the cleanliness of the pistons of automotive engines.
• this document does not disclose an engine lubricating composition comprising at least one organomolybdenum compound.
• the subject of the invention is an engine lubricating composition
• a engine lubricating composition comprising at least one base oil, at least one viscosity index improving polymer, at least one organomolybdenum compound and at least one polyalkylene glycol, obtained by polymerization or copolymerization of oxides.
• alkylene compound comprising from 3 to 8 carbon atoms, of which at least one butylene oxide, the amount of polyalkylene glycol being from 1 to 28% by weight, relative to the total weight of lubricating composition.
• the lubricating composition comprises from 0.1 to 10% by weight, relative to the total mass of lubricating composition, of organomolybdenum compound, preferably from 0.5 to 8%, more preferably from 1 to 5%.
• the organomolybdenum compound is chosen from dithiocarbamates and / or dithiophosphates of molybdenum, taken alone or as a mixture.
• the polyalkylene glycol is a copolymer of butylene oxide and propylene oxide.
• the weight ratio of butylene oxide to propylene oxide is from 3: 1 to 1: 3, preferably from 3: 1 to 1: 1.
• the polyalkylene glycol has a molar mass measured according to ASTM D4274 of 300 to 1000 grams per mole, preferably 500 to 750 grams per mole.
• the polyalkylene glycol has a kinematic viscosity at 100 ° C measured according to ASTM D445 of 1 to 12 cSt, preferably 3 to 7 cSt, more preferably 3.5 to 6.5 cSt.
• the lubricating composition comprises from 2 to 20% by weight of polyalkylene glycol, relative to the total weight of the lubricating composition, preferably from 3 to 15%, still more preferably from 5 to 12%, even more preferably from 6 to 20% by weight. at 10%.
• the viscosity index improving polymer is selected from the group consisting of copolymer olefins, copolymers of ethylene and alpha-olefin, copolymers of styrene and olefin, polyacrylates alone or in admixture. .
• the invention also relates to the use of at least one polyalkylene glycol, obtained by polymerization or copolymerization of alkylene oxides comprising from 3 to 8 carbon atoms, of which at least one butylene oxide in a lubricating composition for lubricating metal surfaces, polymeric surfaces and / or amorphous carbon surfaces, thermal internal combustion engines of vehicles with hybrid and / or microhybrid motorization.
• said polyalkylene glycol is combined with at least one organomolybdenum compound.
• This use is intended to reduce the wear of the internal combustion engine, in particular the wear of the bearings of the internal combustion engine, in particular the wear of the connecting rod bearings of the internal combustion engine.
• Another object of the invention is a method of lubricating at least one part of a motor vehicle engine hybrid and or micro-hybrid, said method comprising at least one step of contacting the lubricant composition as defined above with at least one part of said engine, said part comprising at least one metal surface or a polymeric surface and / or an amorphous carbon surface.
• said piece is a pad, preferably a connecting rod pad.
• the present invention relates to the field of lubrication of internal combustion engines of hybrid or micro-hybrid motor vehicles.
• vehicle with micro-hybrid powertrain means vehicles comprising a thermal internal combustion engine, but no electric motor such as hybrid vehicles, the "hybrid” character being provided by the presence of the Stop and Start system provided by an alternator. -starter or a reinforced starter which ensure the stopping and restarting of the engine when the vehicle comes to rest and then restarts.
• the present invention more preferably relates to the lubrication of thermal internal combustion engines of vehicles equipped with hybrid or micro-hybrid systems circulating in an urban environment, where the Stop-and-Start phenomenon and the resulting wear are increased.
• a fixed part comprising the engine block, the cylinder head, the cylinder head gasket, the liner and various parts ensuring the assembly and sealing of these different parts.
• a movable part comprising the crankshaft, the connecting rod and its bearings, the piston and its segments.
• the role of the connecting rod is to transmit to the crankshaft the forces received by the piston, transforming a reciprocating rectilinear motion into a circular motion in one direction.
• a connecting rod has two circular bores, one of small diameter, called small end, and the other of large diameter called big end. Between these two bores, is the body of the connecting rod connecting the small end and the small end.
• the small end is engaged around the axis of the piston, the friction between the small end and the axis of the piston is reduced by the interposition between the two moving parts of a circular ring covered or made of anti-metal. friction (bronze, for example), or bearings (usually needle).
• crankpin crankpin The big end, it, encloses the crankpin crankpin.
