EP2844726B1 - Lubricant composition for an engine - Google Patents

Description

Technical area

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.

Technical background

Environmental concerns and the search for savings on fossil fuel resources have led to the development of electric motor vehicles. However, the latter are limited in power, autonomy, and require a very long battery recharging time.

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.

In 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.

In addition, 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.

Thus, 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. This potentially generates, for the internal combustion engines of hybrid and micro-hybrid vehicles, specific wear problems, in particular in the long term. These specific wear problems are particularly visible at the bearings of the cone heads.

There is therefore a need to develop new lubricating compositions that allow reliable operation of internal combustion engines of hybrid vehicles and micro-hybrids equipped with the Stop-and-Start system, and in particular that can reduce wear, in particular the wear of the bushings, in particular the wear of the bearings of the big-end bearings, in the internal combustion engines of said vehicles.

Surprisingly, the Applicant has found that the use of certain polyalkylene glycols in the internal combustion engines of hybrid and micro-hybrid vehicles equipped with the Stop-and-Start system makes it possible to considerably reduce the wear of bushings present in said engines, which increases the life of the engine, increase the time interval between engine parts changes.

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. In addition, 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. These particular quantities make it possible to reduce the wear of internal combustion engines. In particular, the compositions according to the invention make it possible to reduce the wear of the bearings present in the engines, in particular engines of vehicles with hybrid powertrain and vehicles with micro-hybrid drive, including in particular the engines of vehicles with micro-hybrid drive. equipped with the "Stop-and-Start" system.

Moreover, 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.

It is known from the document WO11011656 polyalkylene glycols used as additives for lubricating compositions. These compounds have the advantage of being biodegradable and soluble in the four groups of base oils used for the manufacture of lubricating compositions.

dans laquelle:

• R₁, R₂, R₃ représentent indépendamment un atome d'hydrogène ou un groupe hydrocarboné ayant jusqu'à 40 atomes de carbone,
• R₄ est un atome d'hydrogène, un groupement méthyle ou un groupement éthyle,
• L est un groupe de liaison,
• n est un nombre entier compris entre 4 et 40,
• A est un groupe alcoxy ayant de 2 à 25 unités dérivées d'oxyde d'éthylène, d'oxyde de propylène et/ou d'oxyde de butylène et comprend des homopolymères et des copolymères statistiques d'au moins deux des unités ci-dessus et
• z est 1 ou 2.

Cette composition peut également comprendre un polymère améliorant l'indice de viscosité. Toutefois, ce document ne décrit pas une composition lubrifiante pour moteur comprenant au moins un composé organomolybdène.The document US 6,458,750 discloses an oil-motor composition for reducing deposit formation, said composition comprising at least one base oil and at least one alkyl alkoxylate of formula (I),

in which:

• R ₁ , R ₂ and R ₃ independently represent a hydrogen atom or a hydrocarbon group having up to 40 carbon atoms,
• R ₄ is a hydrogen atom, a methyl group or an ethyl group,
• L is a linking group,
• n is an integer between 4 and 40,
• A is an alkoxy group having from 2 to 25 units derived from ethylene oxide, propylene oxide and / or butylene oxide and comprises homopolymers and random copolymers of at least two of the above units and
• z is 1 or 2.

This composition may also comprise a viscosity index improving polymer. However, this document does not disclose an engine lubricating composition comprising at least one organomolybdenum compound.

The document 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. However, this document does not disclose an engine lubricating composition comprising at least one organomolybdenum compound.

In addition, none of these documents describes the use of polyalkylene glycols in a lubricant composition for reducing the wear of internal combustion engines of hybrid or micro-hybrid powered vehicles and in particular for reducing the wear of the bearings.

brief description

The subject of the invention is an 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.

Preferably, 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%.

Preferably, the organomolybdenum compound is chosen from dithiocarbamates and / or dithiophosphates of molybdenum, taken alone or as a mixture.

Preferably, the polyalkylene glycol is a copolymer of butylene oxide and propylene oxide.

Preferably, the weight ratio of butylene oxide to propylene oxide is from 3: 1 to 1: 3, preferably from 3: 1 to 1: 1.

Preferably, 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.

Preferably, 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.

Preferably, 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%.

Preferably, 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. .

• ▪ de 40 à 80% en masse d'huile de base,
• ▪ de 1 à 28% en masse de polyalkylène glycol, obtenu par polymérisation ou copolymérisation d'oxydes d'alkylène comprenant de 3 à 8 atomes de carbone, dont au moins un oxyde de butylène,
• ▪ de 1 à 15% en masse de polymère améliorant l'indice de viscosité,
• ▪ de 1 à 15% en masse d'additifs choisis parmi les additifs anti-usure, les détergents, les dispersants, les anti-oxydants, les modificateurs de frottement, les abaisseurs de point d'écoulement, pris seuls ou en mélange,
• ▪ de 0,1 à 10% en masse d'au moins un composé organomolybdène,
  la somme des constituants étant égale à 100% et les pourcentages étant exprimés par rapport à la masse totale de composition lubrifiante.

