EP3551734A1 - Lubricating composition comprising glycerol monoethers - Google Patents

Lubricating composition comprising glycerol monoethers

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Publication number
EP3551734A1
EP3551734A1 EP17816626.0A EP17816626A EP3551734A1 EP 3551734 A1 EP3551734 A1 EP 3551734A1 EP 17816626 A EP17816626 A EP 17816626A EP 3551734 A1 EP3551734 A1 EP 3551734A1
Authority
EP
European Patent Office
Prior art keywords
glycerol
engine
composition according
ether
lubricating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17816626.0A
Other languages
German (de)
French (fr)
Inventor
Nicolas CHAMPAGNE
Gwendoline GRAVE
Françoise Quignard
Nathalie TANCHOUX
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
TotalEnergies Marketing Services SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Total Marketing Services SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Total Marketing Services SA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3551734A1 publication Critical patent/EP3551734A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16Ethers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic 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
    • C10M2205/0285Organic 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 used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046Hydroxy ethers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/069Linear chain compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/071Branched chain compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

Definitions

  • Lubricating composition comprising glycerol monoethers
  • the invention relates to the field of friction modifiers, and in particular modifiers of organic friction. More particularly, the invention relates to a lubricating composition comprising a friction modifier selected from glycerol monoethers. The invention also relates to the use of this lubricant composition for lubricating an engine.
  • friction modifiers four major groups stand out: nanoparticles, polymers, organomolybdenum compounds and organic molecules.
  • the organic friction modifiers are studied and conventionally used. It has been found that glycerol esters are effective, and in particular glycerol mono-oleate is the most commonly used commercially. It has the advantages of not containing ash, phosphorus or sulfur and being produced from renewable raw materials. However, its properties as a friction modifier are lower than those of molybdenum dithiocarbamate.
  • glycerol ethers as a friction modifier is also known.
  • the application JPS5925890 describes the use of glycerol ethers comprising an alkyl chain comprising from 4 to 28 carbon atoms.
  • the application JP2000273481 also describes the use of glycerol ethers comprising an alkyl chain comprising more than 14 carbons as friction modifiers.
  • an object of the present invention is to provide a friction modifier and a lubricating composition comprising this friction modifier overcoming all or some of the aforementioned drawbacks.
  • Yet another object of the present invention is to provide a lubricant composition for reducing friction and thus reducing the fuel consumption of this engine, preferably a motor vehicle.
  • the present invention thus relates to a lubricant composition
  • a lubricant composition comprising:
  • At least one glycerol mono-ether characterized in that one of the alcohol functions of glycerol forms an ether function with a linear or branched alkyl or alkylene group R comprising from 5 to 8 carbon atoms, preferably from 6 to to 7 carbon atoms, preferably 6 carbon atoms.
  • the group R comprises 6 or 7 carbon atoms.
  • the composition according to the invention is a motor lubricant.
  • the R group of the glycerol monoether according to the invention forms an ether bond with any oxygen atom of glycerol, whether it is bonded to one of the two primary carbons or to the secondary carbon of glycerol. .
  • the glycerol mono-ether is chosen from glycerol monoethers of formula (I) or (II), taken alone or as a mixture:
  • R represents a linear or branched alkyl or alkylene group comprising from 5 to 8 carbon atoms, preferably from 6 to 7 carbon atoms, preferably 6 carbon atoms.
  • the glycerol mono-ether according to the invention is chosen from the compounds of formula (I).
  • the glycerol mono-ether according to the invention is chosen from the compounds of formula (II).
  • the lubricating composition according to the invention comprises from 0.01% to 5% by weight of glycerol mono-ether according to the invention relative to the total mass of the lubricating composition.
  • the lubricating composition comprises from 0.01% to 2% by weight, preferably from 0.1% to 1.5% by weight of glycerol mono-ether as defined above, relative to the total mass. of the lubricating composition.
  • the glycerol monoethers according to the invention can be obtained by any technique known to those skilled in the art.
  • a preferred synthetic route for the preparation of glycerol monoethers of the invention consists in the reaction between glycerol and an alcohol ROH, R having the definition given above.
  • the etherification reaction between glycerol and an alcohol is preferably carried out in the presence of an acid catalyst, preferably an acid heterogeneous catalyst or a homogeneous acid catalyst.
  • the acidic heterogeneous catalysts are chosen from zeolites, resins or oxides of alumina.
  • resins there may be mentioned perfluorinated polymer resins such as National® NR50, cation exchange resins such as Dowex 50wx8, or among ion exchange resins with acidic properties such as Amberlyst® 15 and 36.
  • zeolites that may be mentioned include mordenites, ZMS-5 zeolites of the MFI type, BEA zeolites or faujasites.
  • the acidic heterogeneous catalyst is a zeolite, preferably a mordenite type zeolite, preferably a mordenite with a Si / Al ratio of 1 1.
  • the homogeneous acidic catalysts are chosen from phosphoric acid, para-toluenesulfonic acid (APTS) and triflic acid.
  • the acidic homogeneous catalyst is para-toluenesulfonic acid (APTS).
  • the amount of acidic homogeneous catalyst involved in the reaction is between 1% and 10 mol% relative to the glycerol content. preferably it is between 1% and 2.5% molar.
  • the amount of heterogeneous catalyst involved in the reaction is between 1 and 5 mol% relative to the glycerol content, preferably it is 3.5 mol%.
  • the alcohol / glycerol molar ratio is optimized in order to obtain the best possible yield of glycerol mono-ether while limiting the secondary reactions of glycerol oligomer formation.
  • the alcohol / glycerol molar ratio is between 1/6 and 3/1, preferably it is 1/1.
  • the etherification reaction may also, in another embodiment, be carried out from the di-ether resulting from the reaction of the alcohol on itself.
  • the etherification reaction of glycerol can be carried out in any type of reactor known to those skilled in the art.
  • it is conducted in an autoclave.
  • the conditions of temperature, pressure and the etherification reaction time of the glycerol can be determined in the usual manner by those skilled in the art.
  • the reaction is carried out at a temperature of between 80 and 200 ° C., preferably between 130 and 160 ° C., for example it is carried out at 150 ° C.
  • the reaction is carried out for at least 5 hours, preferably for 5 to 48 hours.
  • the reaction time may be 24 hours or 48 hours.
  • At least one liquid-liquid extraction is conducted, preferably at least two. Even more preferably, three liquid-liquid extractions are carried out.
  • the initial alcohol and the glycerol mono-ether are separated.
  • the process according to the invention makes it possible to selectively obtain glycerol monoethers.
  • the base oil (s) used in the lubricant compositions according to the invention can be chosen from a wide range.
  • the base oil of the lubricant composition used according to the invention may in particular be chosen from mineral, synthetic or natural oils, bio-sourced, animal, plant known to those skilled in the art.
  • the base oil (s) according to the invention may be oils of mineral or synthetic origin, chosen from oils of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) (Table A ), alone or in mixtures.