• the friction between the crankpin and crankpin assembly is reduced by the existence of an oil film and the interposition between the crankpin and the crankpin, pads. In this case we speak of big-end bearings.
• crankshaft is a rotating part. Its positioning and maintenance are achieved by a number of bearings, called trunnions. So we have a fixed part, the bearing crankshaft, which encloses a moving part, the crankshaft journal. Lubrication between these two parts is imperative and pads are put in place to resist the forces applied to these bearings. In this case we speak of trunnion bushings (or bearings of shaft line or crankshaft bearings).
• the role of the bearing in the case of a big end or a trunnion, is to allow a good rotation of the crankshaft.
• the pads are thin shells in the shape of a half-cylinder. These are parts that are extremely sensitive to lubrication conditions. If there is contact between the bushing and the rotating shaft, crankpin or pin, the energy released systematically leads to significant wear or engine breakage. The generated wear can also play the role of amplifying the phenomenon and the severity of the contact.
• the bearings are subject to several types of wear in the motors.
• the different types of wear encountered in motors are: adhesive wear or wear through metal-to-metal contact, abrasive wear, corrosive wear, fatigue wear, or complex forms of wear ( contact corrosion, cavitation erosion, electrical wear).
• the pads are subject in particular to adhesive wear, the invention is particularly useful for improving this type of wear but the invention can nevertheless be applied to the other types of wear mentioned above.
• Surfaces that are sensitive to wear are metal-like surfaces, or metallic-type surfaces coated with another layer which may be either a polymer or an amorphous carbon layer. . Wear occurs at the interface between said surfaces that come into contact when the oil film becomes insufficient.
• the metal type surface may be a surface made of a pure metal such as tin (Sn) or lead (Pb). Most of the time, the metal type surface is a metal type alloy, based on a metal and at least one other metal element or not. A frequently used alloy is steel, iron alloy (Fe) and carbon (C).
• the bearings used in the automotive industry are mostly bearings whose support is made of steel, a support coated or not with another metal alloy.
• the other metal alloys constituting the metal surfaces according to the invention are alloys comprising as base element tin (Sn), lead (Pb), copper (Cu) or aluminum (Al).
• Cadmium (Cd), silver (Ag) or zinc (Zn) may also be basic elements of the metal alloys constituting the metal surfaces according to the invention.
• To these basic elements will be added other elements chosen from antimony (Sb), arsenic (As), chromium (Cr), indium (In), magnesium (Mg), nickel (Ni), platinum (Pt) or silicon (Si).
• Preferred alloys are based on the following combinations Al / Sn, Al / Sn / Cu, Cu / Sn, Cu / Al, Sn / Sb / Cu, Pb / Sb / Sn, Cu / Pb, PB / Sn / Cu, Al / Pb / Si, Pb / Sn, Pb / In, Al / Si, Al / Pb.
• the preferred combinations are Sn / Cu, Sn / Al, Pb / Cu or Pb / Al combinations.
• Copper and lead-based alloys are preferred alloys, and are also known as cupro-lead or white metal alloys.
• the surfaces affected by wear are polymeric surfaces.
• the pads are made of steel and additionally comprise this polymeric surface.
• the polymers that can be used are either thermoplastics such as polyamides, polyethylenes, fluoropolymers such as tetrafluoroethylenes, in particular polytetrafluoroethylenes (PTFE), or thermosetting agents such as polyimides, phenoplasts (or PF phenol-formaldehyde resins).
• the surfaces concerned by the wear are surfaces of amorphous carbon type.
• the bearings are made of steel and include in addition this surface type amorphous carbon.
• the surfaces of amorphous carbon type are also called DLC, or Diamond Like Carbon or Diamond Like Coating, whose carbons are sp 2 and sp 3 hybridizations.
• polyalkylene glycols used in the context of the present invention have properties suitable for use in a motor oil. These are polymers or copolymers (statistics or blocks) of alkylene oxides, which can be prepared according to the known methods described in the application WO 2009/134716 on page 2 line 26 to page 4 line 12, for example by etching an alcohol initiator on the epoxy bond of an alkylene oxide and propagating the reaction.
• R 2x-1 and R 2x are preferably linear.
• At least one at least one of R 2x-1 and R 2x is hydrogen.
• R 2x is preferably hydrogen.
• the sum of the carbon number of R 2x-1 and R 2x is from 1 to 6.
