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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/24—Polyethers
  • C10M145/26—Polyoxyalkylenes
• • 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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/24—Polyethers
  • C10M145/26—Polyoxyalkylenes
  • C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 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
  • 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
  • C10M2205/04—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
  • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two 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
  • 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
  • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • 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
  • C10N2040/253—Small 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.
• coatings for protecting the surface of hybrid or micro-hybrid engine bearings have been developed, in particular polymeric coatings such as polyamide-imide coatings.
• polymeric coatings such as polyamide-imide coatings.
• these technologies can be complex and expensive to implement.
• EP 2 177 596 discloses a hybrid internal engine lubricating oil comprising a synthetic base oil and an additive package comprising at least one dispersant, at least one detergent and at least one phosphorus antiwear agent.
• this document does not describe the presence of at least one polyalkylene glycol in the lubricating oil.
• nothing in this document describes or suggests the specific treatment of the wear of the pads.
• the Applicant has found that the use, in the internal combustion engines of hybrid and hybridized motor vehicles equipped with the Stop-and-Start system, of polyalkylene glycols, in particular polyalkylene glycols obtained by copolymerization.
• polyalkylene glycols in particular polyalkylene glycols obtained by copolymerization.
• ethylene oxides and propylene oxides or polyalkylene glycols obtained by homopolymerization of propylene oxides in lubricating compositions makes it possible to considerably reduce the wear of the bearings present in said engines.
• This use advantageously makes it possible to increase the life of the engine, and in particular to increase the time interval between engine parts changes.
• the invention relates to the use of a lubricating composition comprising at least one base oil and at least one polyalkylene glycol obtained by copolymerization of oxides of ethylene and of propylene oxides or obtained by homopolymerization of oxides of propylene, for the lubrication of metal surfaces, polymeric surfaces and / or amorphous carbon surfaces, thermal internal combustion engines of hybrid and / or microhybrid vehicles.
• the use of such a composition makes it possible to reduce the wear of the bearings, and in particular the wear of the end bearings of the combustion engines of the internal combustion engines of vehicles with hybrid or micro-hybrid engines, without having necessarily need to apply a specific surface treatment to the surface of said pads.
• vehicles with micro-hybrid powertrain are equipped with an alternator-starter or a reinforced starter.
• the use makes it possible 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.
• the use makes it possible to increase the life of the internal combustion engine, in particular the life of the bearings of the internal combustion engine, in particular the service life of the connecting rod bearings of the combustion engine. internal heat.
• the use makes it possible to increase the time interval between the parts changes of the thermal internal combustion engine, in particular the time interval between the changes of the pads of the thermal internal combustion engine, in particular particularly the time interval between the changes of the connecting rod bearings of the internal combustion engine thermal.
• the lubricating composition comprises from 0.1 to 20% by weight, relative to the total weight of the lubricating composition, of polyalkylene glycol, preferably from 0.2 to 15%, more preferably from 0.5 to 10%. more preferably from 1 to 5%, even more preferably from 2 to 4%.
• the polyalkylene glycol is derived from the homopolymerization of propylene oxides.
• the polyalkylene glycol is derived from the copolymerization of ethylene oxide and propylene oxide and comprises at least 60% by weight of propylene oxide, relative to the total weight of polyalkylene glycol .
• the metal surface is an alloy.
• the alloy is steel.
• the alloy comprises as base element tin (Sn), lead (Pb), copper (Cu), aluminum (Al), cadmium (Cd), silver ( Ag) or zinc (Zn).
• the alloy comprises lead (Pb) and copper (Cu).
• the polymeric surface comprises polytetrafluoroethylene.
• the kinematic viscosity at 100 ° C of the lubricating composition is between 5.6 and 12.5 cSt.
• the present invention relates to the field of lubrication of internal combustion engines of hybrid or micro-hybrid motor vehicles.
• Hybrid motorized vehicles are here understood to mean vehicles using two different energy storages capable of moving said vehicles.
• 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:
• the kinetic energy is used to recharge the batteries.
• the thermal internal combustion engine undergoes, during its life, a number of stops and starts much higher than in a conventional vehicle (phenomenon of "Stop-and-Start") .
• 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 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 ring circular coated or made of anti-friction metal (bronze, for example), or bearings (usually needle).
• a ring circular coated or made of anti-friction metal (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 the motors are: adhesive wear or metal-metal contact wear, 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.
• 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.
• the lubricant compositions used in the invention comprise at least one polyalkylene glycol (PAG).
• PAG polyalkylene glycol
• This polyalkylene glycol is either obtained by copolymerization of oxides of ethylene and of propylene oxides, or obtained by homopolymerization of propylene oxides.