  • the mineral base oils useful 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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization and hydrofinishing.
  • Mixtures of synthetic and mineral oils can also be used.
  • lubricating bases for producing the lubricating compositions used according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulfur, oxidation resistance, adapted for use for engines or for vehicle transmissions.
  • the lubricant composition according to the invention may comprise from 50 to 99% of at least one base oil, preferably from 60 to 99%, advantageously from 70 to 99% by weight relative to the total weight of lubricating composition.
  • the lubricating composition according to the invention may also comprise numerous additives.
  • the preferred additives for the lubricant composition used according to the invention are chosen from detergents, antiwear additives, extreme pressure additives, viscosity index improvers, dispersants, antioxidants, d-point improvers and the like. flow, anti-foam agents, and inorganic friction modifiers and mixtures thereof.
  • the detergent additives generally make it possible to reduce the formation of deposits on the surface of the metal parts by dissolving the secondary oxidation and combustion products.
  • the detergent additives that can be used in the lubricant composition according to the invention are generally known to those skilled in the art.
  • the detergent additives may be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation may be a metal cation of an alkali metal or alkaline earth metal.
  • the detergent additives are preferably chosen from the alkali metal or alkaline earth metal salts of carboxylic acids, the sulphonates, the salicylates, the naphthenates and the phenate salts.
  • the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
  • metal salts generally comprise the metal in stoichiometric amount or in excess, therefore in an amount greater than the stoichiometric amount. It is then overbased detergent additives; the excess metal bringing the overbased character to the detergent additive is then generally in the form of an oil insoluble metal salt, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .
  • an oil insoluble metal salt for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .
  • the lubricant composition according to the invention may comprise from 2 to 4% by weight of detergent additive relative to the total mass of the lubricating composition.
  • Anti-wear additives and extreme pressure additives protect friction surfaces by forming a protective film adsorbed on these surfaces.
  • the anti-wear additives are chosen from phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
  • the preferred compounds are of formula Zn ((SP (S) (OR 11 ) (OR 12 )) 2 , in which R 1 1 and R 12 , which are identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to at 18 carbon atoms.
  • Amine phosphates are also anti-wear additives which can be used in the lubricating composition according to the invention.
  • the phosphorus provided by these additives can act as a poison of the catalytic systems of automobiles because these additives are ash generators.
  • these effects can be minimized by partially substituting amine phosphates with non-phosphorus additives, such as, for example, polysulfides, especially sulfur-containing olefins.
  • the lubricant composition according to the invention may comprise from 0.01 to 6% by weight, preferably from 0.05 to 4% by weight, more preferably from 0.1 to 2% by weight relative to the mass. total lubricating composition, anti-wear additives and extreme pressure additives.
  • the lubricant composition according to the invention may also comprise at least one dispersing agent.
  • the dispersing agent may be chosen from Mannich bases, succinimides and their derivatives.
  • the lubricating composition according to the invention may comprise from 0.2 to 10% by weight of dispersing agent relative to the total mass of the lubricating composition.
  • the lubricant composition according to the invention may comprise at least one antioxidant additive.
  • the antioxidant additive generally serves to retard the degradation of the lubricating composition in service. This degradation can notably result in the formation of deposits, the presence of sludge or an increase in the viscosity of the lubricant composition.
  • Antioxidant additives act in particular as radical inhibitors or destroyers of hydroperoxides.
  • antioxidant additives commonly used, mention may be made of antioxidant additives of phenolic type, antioxidant additives of amine type, antioxidant phosphosulfur additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators. Phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts.
  • the antioxidant additives may in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C 12 -C 12 alkyl group, ⁇ , ⁇ ' dialkyl-aryl diamines and mixtures thereof.
  • the sterically hindered phenols are chosen from compounds comprising a phenol group in which at least one vicinal carbon of the carbon bearing the alcohol function is substituted with at least one alkyl group containing 10 carbon atoms, preferably an alkyl group containing CrC 6 , preferably a C 4 alkyl group, preferably by the ter-butyl group.
  • Amino compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives.
  • amine compounds are aromatic amines, for example aromatic amines of formula NR 13 R 14 R 15 in which R 13 represents an optionally substituted aliphatic or aromatic group, R 14 represents an optionally substituted aromatic group, R 15 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R 16 S (O) z R 17 in which R 16 represents an alkylene group or an alkenylene group, R 17 represents an alkyl group, a alkenyl group or an aryl group and z represents 0, 1 or 2.
  • antioxidant additives is copper compounds, for example copper thio- or dithio-phosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper salts I and II, succinic acid or anhydride salts can also be used.
  • the lubricating composition comprises at least one ash-free antioxidant additive.
  • the lubricating composition according to the invention comprises from 0.5 to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.
  • the lubricant composition according to the invention may also comprise at least one pour point depressant additive.
  • pour point depressant additives By slowing the formation of paraffin crystals, pour point depressant additives generally improve the cold behavior of the lubricant composition according to the invention.
  • pour point depressant additives examples include alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes.
  • the lubricating composition may also comprise an anti-foam additive chosen from silicones and their derivatives, such as polysiloxanes and their derivatives.
  • an anti-additive foam may be Bluesil 47V12500® marketed by Bluestar Silicones.
  • the antifoam additive of the lubricant composition according to the invention may also be chosen from acrylics, such as PC1244® marketed by Mosanto.
  • the lubricating composition according to the invention may comprise at least one additional friction-modifying additive, such as an inorganic friction modifier.
  • the inorganic friction modifier additive may be selected from a compound providing metal elements and an ash free compound.
  • the compounds providing metal elements mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu and Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen, sulfur or phosphorus.
  • Molybdenum dithiocarbamate (MoDTC) is the best known compound in this family.
  • the lubricant composition according to the invention may comprise from 0.01 to 5% by weight or from 0.01 to 2% by weight, preferably from 0.1 to 1.5% by weight or 0.1 at 2% by weight relative to the total mass of the lubricant composition, additional friction modifier additive.
  • the invention also relates to the use of a lubricant composition according to the invention for lubricating an engine, preferably a motor vehicle engine.
  • the invention also relates to the use of a lubricant composition according to the invention for reducing the friction in an engine, preferably a motor vehicle engine.
  • the invention also relates to the use of the lubricant composition according to the invention for reducing the fuel consumption of an engine, preferably a motor vehicle engine.
  • the reduction of friction in an engine or the reduction of the fuel consumption of an engine is measured with respect to the friction or fuel consumption measured with a reference composition.
  • said reference composition does not comprise glycerol mono-ether, characterized in that one of the alcohol functions of glycerol forms an ether function with an alkyl or alkylene R group comprising 6 or 7 carbon atoms.
  • the invention also relates to the use of the lubricant composition according to the invention for reducing the fuel consumption at the start and during the operating phase of the engine.