Preferably, the lubricating composition comprises from 1 to 15% by weight of viscosity index improving polymer, relative to the total weight of the lubricating composition, preferably from 2 to 10%, more preferably from 3 to 8%. In one embodiment, the lubricant composition consists of:

• ▪ from 40 to 80% by weight of base oil,
• From 1 to 28% by weight of polyalkylene glycol, obtained by polymerization or copolymerization of alkylene oxides comprising from 3 to 8 carbon atoms, of which at least one butylene oxide,
• From 1 to 15% by weight of viscosity index improving polymer,
• ▪ from 1 to 15% by weight of additives chosen from antiwear additives, detergents, dispersants, antioxidants, friction modifiers, pour point depressants, alone or as a mixture,
• From 0.1 to 10% by weight of at least one organomolybdenum compound,
  the sum of the constituents being equal to 100% and the percentages being expressed relative to the total mass of lubricating composition.

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.

In this use 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.

In one embodiment of said method, said piece is a pad, preferably a connecting rod pad.

detailed description

The present invention relates to the field of lubrication of internal combustion engines of hybrid or micro-hybrid motor vehicles.

• lors des phases stationnaires (où le véhicule est immobile), les deux moteurs sont à l'arrêt,
• au démarrage, c'est le moteur électrique qui assure la mise en mouvement de la voiture, jusqu'à des vitesses plus élevées (25 ou 30 km/h),
• lorsque des vitesses plus élevées sont atteintes, le moteur à combustion interne thermique prend le relais,
• en cas de grande accélération, on observe la mise en marche des deux moteurs à la fois, qui permet d'avoir des accélérations équivalentes au moteur de même puissance, voire supérieures,
• optionnellement, en phase de décélération et de freinage, l'énergie cinétique est utilisée pour recharger les batteries.

Hybrid motorized vehicles are here understood to mean vehicles using two different energy storages capable of moving said vehicles. In particular, hybrid vehicles combine a thermal internal combustion engine and an electric motor, said electric motor participating in the traction of the vehicle. The operating principle of hybrid vehicles is as follows:

• during stationary phases (where the vehicle is stationary), both engines are stopped,
• at the start, it is the electric motor which ensures the setting in motion of the car, up to higher speeds (25 or 30 km / h),
• when higher speeds are reached, the internal combustion engine takes over,
• in case of great acceleration, we observe the start of the two engines at a time, which allows to have accelerations equivalent to the engine of the same power, or even higher,
• optionally, in the deceleration and braking phase, the kinetic energy is used to recharge the batteries.

Thus, in hybrid vehicles, the combustion engine thermal undergoes, during its lifetime, a number of stops and starts much higher than in a conventional vehicle (phenomenon of "Stop-and-Start") .

Here, the term "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.

The wear generated by these frequent stops and restarts is visible in the various parts in contact with the lubricant: piston, piston ring, piston pin, piston pin boss, small end, big end, connecting rod bearings, pin, trunnion, shaft line bearing, shaft line bushings or trunnion bushings or crankshaft bearings, chain pin, oil pump toothing, gear, camshaft, camshaft bearing, timing lifters , latch roller, hydraulic stop for play catch, turbocharger shaft, turbocharger bearing.

In a motor vehicle, there is 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. There is also 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).

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.

The 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.

In the context of frequent stops and restart, as is the case for vehicles with hybrid or micro-hybrid powertrain, the bearings are subject to frequent breaks and reboots of the oil film. Thus at each stop / restart takes place a contact between the metal interfaces and it is the frequency of occurrence of these contacts that is problematic for the pads.

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, in particular the surface of the bearings, 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.

According to another embodiment, the surfaces affected by wear are polymeric surfaces. Most of the time, 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).

According to another embodiment, the surfaces concerned by the wear are surfaces of amorphous carbon type. Most of the time, 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

The 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.

où

• Y₁ et Y₂ sont, indépendamment l'un de l'autre, l'hydrogène, ou un groupe hydrocarboné, par exemple un groupe alkyl ou alkylphényl, ayant entre 1 et 30 atomes de carbone,
• n représente un entier supérieur ou égal à 2, préférentiellement inférieur à 60, préférentiellement allant de 5 à 30, préférentiellement allant de 7 à 15,
• x représente un ou plusieurs entiers allant de 1 à n,
• les groupements R_2x-1 et R_2x sont, indépendamment les uns des autres, l'hydrogène, ou des radicaux hydrocarbonés, comprenant entre 1 et 6 atomes de carbone, préférentiellement alkyl.