• this polyalkylene glycol is called a polypropylene glycol.
• the polyalkylene glycols of the compositions according to the invention are polymers or copolymers (statistics or blocks) of oxides of ethylene and of propylene oxides, which can be prepared according to the known methods described in the application WO 2009/134716, page 2 line 26 to page 4 line 12, for example by etching an alcohol initiator on the epoxy bond of an ethylene or propylene oxide and propagating the reaction.
• polyalkylene glycols that can be used according to the invention are commercially available under the name SYNALOX TM.
• the PAG is a homopolymer of propylene oxides.
• polyalkylene glycol is a copolymer of oxides of ethylene and of propylene oxides
• said polyalkylene glycol comprises at least 60% by weight of units derived from propylene oxides, relative to the total weight of polyalkylene glycol, preferably at least 70%, even more preferably at least 80%, even more preferably at least 90%.
• polyalkylene glycols (PAG) obtained mainly from ethylene oxides 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 viscosity index VI (measured according to the ASTM D2270 standard) of
• PAG according to the invention is greater than or equal to 30, preferably greater than or equal to 65, even more preferably greater than or equal to 150, still more preferably greater than or equal to 300.
• the viscosity at 40 ° C (KV40) measured according to ASTM D445 is between 20 and 800 cSt, preferably between 30 and 400 cSt, more preferably between 140 and 350 cSt.
• the viscosity at 100 ° C (KV100) measured according to ASTM D445 is between 5 and 150 cSt, preferably between 10 and 100 cSt, more preferably between 20 and 60 cSt.
• the weight average molecular weight M w measured according to ASTM D4274 is between 200 and 6000 g / mol, preferably between 400 and 4000 g / mol, more preferably between 1100 and 2600 g / mol.
• the lubricating compositions according to the invention may comprise between 0.1 and 20% by weight, relative to the total mass of lubricating composition, of polyalkylene glycol, of preferably between 0.2 and 15%, more preferably between 0.5 and 10%, even more preferably between 1 and 5%, even more preferably between 2 and 4%.
• 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 base oils of mineral origin according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as extraction. solvent, deasphalting, solvent dewaxing, hydrotreating, 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 D). 445). Their weight average molecular weight is typically between 250 and 3000 g / mol (ASTM D5296).
• Mixtures of synthetic and mineral oils may also be employed, for example when formulating multi-grade lubricating compositions to avoid cold start problems.
• the lubricating compositions may further comprise viscosity index (VI) improving polymers, such as, for example, polymeric esters, olefin copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene. polymethacrylates (PMA).
• VI viscosity index
• PMA polymethacrylates
• the lubricant compositions according to the present invention may contain from 0 to 20%, or from 5 to 15%, or from 7 to 10% by weight, based on the total weight of the lubricating composition, of improving polymers.
• the viscosity number for example chosen from polymeric esters, olefins copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA).
• 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. 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, in particular, lubricant compositions for a multigrade engine of grade 0W or 5W when cold, and 20 or 30 when hot according to the SAE J 300 classification.
• the lubricant compositions for engines used according to the invention may further contain any type 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 (or additive compositions) 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, overbased or non-overbased detergents, pour point improvers, dispersants, defoamers, 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 additive 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 the lubricating compositions used as motor oils is that of phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates. or ZnDTP.
• the preferred compounds have the formula Zn ((SP (S) (OR 9 ) (ORio)) 2 , or R 9 and Ri 0 are linear or branched, saturated or unsaturated alkyl groups, preferably containing from 1 to 18 carbon atoms.
• the 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-containing olefins, are also commonly used anti-wear additives.
• Anti-wear and extreme-pressure additives are generally present in engine lubricating compositions 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 the oils in use, which degradation can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the lubricant composition. 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 groups hydroxyls are in the ortho or para position of each other, or that the phenol is substituted by an alkyl group having 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 Ru is an aliphatic group, or an optionally substituted aromatic group, R 12 is an optionally substituted aromatic group, R 13 is hydrogen, or a alkyl group or aryl, or a group of formula R 4 S (0) x R 5 where R i4 and R 5 are alkylene, alkenylene, or aralkylene, and x is an integer equal to 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.
• These compounds are typically present in the 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.
• the detergents reduce the formation of deposits on the surface of the metal parts by dissolving the secondary oxidation and combustion products, and allow the neutralization of certain acid impurities from the combustion and found in the lubricant composition.
• 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 detergents.