  • the invention also relates to the use of a glycerol mono-ether as defined above in a lubricant composition to reduce the friction in an engine or to reduce the fuel consumption of an engine, preferably a fuel engine. motor vehicle.
  • a glycerol mono-ether of formula according to the invention allows a reduction in fuel consumption at startup and during the operating phase of the engine.
  • the invention also relates to a method of lubricating an engine, preferably a motor vehicle engine comprising the implementation of a lubricant composition according to the invention.
  • the invention also relates to a method for reducing the fuel consumption of an engine, preferably a motor vehicle engine comprising the implementation in said engine of a lubricant composition according to the invention.
  • an engine preferably a motor vehicle engine comprising the implementation in said engine of a lubricant composition according to the invention.
  • the different glycerol monoethers tested are described in Table I below.
  • the synthetic route requires that the glycerol and fatty alcohol used be soluble one in the other. However, any fatty alcohol comprising 8 or more carbons is not soluble in glycerol, the corresponding glycerol ethers can not be synthesized according to the described synthetic route.
  • the reactors used are the following:
  • the amount of catalyst is a molar amount relative to the amount of glycerol used.
  • the mixture thus obtained is first purified by decantation without solvent, then subjected to a liquid-liquid extraction and finally subjected to fractional distillation to recover the glycerol mono-ether.
  • the amount of glycerol monoethers obtained at the end of the reaction is measured by gas chromatography.
  • Thermogravimetric analysis gives the mass loss of a sample as a function of temperature.
  • the sample is heated according to programmed temperature ramps.
  • the mass losses are determined using a scale that continuously measures the mass of the sample during its rise in temperature.
  • the glycerol monoethers according to the invention have a loss of mass of 100% for higher temperatures, and in particular may be greater than 200 ° C. which makes them fully compatible with use in a lubricant composition for engine application.
  • the HFRR (High Frequency Reciprocating Rig) test is used to evaluate the performance of fuels and lubricants in terms of friction in the mixed / limit regime.
  • a load of 200g is applied to the ball, which corresponds to a The oil is heated to 100 ° C.
  • the MTM (Traction Machine or Mini Traction Machine) test is used to evaluate the lubricant performance in terms of friction in the mixed / hydrodynamic regime. in relative motion a steel ball and a steel plane, at different speeds, to define the% SSR (Ratio speed of slip / speed of drive or Slide-to-Roll Ratio) which corresponds to the speed of slip / training speed.
  • the tests carried out consist of a accumulation period of 120 min where the ball rotates at 100 mm. s "1 (hydrodynamic regime) with a% SSR of 50%, for a load of 1, 1 GPa and an oil temperature of 100 ° C.
  • a friction modifier is considered effective if it lowers the coefficient of friction.
  • Each glycerol mono-ether is added at a content of 1% by weight relative to the total weight of the reference lubricating composition.
  • the various lubricating compositions tested are described in Table V below.
  • Table VI represents the coefficients of friction of the reference composition and compositions 3, 4, 5 and 6; the values were taken after 900 seconds of testing.
  • compositions 3 to 6 significantly lower the coefficient of friction on this HFRR test under severe conditions.
  • composition 3 and the composition 6 have been evaluated comparatively by the implementation of the motor test described below:
  • the fluid temperature water / oil
  • the engine is then positioned at a selected operating point (rpm / torque) and the fuel consumption is then measured at this point.
  • a consumption map is thus produced by this means.
  • the test engine is a Renault R9M engine.
  • Table VIII shows the gains in terms of% fuel consumption compared to the reference composition at a temperature (water / oil) set at 90 ° C.
  • the threshold of significance of the test is equal to 0.15%.
  • the lubricant compositions according to the invention significantly improve the fuel consumption, especially when hot.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a lubricating composition comprising: at least one base oil; and at least one glycerol monoether characterised in that one of the alcohol functions of the glycerol forms an ether function with a linear or branched, alkyl or alkylene R group comprising 6 or 7 carbon atoms, said composition being an engine lubricant.

Description

Composition lubrifiante comprenant des mono-éthers de glycérol  Lubricating composition comprising glycerol monoethers
L'invention concerne le domaine des modificateurs de frottements, et notamment des modificateurs de frottements organiques. Plus particulièrement, l'invention concerne une composition lubrifiante comprenant un modificateur de frottement choisi parmi les mono- éthers de glycérol. L'invention concerne également l'utilisation de cette composition lubrifiante pour lubrifier un moteur. The invention relates to the field of friction modifiers, and in particular modifiers of organic friction. More particularly, the invention relates to a lubricating composition comprising a friction modifier selected from glycerol monoethers. The invention also relates to the use of this lubricant composition for lubricating an engine.
Un des objectifs majeurs de l'industrie automobile actuelle est à la réduction de consommation de carburant des moteurs, en particulier des moteurs de véhicules automobiles, et ainsi l'amélioration du « Fuel Eco » des véhicules. Diminuer les frottements dans un moteur est un moyen efficace de parvenir à une économie de carburant. Ainsi, de nombreuses recherches ont été menées sur les modificateurs de frottement. One of the major objectives of the current automotive industry is the reduction of fuel consumption of engines, especially motor vehicle engines, and thus the improvement of "Fuel Eco" vehicles. Reducing friction in an engine is an effective way to achieve fuel economy. Thus, much research has been done on friction modifiers.
Parmi les modificateurs de frottement, quatre grands groupes se distinguent : les nanoparticules, les polymères, les composés organomolybdène et les molécules organiques. Among the friction modifiers, four major groups stand out: nanoparticles, polymers, organomolybdenum compounds and organic molecules.
Si les nanoparticules et les polymères sont peu utilisés aujourd'hui, ce n'est pas le cas des composés organomolybdène qui représentent la famille la plus importante de modificateurs de frottement. Le modificateur de frottement inorganique le plus connu et le plus utilisé est le dithiocarbamate de molybdène (MoDTC). Ces modificateurs de frottements inorganiques, bien que très efficaces, présentent certains inconvénients. En effet, ils peuvent induire un certain encrassage et une corosion des pièces du moteur. Par ailleurs, ils ne sont actifs qu'à haute température et peuvent détériorer certains type de surface en carbone amorphe (DLC).  Although nanoparticles and polymers are little used today, this is not the case for organomolybdenum compounds, which represent the most important family of friction modifiers. The best-known and most widely used inorganic friction modifier is molybdenum dithiocarbamate (MoDTC). These inorganic friction modifiers, although very effective, have certain disadvantages. Indeed, they can induce some fouling and corosion of engine parts. In addition, they are only active at high temperatures and can damage certain types of amorphous carbon (DLC) surfaces.
En outre, d'un point de vue écologique, il est nécessaire de réduire la teneur en éléments soufrés ou phosphorés des compositions lubrifiantes utilisées.  In addition, from an ecological point of view, it is necessary to reduce the content of sulfur or phosphorus elements of the lubricating compositions used.