The polyalkylene glycols (PAG) according to the invention correspond in particular to the general formula (A):

or

• Y ₁ and Y ₂ are, independently of one another, hydrogen, or a hydrocarbon group, for example an alkyl or alkylphenyl group, having between 1 and 30 carbon atoms,
• n represents an integer greater than or equal to 2, preferably less than 60, preferably ranging from 5 to 30, preferentially ranging from 7 to 15,
• x represents one or more integers ranging from 1 to n,
• the groups R _2x-1 and R _2x are, independently of each other, hydrogen, or hydrocarbon radicals, comprising between 1 and 6 carbon atoms, preferably alkyl.

R _2x-1 and R _2x are preferably linear.

Preferably 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.

For at least one value of x, 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.

Indeed, 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. In particular, they can not be used in combination with other mineral, synthetic or natural base oils.

The use of 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.

Preferably, 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.

In order to give them a sufficient lipophilic character, and therefore a good solubility in synthetic base oils, mineral or natural base oils, and good compatibility with certain essential additives for motor oils, the PAGs according to the invention are obtained from alkylene oxides comprising at least one butylene oxide.

Among these PAGs, 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.

The demand WO2011 / 011656 , paragraphs [011] to [014] describes the method of preparation, characteristics, and properties (especially of solubility and miscibility in base oils) of such PAG copolymers of butylene oxide and propylene oxide.

These PAGs are prepared by reacting one or more alcohols with a mixture of butylene oxide and propylene oxide.

In order to give the PAGs good solubility and good miscibility in the mineral, synthetic and natural base oils, it is preferred to use, in the compositions according to the invention, PAGs prepared with a mixture of butylene oxide and propylene oxide wherein the weight ratio of butylene oxide to propylene oxide is from 3: 1 to 1: 3. 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).

According to a preferred embodiment, 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.

According to a preferred embodiment, 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.

This gives them 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.

Lubricating composition

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.

Preferably, 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%.

Basic oils

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. In addition, 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. Saturated content Sulfur content Viscosity index (VI) Group I Mineral oils <90% > 0.03% 80 ≤ VI <120 Group II Hydrocracked oils ≥ 90% ≤ 0.03% 80 ≤ VI <120 Group III Hydrocracked or hydro-isomerized oils ≥ 90% ≤ 0.03% ≥ 120 Group IV (PAO) Polyalphaolefins Group V Esters and other bases not included in groups I to IV Group VI * (PIO) Internal Polyolefins (in English term Poly Internal Olefins) * for ATIEL classification only

These 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.

Organomolybdenum compounds

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.

In particular, 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.

The same applies to molybdenum dithiophosphates. These 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%.

Surprisingly, the applicant has demonstrated that the use of the polyalkylene glycols described above in combination with these organomolybdenum compounds, in a motor oil, can significantly reduce the wear of the connecting rod bearings of the engines of hybrid vehicles or micro-hybrids, without altering fuel consumption or reducing fuel consumption.

The 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%.

The organomolybdenum compounds that can be used in the compositions according to the invention comprise from 1 to 30% by weight of sulfur, 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%.

The 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%.

Polymer improving the viscosity index

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).

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%.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Other additives

The lubricant compositions for engines used according to the invention may furthermore contain all types of additives suitable for use as engine oil. These 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). These additive packages (or additive compositions) are concentrates comprising about 30% by weight of dilution base oil.

Thus, 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.

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. Among the commonly used 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.

Another class of antioxidants is 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.

These 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.

Preferably, 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.

In one embodiment of said method, 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. Advantageously, the method according to the invention makes it possible to reduce the wear of the bearings, in particular connecting rod bearings.

Examples

1. 1) Démarrage moteur,
2. 2) Fonctionnement 10 secondes sur point de ralenti,
3. 3) Arrêt moteur,

Reprise de la séquence 1 à 3.The aggravation on the wear of the bearings of an engine equipped with a Stop-and-Start system was simulated by a test consisting of a succession of 12000 cycles stop / start for 150 hours:

1. 1) Engine start,
2. 2) 10 seconds operation on idle point,
3. 3) Engine stop,

Resumption of sequence 1 to 3.

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).

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 mass compositions and properties of the lubricating compositions tested are summarized in Table I below: Table I AT B C D E F G Base oil * 70% 68% 42% 41% 41% 69% 69% Package of additives 12.3% 12.3% 12.3% 12.3% 12.3% 12.3% 12.3% Polymer 16.6% 16.6% 16.6% 16.6% 16.6% 16.6% 16.6% Antioxidant 0.8% 0.8% 0.8% 0.8% 0.8% 0.8% 0.8% PPD 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% PAG PO / BO - 2% 28% 28% 28% - - MoDTC - - - 1% - 1% - MoDTP - - - - 1% - 1% HTHS (High Temperature High Shear), mPa.s, ASTM D4741 3.5 3.5 3.5 3.5 3.5 3.5 3.5 KV100, cSt, ASTM D445 12.0 11.8 11.9 11.8 11.7 11.8 12.1 CCS (Cold Crank Simulator), -30 ° C, mPa.s, ASTM D5293 6360 6400 6350 6340 6520 6460 6490 SAE grade 5W-30 5W-30 5W-30 5W-30 5W-30 5W-30 5W-30 Wear 100% 46% 57% 34% 31% 51% 40% * excluding base oil dilution of the additive package

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.