• the excess metal providing the overbased detergent character is in the form of metal salts insoluble in the oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferentially 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 the detergents is measured according to ASTM D2896 and expressed as mg KOH per gram of lubricating composition.
• the amounts of detergents included in the lubricant compositions 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 lubricating composition, preferably between 8 and 15 mg of KOH per gram of lubricating composition.
• Pour point depressant additives improve the cold behavior of the lubricating compositions 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 lubricant compositions according to the invention at contents of between 0.1 and 0.5% by weight, relative to the weight of lubricating composition.
• Dispersants for example succinimides, PIBs (polyisobutene) succinimides, Mannich bases. They ensure the suspension and evacuation of insoluble solid contaminants consisting of secondary oxidation products that form when the lubricant composition is in use.
• 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.
• the lubricant compositions according to the invention may also comprise friction modifiers, for example inorganic friction modifiers 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.
• friction modifiers for example inorganic friction modifiers 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 lubricating compositions according to the invention are, for example, molybdenum dithiophosphates, molybdenum dithiocarbamates, molybdenum dithiophosphinates, molybdenum xanthates, molybdenum thioxanthates, and various organic complexes of molybdenum such as molybdenum carboxylates, molybdenum esters, molybdenum amides, obtainable by reaction of molybdenum oxide or ammonium molybdates with fatty substances, glycerides or fatty acids, or derivatives of fatty acids (esters, amines, amides ).
• Organomolybdenum compounds used in the lubricating compositions according to the present invention are for example described in application EP2078745, of paragraph [0036] in paragraph [062].
• Preferred organomolybdenum compounds are molybdenum dithiophosphates and / or molybdenum dithiocarbamates.
• molybdenum dithiocarbamates have been found to be very effective in combination with polyalkylene glycols to reduce 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 from 4 to 5 carbon atoms. 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%.
• the organomolybdenum compounds used in the lubricant compositions according to the invention comprise from 1 to 30% by weight of molybdenum, relative to the total weight of organomolybdenum compound, preferably from 2 to 20%, more preferably from 4 to 10%, more preferably more preferably 8 to 5%.
• the organomolybdenum compounds used in the lubricant 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%, more preferably more preferably 8 to 5%.
• organomolybdenum compounds used in the lubricant compositions according to the invention comprise from 1 to 10% by weight of phosphorus, relative to the total mass of organomolybdenum compound, preferably from 2 to 8%, more preferably from 3 to 6%, more preferably more preferably 4 to 5%.
• 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 lubricating composition is maintained at about 100 ° C in these tests.
• the wear is followed by a conventional 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 the radioactivity of the engine lubricating composition. that is, the rate of loading of the lubricant composition into irradiated metal particles. This speed is directly proportional to the wear speed of the bearings.
• the results are based on the comparative analysis of these damage rates (reference lubricating composition and lubricating composition to be tested) and are validated by a frame with a reference lubricating composition in order to integrate positive surface adaptation elements or negative at the speed of damage.
• the damage rates of the lubricating compositions tested are all compared to the rate of damage of the reference lubricant composition and quantified as the speed% ratio named Wear in Table I below.
• the lubricant composition A is a grade reference lubricant composition
• the lubricating composition B is a lubricating composition additive with a polyalkylene glycol resulting from the homopolymerization of propylene oxides (100% PO).
• the molecular weight of this polyakylene glycol is 400 g / mol (ASTM D4274), its viscosity number is 65 (ASTM D2270), its KV40 is 30 cSt (ASTM D445), its KV100 is 5 cSt (ASTM D445 ).
• 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 of mass M w equal to 139,700 (measured according to ASTM D5296), of mass M n equal to 133,000 (measured according to ASTM D5296), 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. It is found that the use of a polyalkylene glycol in the lubricating composition B reduces the wear compared with the lubricating composition A.

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

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• 2012
  • 2012-05-04 FR FR1254151A patent/FR2990214B1/fr not_active Expired - Fee Related
• 2013
  • 2013-05-03 KR KR20147030983A patent/KR20150020533A/ko not_active Application Discontinuation
  • 2013-05-03 JP JP2015509452A patent/JP6190449B2/ja not_active Expired - Fee Related
  • 2013-05-03 IN IN9186DEN2014 patent/IN2014DN09186A/en unknown
  • 2013-05-03 WO PCT/EP2013/059274 patent/WO2013164459A1/fr active Application Filing
  • 2013-05-03 AR ARP130101523A patent/AR090936A1/es unknown
  • 2013-05-03 EP EP13720405.3A patent/EP2844725A1/fr not_active Withdrawn
  • 2013-05-03 CN CN201380027812.9A patent/CN104334697A/zh active Pending

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