• the sum of the carbon number of R 2x-1 and R 2x is 2.
• the corresponding alkylene oxide monomer is butylene oxide.
• the alkylene oxides used in the structure of the PAGs used in the compositions according to the invention contain from 3 to 8 carbon atoms. At least one of the alkylene oxides entering into the structure of these PAGs is a butylene oxide, said butylene oxide being 1,2-butylene oxide or 2,3-butylene oxide, preferably 1,2 butylene oxide.
• the PAG obtained, in part or in full, from ethylene oxide do not have a lipophilic character sufficient to be used in engine oil formulations.
• they can not be used in combination with other mineral, synthetic or natural base oils.
• alkylene oxides comprising more than 8 carbon atoms is also not desired because, to produce bases having the molar mass and therefore the targeted viscosimetric grade for the motor applications, then there will be a number of reduced monomers (n low in formula (A) above), with side chains R 2x-1 and R 2x long. This adversely affects the overall linear character of the PAG molecule and leads to viscosity indices (VI) that are too low for engine oil application.
• the viscosity index VI (measured according to standard NFT 60136) of the PAGs of formula (A) used in the invention is greater than or equal to 100, preferably greater than or equal to 120.
• the PAGs according to the invention are obtained from alkylene oxides comprising at least one butylene oxide.
• copolymers of butylene oxide (BO) and propylene oxide (PO) are particularly preferred because they have both good tribological and rheological properties of PAGs containing ethylene oxide and / or polypropylene units, and good solubility in conventional mineral, synthetic, and natural bases, and other oily compounds.
• PAGs are prepared by reacting one or more alcohols with a mixture of butylene oxide and propylene oxide.
• PAGs prepared with a mixture where this ratio is from 3: 1 to 1: 1 are particularly well miscible and soluble in base oils, including Group IV synthetic oils (polyalphaolefins).
• the PAGs according to the invention are prepared from alcohol containing from 8 to 12 carbon atoms. 2-Ethylhexanol and dodecanol, alone or in a mixture, and in particular dodecanol, are particularly preferred since the PAGs prepared from these alcohols have very low traction coefficients.
• the PAGs according to the invention are such that their molar carbon to oxygen ratio is greater than 3: 1, preferably ranging from 3: 1 to 6: 1. This gives said PAG polarity and viscosity index properties particularly suitable for use in motor oil.
• the molar mass, measured according to the ASTM D2502 standard, of the PAGs according to the invention is preferably between 300 and 1000 grams per mole (g / mol), preferably between 350 and 600 g / mol (that is why they contain a number of alkylene oxide units n limited as described above in the formula (A)).
• the molar mass, measured according to the ASTM D4274 standard, of the PAGs according to the invention has a value preferably ranging from 300 to 1000 grams per mole (g / mol), preferably ranging from 500 to 750 g / mol.
• KV100 kinematic viscosities at 100 ° C.
• KV100 generally ranging from 1 to 12 cSt, preferably from 3 to 7 cSt, preferentially from 3.5 to 6.5 cSt, or from 4 to 6 cSt or 3.5 at 4.5 cSt.
• the KV100 of the compositions is measured according to ASTM D445.
• the use of light PAGs (KV100 approximately from 2 to 6.5 cSt) is preferably chosen, in order to be able to more easily formulate cold grade 5W or 0W multigrade oils according to the SAEJ300 classification, since the heavier PAGs (a) have cold properties (high SCC) that do not easily achieve these grades.
• Another object of the invention is a lubricant composition for an engine, in particular for a hybrid or micro-hybrid engine, said lubricant composition comprising at least one base oil, at least one organomolybdenum compound and from 1 to 28% by weight of a or more polyalkylene glycols described above, with respect to the total weight of lubricating composition.
• the lubricating compositions according to the invention comprise from 2 to 20% by weight of one or more polyalkylene glycols described above, relative to the total mass of lubricating composition, more preferably from 3 to 15%, and even more preferably from 5 to 12%, even more preferably from 6 to 10%.
• the lubricating compositions used according to the present invention comprise one or more base oils, generally representing from 50% to 90% by weight, relative to the total mass of the lubricating composition, preferably from 60% to 85%, more preferably from 65 to 80%, even more preferably 70 to 75%.
• the base oil (s) used in the lubricant compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized. below, alone or mixed.
• the base oil (s) used in the lubricant compositions according to the invention may be chosen from the oils of synthetic origin of group VI according to the ATIEL classification.