Ainsi, les modificateurs de frottement organiques sont étudiés et classiquement utilisés. Il est apparu que les esters de glycérol étaient efficaces, et en particulier le mono-oléate de glycérol est le plus utilisé commercialement. Il présente les avantages de ne pas contenir de cendres, de phosphore ou de soufre et d'être produit à partir de matières premières renouvelables. Toutefois ses propriétés en tant que modificateur de frottement sont inférieures à celles du dithiocarbamate de molybdène.  Thus, the organic friction modifiers are studied and conventionally used. It has been found that glycerol esters are effective, and in particular glycerol mono-oleate is the most commonly used commercially. It has the advantages of not containing ash, phosphorus or sulfur and being produced from renewable raw materials. However, its properties as a friction modifier are lower than those of molybdenum dithiocarbamate.
L'utilisation des éthers de glycérol en tant que modificateur de frottement est également connue. Ainsi, la demande JPS5925890 décrit l'utilisation d'éthers de glycérol comprenant une chaîne alkyle comprenant de 4 à 28 atomes de carbone. La demande JP2000273481 décrit également l'utilisation des éthers de glycérol comprenant une chaîne alkyle comprenant plus de 14 carbones en tant que modificateurs de frottement. The use of glycerol ethers as a friction modifier is also known. Thus, the application JPS5925890 describes the use of glycerol ethers comprising an alkyl chain comprising from 4 to 28 carbon atoms. The application JP2000273481 also describes the use of glycerol ethers comprising an alkyl chain comprising more than 14 carbons as friction modifiers.
Il existe donc un intérêt à proposer de nouveaux modificateurs de frottement permettant de gagner en efficacité. There is therefore an interest in proposing new friction modifiers to improve efficiency.
Ainsi, un objectif de la présente invention est de fournir un modificateur de frottement ainsi qu'une composition lubrifiante comprenant ce modificateur de frottement palliant tout ou partie des inconvénients précités. Thus, an object of the present invention is to provide a friction modifier and a lubricating composition comprising this friction modifier overcoming all or some of the aforementioned drawbacks.
Un autre objectif de la présente invention est de fournir un modificateur de frottement organique issu de matières premières renouvelables qui n'a pas les défauts du MoDTC et qui est efficace à basse température.  Another object of the present invention is to provide an organic friction modifier derived from renewable raw materials that does not have the defects of MoDTC and is effective at low temperatures.
Un autre objectif encore de la présente invention est de fournir une composition lubrifiante permettant de diminuer le frottement et donc réduire la consommation de carburant de ce moteur, de préférence de véhicule automobile.  Yet another object of the present invention is to provide a lubricant composition for reducing friction and thus reducing the fuel consumption of this engine, preferably a motor vehicle.
La présente invention a ainsi pour objet une composition lubrifiante comprenant : The present invention thus relates to a lubricant composition comprising:
- au moins une huile de base ; et  at least one base oil; and
- au moins un mono-éther de glycérol caractérisé en ce que l'une des fonctions alcool du glycérol forme une fonction éther avec un groupe R alkyle ou alkylène, linéaire ou ramifié, comprenant de 5 à 8 atomes de carbone, de préférence de 6 à 7 atomes de carbone, de préférence 6 atomes de carbone.  at least one glycerol mono-ether, characterized in that one of the alcohol functions of glycerol forms an ether function with a linear or branched alkyl or alkylene group R comprising from 5 to 8 carbon atoms, preferably from 6 to to 7 carbon atoms, preferably 6 carbon atoms.
De préférence, dans la composition selon l'invention, le groupe R comprend 6 ou 7 atomes de carbone. Preferably, in the composition according to the invention, the group R comprises 6 or 7 carbon atoms.
De préférence, la composition selon l'invention est un lubrifiant moteur. Preferably, the composition according to the invention is a motor lubricant.
De façon avantageuse, le groupe R du mono-éther de glycérol selon l'invention forme une liaison éther avec n'importe quel atome d'oxygène du glycérol, qu'il soit lié à un des deux carbones primaires ou au carbone secondaire du glycérol. Advantageously, the R group of the glycerol monoether according to the invention forms an ether bond with any oxygen atom of glycerol, whether it is bonded to one of the two primary carbons or to the secondary carbon of glycerol. .
De manière avantageuse selon l'invention, le mono-éther de glycérol est choisi parmi les mono-éthers de glycérol de formule (I) ou (II), pris seuls ou en mélange : Advantageously according to the invention, the glycerol mono-ether is chosen from glycerol monoethers of formula (I) or (II), taken alone or as a mixture:
dans lesquels R représente un groupe alkyle ou alkylène, linéaire ou ramifié, comprenant de 5 à 8 atomes de carbone, de préférence de 6 à 7 atomes de carbone, de préférence 6 atomes de carbone. in which R represents a linear or branched alkyl or alkylene group comprising from 5 to 8 carbon atoms, preferably from 6 to 7 carbon atoms, preferably 6 carbon atoms.
De préférence, dans les composés de formule (I) ou (II) R représente un groupe alkyle ou alkylène, linéaire ou ramifié, comprenant 6 ou 7 atomes de carbone. Preferably, in the compounds of formula (I) or (II) R represents a linear or branched alkyl or alkylene group comprising 6 or 7 carbon atoms.
De préférence, le mono-éther de glycérol selon l'invention est choisi parmi les composés de formule (I). Preferably, the glycerol mono-ether according to the invention is chosen from the compounds of formula (I).
De préférence, le mono-éther de glycérol selon l'invention est choisi parmi les composés de formule (II).  Preferably, the glycerol mono-ether according to the invention is chosen from the compounds of formula (II).
De préférence, le mono-éther de glycérol selon l'invention est un mélange d'au moins un composé de formule (I) et d'au moins un composé de formule (II). Preferably, the glycerol mono-ether according to the invention is a mixture of at least one compound of formula (I) and at least one compound of formula (II).
Avantageusement, la composition lubrifiante selon l'invention comprend de 0,01 % à 5% en masse de mono-éther de glycérol selon l'invention par rapport à la masse totale de la composition lubrifiante. De manière préférée, la composition lubrifiante comprend de 0,01 % à 2% en masse, de préférence de 0,1 % à 1 ,5% en masse de mono-éther de glycérol tel que définit auparavant, par rapport à la masse totale de la composition lubrifiante. Les mono-éthers de glycérol selon l'invention peuvent être obtenus par toute technique connue de l'homme du métier. Notamment, une voie de synthèse préférée pour la préparation des mono-éthers de glycérol de l'invention consiste en la réaction entre le glycérol et un alcool ROH, R ayant la définition donnée ci-dessus. Advantageously, the lubricating composition according to the invention comprises from 0.01% to 5% by weight of glycerol mono-ether according to the invention relative to the total mass of the lubricating composition. Preferably, the lubricating composition comprises from 0.01% to 2% by weight, preferably from 0.1% to 1.5% by weight of glycerol mono-ether as defined above, relative to the total mass. of the lubricating composition. The glycerol monoethers according to the invention can be obtained by any technique known to those skilled in the art. In particular, a preferred synthetic route for the preparation of glycerol monoethers of the invention consists in the reaction between glycerol and an alcohol ROH, R having the definition given above.