It is found that the use of a polyalkylene glycol makes it possible to reduce the wear in compositions B and C. Furthermore, the joint use of a polyalkylene glycol and of an organomolybdenum compound makes it possible to reduce the rate of wear in compositions D and E.

Claims (14)

1. Lubricating composition for a motor, comprising at least one base oil, at least one polymer improving the viscosity index, at least one organomolybdenum compound and at least one polyalkylene glycol, obtained by polymerisation or copolymerisation of alkylene oxides comprising from 3 to 8 carbon atoms, including at least one butylene oxide, the quantity of polyalkylene glycol being from 1 to 28% by mass, relative to the total mass of the lubricating composition.
2. Lubricating composition according to claim 1, comprising from 0.1 to 10% by mass, relative to the total mass of lubricating composition, of organomolybdenum compound, preferably from 0.5 to 8%, more preferably from 1 to 5%.
3. Lubricating composition according to claim 1 or 2, in which the organomolybdenum compound is chosen amongst molybdenum dithiocarbamates and/or dithiophosphates, taken alone or in a mixture.
4. Lubricating composition according to any of the claims 1 to 3, in which the polyalkylene glycol is a copolymer of butylene oxide and propylene oxide.
5. Lubricating composition according to any of the claims 1 to 4, in which the mass ratio of butylene oxide to propylene oxide is of a value going from 3 : 1 to 1 : 3, preferably from 3 : 1 to 1 : 1.
6. Lubricating composition according to any of the claims 1 to 5, in which the polyalkylene glycol has a molar mass measured according to the ASTM D4274 standard of 300 to 1,000 grams per mol, preferably of 500 to 750 grams per mol.
7. Lubricating composition according to any of the claims 1 to 6, in which the polyalkylene glycol has a kinematic viscosity at 100°C, measured according to the ASTM D445 standard of 1 to 12 cSt, preferably of 3 to 7 cSt, more preferably of 3.5 to 6.5 cSt.
8. Lubricating composition according to any of the claims 1 to 7, comprising from 2 to 20% by mass of polyalkylene glycol, relative to the total mass of the lubricating composition, preferably from 3 to 15%, even more preferably from 5 to 12%, even more preferably from 6 to 10%.
9. Lubricating composition according to any of the claims 1 to 8, in which the polymer improving the viscosity index is chosen within the group constituted by olefin copolymers, ethylene and alpha-olefin copolymers, styrene and olefin copolymers, the polyacrylates taken alone or in a mixture.
10. Lubricating composition according to any of the claims 1 to 9, comprising from 1 to 15% by mass of polymer improving the viscosity index, relative to the total mass of the lubricating composition, preferably from 2 to 10%, more preferably from 3 to 8%.
11. Lubricating composition according to any of the claims 1 to 10, consisting of:

    ▪ from 40 to 80% by mass of base oil,

    ▪ from 1 to 28% by mass of polyalkylene glycol, obtained by polymerisation or copolymerisation of alkylene oxides, comprising from 3 to 8 carbon atoms, including at least one butylene oxide,

    ▪ from 1 to 15% by mass of polymer improving the viscosity index,

    ▪ from 1 to 15% by mass of additives chosen amongst anti-wear additives, detergents, dispersants, antioxidants, friction modifiers, flow point reducers, taken alone or in a mixture,

    ▪ from 0.1 to 10% by mass of at least one organomolybdenum compound,

    the sum of the constituents being equal to 100% and the percentages being expressed relative to the total mass of lubricating composition.
12. Use of at least one polyalkylene glycol, obtained by polymerisation or copolymerisation of alkylene oxides, comprising from 3 to 8 carbon atoms, including at least one butylene oxide in a lubricating composition for lubricating metallic surfaces, polymeric surfaces and/or amorphous carbon surfaces, thermal internal combustion engines of hybrid and/or microhybrid motorised vehicles and in order to reduce wear and tear of the thermal internal combustion engine, in which said polyalkylene glycol is combined with at least one organomolybdenum compound.
13. Use according to claim 12 for reducing the wear and tear of the bearings of the thermal internal combustion engine.
14. Use according to claim 12 for reducing the wear and tear of the connecting rod bearings of the thermal internal combustion engine.