• oils can be oils of vegetable, animal or mineral origin.
• the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
• the base oils of the compositions according to the present invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
• the polyalphaolefins used as base oils are, for example, obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C. of between 1.5 and 15 cSt (ASTM D445). ). Their weight average molecular weight is typically between 250 and 3000 (ASTM D5296).
• Mixtures of synthetic and mineral oils may also be employed, for example when formulating multigrade oils to avoid cold start problems.
• the lubricant compositions according to the invention also comprise at least one inorganic friction modifier chosen from organomolybdenum compounds. These compounds are, as their name indicates, compounds based on molybdenum, carbon and hydrogen, but these compounds also contain sulfur and phosphorus, and also oxygen and nitrogen.
• the organomolybdenum compounds used in the compositions according to the invention are, for example, molybdenum dithiophosphates, molybdenum dithiocarbamates, molybdenum dithiophosphinates, molybdenum xanthates, molybdenum thioxanthates, and various organic molybdenum complexes such as carboxylates.
• molybdenum esters, molybdenum esters, molybdenum amides obtainable by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides or fatty acids, or fatty acid derivatives (esters , amines, amides ).
• Organomolybdenum compounds which are suitable for the lubricating compositions according to the present invention are for example described in the application EP2078745 , from paragraph [0036] to paragraph [062].
• Preferred organomolybdenum compounds are molybdenum dithiophosphates and / or molybdenum dithiocarbamates.
• molybdenum dithiocarbamates have been found to be very effective in reducing pad wear.
• These molybdenum dithiocarbamates have the following general formula (I) in which R 1 , R 2 , R 3 or R 4 are independently of each other linear or branched alkyl groups, saturated or unsaturated, comprising 4 to 18 carbon atoms, preferably 8 to 13.
• molybdenum dithiophosphates have the following general formula (II) in which R 5 , R 6 , R 7 or R 8 are independently of each other linear or branched alkyl groups, saturated or unsaturated, comprising 4 to 18 carbon atoms, preferably 8 to 13.
• the lubricating compositions according to the invention may comprise between 0.1 and 10% by weight, relative to the total mass of lubricating composition, of organomolybdenum compound, preferably between 0.5 and 8%, more preferably between 1 and 5% more preferably between 2 and 4%.
• organomolybdenum compounds that may be used in the compositions according to the invention comprise from 1 to 30% by weight of molybdenum, relative to the total mass of organomolybdenum compound, preferably from 2 to 20%, more preferably from 4 to 10%, and even more preferably 8 to 5%.
• organomolybdenum compounds that can be used in the compositions according to the invention comprise from 1 to 10% by weight of phosphorus, with respect to the total weight of organomolybdenum compound, preferably from 2 to 8%, more preferably from 3 to 6%, and even more preferably from 4 to 5%.
• the lubricating compositions may comprise at least one or more viscosity index (VI) improving polymers, such as for example Olefins Copolymers (OCP), copolymers of ethylene and alpha-olefin, copolymers of styrene and olefin such as copolymers of styrene and isoprene, polyacrylates such as polymethacrylates (PMA).
• VI viscosity index
• OCP Olefins Copolymers
• COP Olefins Copolymers
• styrene and olefin such as copolymers of styrene and isoprene
• polyacrylates such as polymethacrylates (PMA).
• the lubricating compositions according to the present invention may contain from 1 to 15% by weight, relative to the total weight of the lubricating composition, of at least one viscosity index improving polymer, preferably from 2 to 10%, more preferably 3 to 8%.
• the lubricant compositions according to the invention preferably have a viscosity index value or VI, measured according to ASTM D2270 greater than 130, preferably greater than 140, preferably greater than 150.
• the lubricant compositions according to the invention have a kinematic viscosity (KV100) at 100 ° C., measured according to ASTM D445, of between 3.8 cSt and 26.1 cSt, preferably between 5.6 and 12.5 cSt. which corresponds, according to the SAE J 300 classification, to grades 20 (5.6 to 9.3 cSt) or 30 (9.3 to 12.5 cSt) hot.
• KV100 kinematic viscosity
• the lubricant compositions according to the invention are multigrade engine oils grade 0W or 5W cold, and 20 or 30 hot according to classification SAE J 300.
• the lubricant compositions for engines used according to the invention may furthermore contain all types of additives suitable for use as engine oil.