La réaction d'éthérification entre le glycérol et un alcool est de préférence mise en œuvre en présence d'un catalyseur acide, de préférence un catalyseur hétérogène acide ou un catalyseur homogène acide. The etherification reaction between glycerol and an alcohol is preferably carried out in the presence of an acid catalyst, preferably an acid heterogeneous catalyst or a homogeneous acid catalyst.
De préférence, les catalyseurs hétérogènes acides sont choisis parmi les zéolithes, des résines ou des oxydes d'alumine. Parmi les résines on peut notamment citer les résines polymères perfluorées tel que le Nation® NR50, les résines échangeuses de cations tel que le Dowex 50wx8, ou parmi les résines échangeuses d'ions aux propriétés acides telles que les Amberlyst® 15 et 36. Parmi les zéolithes on peut notamment citer les mordénites, les zéolithes ZMS-5 de type MFI, les zéolithes BEA ou les faujasites. De préférence, le catalyseur hétérogène acide est une zéolithe, de préférence une zéolithe de type mordénite, de préférence une mordénite avec un rapport Si/AI de 1 1 . Preferably, the acidic heterogeneous catalysts are chosen from zeolites, resins or oxides of alumina. Among the resins there may be mentioned perfluorinated polymer resins such as Nation® NR50, cation exchange resins such as Dowex 50wx8, or among ion exchange resins with acidic properties such as Amberlyst® 15 and 36. zeolites that may be mentioned include mordenites, ZMS-5 zeolites of the MFI type, BEA zeolites or faujasites. Preferably, the acidic heterogeneous catalyst is a zeolite, preferably a mordenite type zeolite, preferably a mordenite with a Si / Al ratio of 1 1.
De préférence, les catalyseurs acides homogènes sont choisis parmi l'acide phosphorique, l'acide para-toluènesulfonique (APTS) et l'acide triflique. De préférence le catalyseur homogène acide est l'acide para-toluènesulfonique (APTS).  Preferably, the homogeneous acidic catalysts are chosen from phosphoric acid, para-toluenesulfonic acid (APTS) and triflic acid. Preferably, the acidic homogeneous catalyst is para-toluenesulfonic acid (APTS).
De manière avantageuse selon l'invention et dans le but de privilégier la synthèse du mono-éther de glycérol, la quantité de catalyseur homogène acide mise en jeu dans la réaction est comprise entre 1 % et 10 % molaire par rapport à la teneur en glycérol, de préférence elle est comprise entre 1 % et 2,5% molaire. De manière avantageuse, la quantité de catalyseur hétérogène mise en jeu dans la réaction est comprise entre 1 et 5% molaire par rapport à la teneur en glycérol, de préférence elle est de 3,5% molaire. Le rapport molaire alcool/glycérol est optimisé afin d'obtenir le meilleur rendement possible en mono-éther de glycérol tout en limitant les réactions secondaires de formation d'oligomères de glycérol. De préférence, le rapport molaire alcool/glycérol est compris entre 1/6 et 3/1 , de préférence il est de 1/1 . Advantageously according to the invention and in order to favor the synthesis of the glycerol mono-ether, the amount of acidic homogeneous catalyst involved in the reaction is between 1% and 10 mol% relative to the glycerol content. preferably it is between 1% and 2.5% molar. Advantageously, the amount of heterogeneous catalyst involved in the reaction is between 1 and 5 mol% relative to the glycerol content, preferably it is 3.5 mol%. The alcohol / glycerol molar ratio is optimized in order to obtain the best possible yield of glycerol mono-ether while limiting the secondary reactions of glycerol oligomer formation. Preferably, the alcohol / glycerol molar ratio is between 1/6 and 3/1, preferably it is 1/1.
La réaction d'éthérification peut également, dans un autre mode de réalisation, être réalisée à partir du di-éther issu de la réaction de l'alcool sur lui-même.  The etherification reaction may also, in another embodiment, be carried out from the di-ether resulting from the reaction of the alcohol on itself.
La réaction d'éthérification du glycérol peut être menée dans tout type de réacteur connu de l'homme du métier. De manière avantageuse, elle est menée en autoclave.  The etherification reaction of glycerol can be carried out in any type of reactor known to those skilled in the art. Advantageously, it is conducted in an autoclave.
Les conditions de température, pression et la durée de réaction d'éthérification du glycérol peuvent être déterminées de manière usuelle par l'homme du métier. De manière avantageuse, la réaction est menée à une température comprise entre 80 et 200°C, de préférence comprise entre 130 et 160°C, par exemple elle est menée à 150°C.  The conditions of temperature, pressure and the etherification reaction time of the glycerol can be determined in the usual manner by those skilled in the art. Advantageously, the reaction is carried out at a temperature of between 80 and 200 ° C., preferably between 130 and 160 ° C., for example it is carried out at 150 ° C.
De manière avantageuse selon l'invention, la réaction est menée pendant au moins 5 heures, de préférence pendant 5 à 48 heures. La durée de réaction peut être égale à 24 heures ou 48 heures. Advantageously according to the invention, the reaction is carried out for at least 5 hours, preferably for 5 to 48 hours. The reaction time may be 24 hours or 48 hours.
De manière avantageuse selon l'invention, le procédé comprend une étape de purification. Cette étape de purification peut comprendre les étapes suivantes : extraction liquide-liquide et/ou distillation fractionnée sous pression réduite. L'extraction liquide- liquide est menée en présence d'un couple de solvants, déterminable de manière usuelle par l'homme du métier. Advantageously according to the invention, the process comprises a purification step. This purification step may comprise the following steps: liquid-liquid extraction and / or fractional distillation under reduced pressure. Liquid extraction liquid is conducted in the presence of a pair of solvents, usually determined by those skilled in the art.
De préférence, le couple acétonitrile/heptane peut être employé.  Preferably, the acetonitrile / heptane pair can be used.
De manière avantageuse, au moins une extraction liquide-liquide est menée, de préférence au moins deux. De manière encore plus préférée, trois extractions liquide- liquide sont réalisées.  Advantageously, at least one liquid-liquid extraction is conducted, preferably at least two. Even more preferably, three liquid-liquid extractions are carried out.
De manière préférée selon l'invention, pendant l'étape de distillation, l'alcool initial et le mono-éther de glycérol sont séparés.  In a preferred manner according to the invention, during the distillation step, the initial alcohol and the glycerol mono-ether are separated.
De manière avantageuse, le procédé selon l'invention permet d'obtenir sélectivement des mono-éthers de glycérol.  Advantageously, the process according to the invention makes it possible to selectively obtain glycerol monoethers.