• additives can be introduced individually and / or included in packages of additives used in commercial lubricant formulations, performance levels as defined by the ACEA (Association of European Automobile Manufacturers) and / or the API. (American Petroleum Institute).
• ACEA Association of European Automobile Manufacturers
• API API.
• These additive packages are concentrates comprising about 30% by weight of dilution base oil.
• the lubricant compositions according to the invention may contain, in particular and without limitation, anti-wear and extreme pressure additives, antioxidants, detergents or overbased detergents, pour point improvers, dispersants, antifoams, thickeners. ...
• the anti-wear and extreme pressure additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
• the most commonly used is zinc dithiophosphate or ZnDTP. This category also contains various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
• anti-wear additives there is a wide variety of anti-wear additives, but the most used category in engine oils is that of phosphosulfur additives such as metal alkylthiophosphates, particularly zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
• the preferred compounds are of formula Zn ((SP (S) (OR 9 ) (OR 10 )) 2 , or R 9 and R 10 are linear or branched, saturated or unsaturated alkyl groups, preferably containing from 1 to 18 atoms ZnDTP is typically present at levels of the order of 0.1 to 2% by weight, based on the total weight of the lubricating composition.
• Amine phosphates, polysulfides, especially sulfur olefins, are also commonly used antiwear additives.
• the anti-wear and extreme-pressure additives are generally present in the compositions for motor lubricants at contents of between 0.5 and 6% by weight, preferably between 0.7 and 2%, preferably between 1 and 1.5%. relative to the total mass of the lubricating composition.
• Antioxidants delay the degradation of oils in service, degradation that can result in the formation of deposits, the presence of sludge, or an increase the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides.
• antioxidants are phenolic and / or amine antioxidants.
• Phenolic antioxidants may be ashless, or may be in the form of neutral or basic metal salts. Typically, these are compounds containing a sterically hindered hydroxyl group, for example when two hydroxyl groups are in the ortho or para position of each other, or when the phenol is substituted by an alkyl group comprising at least 6 carbon atoms. .
• Amino compounds are another class of antioxidants that can be used alone or possibly in combination with phenolic compounds.
• Typical examples are aromatic amines, of formula R 11 R 12 R 13 N, where R 11 is an optionally substituted aromatic group, or aromatic group, R 12 is an optionally substituted aromatic group, R 13 is hydrogen, or an alkyl or aryl group, or a group of the formula R 14 S (O) x R 15 , where R 14 and R 15 are alkylene, alkenylene, or aralkylene, and x is an integer of 0, 1 or 2.
• Sulfurized alkyl phenols or their alkali and alkaline earth metal salts are also used as antioxidants.
• antioxidants are that of oil-soluble copper compounds, for example copper thio- or dithiophosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, acetylacetonates of copper.
• the copper salts I and II, succinic acid or anhydride are used.
• Antioxidants alone or as a mixture, are typically present in engine lubricating compositions in amounts of between 0.1 and 5% by weight, preferably between 0.3 and 2%, even more preferably between 0.5 and 1, 5%, based on the total mass of the lubricating composition.
• Detergents reduce the formation of deposits on the surface of metal parts by dissolving the secondary products of oxidation and combustion, and allow the neutralization of certain acidic impurities from combustion and found in the oil.
• the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
• the associated cation is typically a metal cation of an alkali or alkaline earth metal.
• the detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates, preferably of calcium, magnesium, sodium or barium.
• metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.
• the excess metal providing the overbased detergent character is in the form of oil-insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate, preferably calcium, magnesium, sodium or barium.
• the lubricant compositions according to the present invention may contain any type of detergent known to those skilled in the art, neutral or overbased.
• the more or less overbased character of the detergents is characterized by the BN (base number), measured according to the ASTM D2896 standard, and expressed in mg of KOH per gram.
• Neutral detergents have a BN between about 0 and 80 mg KOH / g.
• Overbased detergents they, BN values typically of the order of 150 mg KOH / g and more, or 250 mg KOH / g or 450 mg KOH / g or more.
• the BN of the lubricant composition containing detergents is measured by ASTM D2896 and expressed as mg KOH per gram of lubricant.
• the amounts of detergents included in the motor oils according to the invention are adjusted so that the BN of said oils, measured according to ASTM D2896, is between 5 and less than or equal to 20 mg of KOH per gram of d motor oil, preferably between 8 and 15 mg KOH per gram of engine oil.