La composition lubrifiante selon l'invention comprend au moins une huile de base. The lubricating composition according to the invention comprises at least one base oil.
La ou les huiles de base utilisée(s) dans les compositions lubrifiantes selon l'invention peuvent être choisies dans une large gamme. L'huile de base de la composition lubrifiante utilisée selon l'invention peut notamment être choisie parmi des huiles minérales, synthétiques ou naturelles, bio-sourcées, animales, végétales connues de l'homme du métier. The base oil (s) used in the lubricant compositions according to the invention can be chosen from a wide range. The base oil of the lubricant composition used according to the invention may in particular be chosen from mineral, synthetic or natural oils, bio-sourced, animal, plant known to those skilled in the art.
La ou les huiles de base selon l'invention peuvent être des huiles d'origine minérale ou synthétique, choisies parmi les huiles des groupes I à V selon les classes définies dans la classification API (ou leurs équivalents selon la classification ATIEL) (tableau A), seules ou en mélanges.  The base oil (s) according to the invention may be oils of mineral or synthetic origin, chosen from oils of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) (Table A ), alone or in mixtures.
Tableau A Les huiles de base minérales utiles selon l'invention incluent tous types de bases obtenues par distillation atmosphérique et sous vide du pétrole brut, suivies d'opérations de raffinage telles qu'extraction au solvant, désalphatage, déparaffinage au solvant, hydrotraitement, hydrocraquage, hydroisomérisation et hydrofinition. Table A The mineral base oils useful 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, desalphating, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization and hydrofinishing.
Des mélanges d'huiles synthétiques et minérales peuvent également être employés. Mixtures of synthetic and mineral oils can also be used.
Il n'existe généralement aucune limitation quant à l'emploi de bases lubrifiantes différentes pour réaliser les compositions lubrifiantes utilisées selon l'invention, si ce n'est qu'elles doivent avoir des propriétés, notamment de viscosité, indice de viscosité, teneur en soufre, résistance à l'oxydation, adaptées à une utilisation pour des moteurs ou pour des transmissions de véhicule. There is generally no limitation on the use of different lubricating bases for producing the lubricating compositions used according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulfur, oxidation resistance, adapted for use for engines or for vehicle transmissions.
La composition lubrifiante selon l'invention peut comprendre de 50 à 99% d'au moins une huile de base, de préférence de 60 à 99%, avantageusement de 70 à 99% en masse par rapport à la masse totale de composition lubrifiante.  The lubricant composition according to the invention may comprise from 50 to 99% of at least one base oil, preferably from 60 to 99%, advantageously from 70 to 99% by weight relative to the total weight of lubricating composition.
La composition lubrifiante selon l'invention peut également comprendre de nombreux additifs. Les additifs préférés pour la composition lubrifiante utilisée selon l'invention sont choisis parmi les détergents, les additifs anti-usure, les additifs extrême-pression, les améliorants de l'indice de viscosité, les dispersants, les antioxydants, les améliorants du point d'écoulement, les agents anti-mousse, et les modificateurs de frottements inorganiques et leurs mélanges. The lubricating composition according to the invention may also comprise numerous additives. The preferred additives for the lubricant composition used according to the invention are chosen from detergents, antiwear additives, extreme pressure additives, viscosity index improvers, dispersants, antioxidants, d-point improvers and the like. flow, anti-foam agents, and inorganic friction modifiers and mixtures thereof.
La composition lubrifiante selon l'invention peut également comprendre au moins un additif détergent. The lubricant composition according to the invention may also comprise at least one detergent additive.
Les additifs détergents permettent généralement de réduire la formation de dépôts à la surface des pièces métalliques par dissolution des produits secondaires d'oxydation et de combustion.  The detergent additives generally make it possible to reduce the formation of deposits on the surface of the metal parts by dissolving the secondary oxidation and combustion products.
Les additifs détergents utilisables dans la composition lubrifiante selon l'invention sont généralement connus de l'homme de métier. Les additifs détergents peuvent être des composés anioniques comprenant une longue chaîne hydrocarbonée lipophile et une tête hydrophile. Le cation associé peut être un cation métallique d'un métal alcalin ou alcalino- terreux. Les additifs détergents sont préférentiellement choisis parmi les sels de métaux alcalins ou de métaux alcalino-terreux d'acides carboxyliques, les sulfonates, les salicylates, les naphténates, ainsi que les sels de phénates. Les métaux alcalins et alcalino-terreux sont préférentiellement le calcium, le magnésium, le sodium ou le baryum. The detergent additives that can be used in the lubricant composition according to the invention are generally known to those skilled in the art. The detergent additives may be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation may be a metal cation of an alkali metal or alkaline earth metal. The detergent additives are preferably chosen from the alkali metal or alkaline earth metal salts of carboxylic acids, the sulphonates, the salicylates, the naphthenates and the phenate salts. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
Ces sels métalliques comprennent généralement le métal en quantité stœchiométrique ou bien en excès, donc en quantité supérieure à la quantité stœchiométrique. Il s'agit alors d'additifs détergents surbasés ; le métal en excès apportant le caractère surbasé à l'additif détergent est alors généralement sous la forme d'un sel métallique insoluble dans l'huile, par exemple un carbonate, un hydroxyde, un oxalate, un acétate, un glutamate, préférentiellement un carbonate. These metal salts generally comprise the metal in stoichiometric amount or in excess, therefore in an amount greater than the stoichiometric amount. It is then overbased detergent additives; the excess metal bringing the overbased character to the detergent additive is then generally in the form of an oil insoluble metal salt, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .
De manière avantageuse, la composition lubrifiante selon l'invention peut comprendre de 2 à 4 % en poids d'additif détergent par rapport à la masse totale de la composition lubrifiante. Les additifs anti-usure et les additifs extrême pression protègent les surfaces en frottement par formation d'un film protecteur adsorbé sur ces surfaces.  Advantageously, the lubricant composition according to the invention may comprise from 2 to 4% by weight of detergent additive relative to the total mass of the lubricating composition. Anti-wear additives and extreme pressure additives protect friction surfaces by forming a protective film adsorbed on these surfaces.
Il existe une grande variété d'additifs anti-usure. De manière préférée pour la composition lubrifiante selon l'invention, les additifs anti-usure sont choisis parmi des additifs phospho- soufrés comme les alkylthiophosphates métalliques, en particulier les alkylthiophosphates de zinc, et plus spécifiquement les dialkyldithiophosphates de zinc ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR11)(OR12))2, dans laquelle R1 1 et R12, identiques ou différents, représentent indépendamment un groupement alkyle, préférentiellement un groupement alkyle comportant de 1 à 18 atomes de carbone. There is a wide variety of anti-wear additives. In a preferred manner for the lubricating composition according to the invention, the anti-wear additives are chosen from phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs. The preferred compounds are of formula Zn ((SP (S) (OR 11 ) (OR 12 )) 2 , in which R 1 1 and R 12 , which are identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to at 18 carbon atoms.
Les phosphates d'amines sont également des additifs anti-usure qui peuvent être employés dans la composition lubrifiante selon l'invention. Toutefois, le phosphore apporté par ces additifs peut agir comme poison des systèmes catalytiques des automobiles car ces additifs sont générateurs de cendres. On peut minimiser ces effets en substituant partiellement les phosphates d'amines par des additifs n'apportant pas de phosphore, tels que, par exemple, les polysulfures, notamment les oléfines soufrées. De manière avantageuse, la composition lubrifiante selon l'invention peut comprendre de 0,01 à 6 % en masse, préférentiellement de 0,05 à 4 % en masse, plus préférentiellement de 0,1 à 2 % en masse par rapport à la masse totale de composition lubrifiante, d'additifs anti-usure et d'additifs extrême-pression. La composition lubrifiante de la présente invention peut également comprendre au moins un additif améliorant l'indice de viscosité. Comme exemple d'additifs améliorant l'indice de viscosité, on peut citer les esters polymères, les homopolymères ou les copolymères, hydrogénés ou non-hydrogénés, du styrène, du butadiène et de l'isoprène, notamment les polyacrylates, les polyméthacrylates (PMA) ou encore les copolymères oléfines, notamment les copolymères ethylène/propylène. Amine phosphates are also anti-wear additives which can be used in the lubricating composition according to the invention. However, the phosphorus provided by these additives can act as a poison of the catalytic systems of automobiles because these additives are ash generators. These effects can be minimized by partially substituting amine phosphates with non-phosphorus additives, such as, for example, polysulfides, especially sulfur-containing olefins. Advantageously, the lubricant composition according to the invention may comprise from 0.01 to 6% by weight, preferably from 0.05 to 4% by weight, more preferably from 0.1 to 2% by weight relative to the mass. total lubricating composition, anti-wear additives and extreme pressure additives. The lubricating composition of the present invention may also comprise at least one viscosity index improving additive. As an example of additives improving the viscosity, mention may be made of polymeric esters, homopolymers or copolymers, hydrogenated or non-hydrogenated, of styrene, butadiene and isoprene, in particular polyacrylates, polymethacrylates (PMA) or even olefin copolymers, in particular copolymers ethylene / propylene copolymer.
De manière avantageuse, la composition lubrifiante selon l'invention peut également comprendre au moins un agent dispersant. Advantageously, the lubricant composition according to the invention may also comprise at least one dispersing agent.
L'agent dispersant peut être choisi parmi les bases de Mannich, les succinimides et leurs dérivés.  The dispersing agent may be chosen from Mannich bases, succinimides and their derivatives.
De manière également avantageuse, la composition lubrifiante selon l'invention peut comprendre de 0,2 à 10 % en masse d'agent dispersant par rapport à la masse totale de la composition lubrifiante. Also advantageously, the lubricating composition according to the invention may comprise from 0.2 to 10% by weight of dispersing agent relative to the total mass of the lubricating composition.
De manière avantageuse, la composition lubrifiante selon l'invention peut comprendre au moins un additif antioxydant. Advantageously, the lubricant composition according to the invention may comprise at least one antioxidant additive.
L'additif antioxydant permet généralement de retarder la dégradation de la composition lubrifiante en service. Cette dégradation peut notamment se traduire par la formation de dépôts, par la présence de boues ou par une augmentation de la viscosité de la composition lubrifiante.  The antioxidant additive generally serves to retard the degradation of the lubricating composition in service. This degradation can notably result in the formation of deposits, the presence of sludge or an increase in the viscosity of the lubricant composition.
Les additifs antioxydants agissent notamment comme inhibiteurs radicalaires ou destructeurs d'hydropéroxydes. Parmi les additifs antioxydants couramment employés, on peut citer les additifs antioxydants de type phénolique, les additifs antioxydants de type aminé, les additifs antioxydants phosphosoufrés. Certains de ces additifs antioxydants, par exemple les additifs antioxydants phosphosoufrés, peuvent être générateurs de cendres. Les additifs antioxydants phénoliques peuvent être exempts de cendres ou bien être sous forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, les esters de phénol stériquement encombrés et les phénols stériquement encombrés comprenant un pont thioéther, les diphénylamines, les diphénylamines substituées par au moins un groupement alkyle en CrC12, les Ν,Ν'-dialkyle-aryle-diamines et leurs mélanges. Antioxidant additives act in particular as radical inhibitors or destroyers of hydroperoxides. Among the antioxidant additives commonly used, mention may be made of antioxidant additives of phenolic type, antioxidant additives of amine type, antioxidant phosphosulfur additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators. Phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts. The antioxidant additives may in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C 12 -C 12 alkyl group, Ν, Ν ' dialkyl-aryl diamines and mixtures thereof.
De préférence selon l'invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupement phénol dont au moins un carbone vicinal du carbone portant la fonction alcool est substitué par au moins un groupement alkyle en C C10, de préférence un groupement alkyle en CrC6, de préférence un groupement alkyle en C4, de préférence par le groupement ter-butyle. Les composés aminés sont une autre classe d'additifs antioxydants pouvant être utilisés, éventuellement en combinaison avec les additifs antioxydants phénoliques. Des exemples de composés aminés sont les aminés aromatiques, par exemple les aminés aromatiques de formule NR13R14R15 dans laquelle R13 représente un groupement aliphatique ou un groupement aromatique, éventuellement substitué, R14 représente un groupement aromatique, éventuellement substitué, R15 représente un atome d'hydrogène, un groupement alkyle, un groupement aryle ou un groupement de formule R16S(0)zR17 dans laquelle R16 représente un groupement alkylène ou un groupement alkenylène, R17 représente un groupement alkyle, un groupement alcényle ou un groupement aryle et z représente 0, 1 ou 2. Preferably, according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group in which at least one vicinal carbon of the carbon bearing the alcohol function is substituted with at least one alkyl group containing 10 carbon atoms, preferably an alkyl group containing CrC 6 , preferably a C 4 alkyl group, preferably by the ter-butyl group. Amino compounds are another class of antioxidant additives that can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, for example aromatic amines of formula NR 13 R 14 R 15 in which R 13 represents an optionally substituted aliphatic or aromatic group, R 14 represents an optionally substituted aromatic group, R 15 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R 16 S (O) z R 17 in which R 16 represents an alkylene group or an alkenylene group, R 17 represents an alkyl group, a alkenyl group or an aryl group and z represents 0, 1 or 2.
Des alkyl phénols sulfurisés ou leurs sels de métaux alcalins et alcalino-terreux peuvent également être utilisés comme additifs antioxydants.  Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used as antioxidant additives.
Une autre classe d'additifs antioxydants est celle des composés cuivrés, par exemples les thio- ou dithio-phosphates de cuivre, les sels de cuivre et d'acides carboxyliques, les dithiocarbamates, les sulphonates, les phénates, les acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d'acide ou d'anhydride succiniques peuvent également être utilisés.  Another class of antioxidant additives is copper compounds, for example copper thio- or dithio-phosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper salts I and II, succinic acid or anhydride salts can also be used.