• Pour point depressant additives improve the cold behavior of oils by slowing the formation of paraffin crystals. They are for example alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrene. They are generally present in the oils according to the invention at contents of between 0.1 and 0.5% by weight, relative to the mass of lubricating composition.
• Dispersants such as, for example, succinimides, PIBs (polyisobutene) succinimides, Mannich bases, ensure the suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products which are formed when the engine oil is service.
• the dispersant level is typically between 0.5 and 10% by weight, preferably between 1 and 5%, relative to the total weight of the lubricant composition.
• Another object of the invention is a method of lubricating at least one part of a hybrid and / or micro-hybrid motor vehicle engine, said method comprising at least one step of bringing the lubricant composition into contact with one another. as defined above with at least one part of said engine, said part comprising at least one metal surface or a polymeric surface and / or an amorphous carbon surface.
• the motor part is a pad, preferably a connecting rod pad.
• the method according to the invention makes it possible to reduce the wear of the internal combustion engine of vehicles with hybrid or micro-hybrid powertrain.
• the method according to the invention makes it possible to reduce the wear of the bearings, in particular connecting rod bearings.
• the system tested includes a 4-cylinder diesel engine with a maximum torque of 200 Nm from 1750 to 2500 rpm. It is of the Stop-and-Start type and includes an alternator-starter between the clutch and the gearbox of the vehicle.
• the engine oil is maintained at about 100 ° C in these tests.
• the wear is followed by a usual technique of radiotracers, consisting of irradiating the surface of the connecting rod bearings whose wear is to be tested, and measuring during the test the increase in radioactivity of the engine oil, that is, the rate of loading of the oil into irradiated metal particles. This speed is directly proportional to the wear speed of the bearings.
• the results are based on a comparative analysis of these damage rates (reference oil and test oil) and are validated by a frame with a reference oil in order to integrate positive or negative surface adaptation elements to the speed of damage.
• the damage rates of the oils tested are all compared to the rate of damage of the reference oil and quantified as a speed ratio named Usure in Table I below.
• the lubricant composition A is a grade 5W-30 reference lubricant composition.
• the lubricating compositions B and C are lubricating compositions according to the invention additive with a polyalkylene glycol which is a PAG BO / PO (butylene oxide / propylene oxide) having a mass ratio 50/50, of KV100 equal to 6 cSt ( measured according to ASTM D445) and with a molecular weight of 750 g / mol (measured according to ASTM D4274).
• a polyalkylene glycol which is a PAG BO / PO (butylene oxide / propylene oxide) having a mass ratio 50/50, of KV100 equal to 6 cSt ( measured according to ASTM D445) and with a molecular weight of 750 g / mol (measured according to ASTM D4274).
• the lubricating composition D is a lubricant composition according to the invention, additive with the PAG described above, and an organomolybdenum compound of general formula (I) with R 1 , R 2 , R 3 , R 4 which are alkyl groups of 13 and or 18 carbon atoms, the amount of molybdenum by weight, relative to the weight of the compound, is 10%, the amount of sulfur by weight, relative to the weight of the compound, is 11%.
• the lubricating composition E is a lubricant composition according to the invention, additive with the PAG described above, and an organomolybdenum compound of general formula (II) with R 5 , R 6 , R 7 and R 8 which are alkyl groups of 8 atoms. of carbon, the amount of molybdenum by weight, relative to the weight of the compound, is 9%, the amount of sulfur by weight, relative to the weight of the compound, is 10.1%, the amount of phosphorus in mass, based on the mass of the compound, is 3.2%.
• Lubricating compositions F and G are control compositions respectively comprising an organomolybdenum compound of general formula (I) and an organomolybdenum compound of general formula (II) as described above.
• the base oil used is a blend of Group III base oils with a viscosity number of 171.
• the viscosity index improving polymer used is a linear styrene / butadiene polymer with a mass M W equal to 139,700 (measured according to ASTM D5296), with a mass M n equal to 133,000 (measured according to the ASTM D5296 standard), of polydispersity index equal to 1.1, 8% active ingredient in a Group III base oil.
• the antioxidant is an amine antioxidant of alkylarylamine structure.
• PPD or Depressant Point or Pour Point Depressant is polymethacrylate type.
• the additive package used includes conventional anti-wear, anti-oxidant, dispersant and detergent additives.
• the lubricant composition A is taken as a reference.

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