La composition lubrifiante selon l'invention peut contenir tous types d'additifs antioxydants connus de l'homme du métier.  The lubricant composition according to the invention may contain all types of antioxidant additives known to those skilled in the art.
De manière avantageuse, la composition lubrifiante comprend au moins un additif antioxydant exempt de cendres. Advantageously, the lubricating composition comprises at least one ash-free antioxidant additive.
De manière également avantageuse, la composition lubrifiante selon l'invention comprend de 0,5 à 2 % en poids par rapport à la masse totale de la composition, d'au moins un additif antioxydant.  Also advantageously, the lubricating composition according to the invention comprises from 0.5 to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.
De manière également avantageuse, la composition lubrifiante selon l'invention peut également comprendre au moins un additif abaisseur de point d'écoulement. Also advantageously, the lubricant composition according to the invention may also comprise at least one pour point depressant additive.
En ralentissant la formation de cristaux de paraffine, les additifs abaisseurs de point d'écoulement améliorent généralement le comportement à froid de la composition lubrifiante selon l'invention. By slowing the formation of paraffin crystals, pour point depressant additives generally improve the cold behavior of the lubricant composition according to the invention.
Comme exemple d'additifs abaisseurs de point d'écoulement, on peut citer les polyméthacrylates d'alkyle, les polyacrylates, les polyarylamides, les polyalkylphénols, les polyalkylnaphtalènes, les polystyrènes alkylés. La composition lubrifiante peut comprendre également un additif anti-mousse choisi parmi les silicones et leurs dérivés, tels que les polysiloxanes et leurs dérivés. Un tel additif anti- mousse peut être le Bluesil 47V12500® commercialisé par la société Bluestar Silicones. L'additif anti-mousse de la composition lubrifiante selon l'invention peut également être choisi parmi les acryliques, tel que le PC1244® commercialisé par la société Mosanto. De manière avantageuse, la composition lubrifiante selon l'invention peut comprendre au moins un additif modificateur de frottement supplémentaire, comme un modificateur de frottement inorganique. L'additif modificateur de frottement inorganique peut être choisi parmi un composé apportant des éléments métalliques et un composé exempt de cendres. Parmi les composés apportant des éléments métalliques, on peut citer les complexes de métaux de transition tels que Mo, Sb, Sn, Fe, Cu, Zn dont les ligands peuvent être des composés hydrocarbonés comprenant des atomes d'oxygène, d'azote, de soufre ou de phosphore. As examples of pour point depressant additives, mention may be made of alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes. The lubricating composition may also comprise an anti-foam additive chosen from silicones and their derivatives, such as polysiloxanes and their derivatives. Such an anti-additive foam may be Bluesil 47V12500® marketed by Bluestar Silicones. The antifoam additive of the lubricant composition according to the invention may also be chosen from acrylics, such as PC1244® marketed by Mosanto. Advantageously, the lubricating composition according to the invention may comprise at least one additional friction-modifying additive, such as an inorganic friction modifier. The inorganic friction modifier additive may be selected from a compound providing metal elements and an ash free compound. Among the compounds providing metal elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu and Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen, sulfur or phosphorus.
En particulier peuvent être cités les composés d'organomolybdène qui représentent la famille la plus importante de modificateurs de frottements. Le dithiocarbamate de molybdène (MoDTC) est le composé le plus connu de cette famille.  In particular, mention may be made of organomolybdenum compounds which represent the most important family of friction modifiers. Molybdenum dithiocarbamate (MoDTC) is the best known compound in this family.
De manière avantageuse, la composition lubrifiante selon l'invention peut comprendre de 0,01 à 5 % en masse ou de 0,01 à 2 % en masse, préférentiellement de 0,1 à 1 ,5 % en masse ou de 0,1 à 2 % en masse par rapport à la masse totale de la composition lubrifiante, d'additif modificateur de frottement supplémentaire.  Advantageously, the lubricant composition according to the invention may comprise from 0.01 to 5% by weight or from 0.01 to 2% by weight, preferably from 0.1 to 1.5% by weight or 0.1 at 2% by weight relative to the total mass of the lubricant composition, additional friction modifier additive.
L'invention concerne également l'utilisation d'une composition lubrifiante selon l'invention pour lubrifier un moteur, de préférence un moteur de véhicule automobile. The invention also relates to the use of a lubricant composition according to the invention for lubricating an engine, preferably a motor vehicle engine.
L'invention concerne également l'utilisation d'une composition lubrifiante selon l'invention pour diminuer le frottement dans un moteur, de préférence un moteur de véhicule automobile. The invention also relates to the use of a lubricant composition according to the invention for reducing the friction in an engine, preferably a motor vehicle engine.
L'invention concerne également l'utilisation de la composition lubrifiante selon l'invention pour réduire la consommation de carburant d'un moteur, de préférence d'un moteur de véhicule automobile. The invention also relates to the use of the lubricant composition according to the invention for reducing the fuel consumption of an engine, preferably a motor vehicle engine.
De préférence, la diminution du frottement dans un moteur ou la réduction de la consommation de carburant d'un moteur sont mesurées par rapport au frottement ou à la consommation de carburant mesurées avec une composition de référence. Avantageusement, ladite composition de référence ne comprend pas de mono-éther de glycérol caractérisé en ce que l'une des fonctions alcool du glycérol forme une fonction éther avec un groupe R alkyle ou alkylène comprenant 6 ou 7 atomes de carbone. De manière avantageuse, l'invention concerne également l'utilisation de la composition lubrifiante selon l'invention pour réduire la consommation de carburant au démarrage et pendant la phase de fonctionnement du moteur. Preferably, the reduction of friction in an engine or the reduction of the fuel consumption of an engine is measured with respect to the friction or fuel consumption measured with a reference composition. Advantageously, said reference composition does not comprise glycerol mono-ether, characterized in that one of the alcohol functions of glycerol forms an ether function with an alkyl or alkylene R group comprising 6 or 7 carbon atoms. Advantageously, the invention also relates to the use of the lubricant composition according to the invention for reducing the fuel consumption at the start and during the operating phase of the engine.
L'invention concerne également l'utilisation d'un mono-éther de glycérol tel que défini ci- dessus dans une composition lubrifiante pour diminuer le frottement dans un moteur ou pour réduire la consommation de carburant d'un moteur, de préférence un moteur de véhicule automobile. The invention also relates to the use of a glycerol mono-ether as defined above in a lubricant composition to reduce the friction in an engine or to reduce the fuel consumption of an engine, preferably a fuel engine. motor vehicle.
De préférence, l'utilisation d'un mono-éther de glycérol de formule selon l'invention tel que défini ci-dessus permet une réduction de la consommation de carburant au démarrage et pendant la phase de fonctionnement du moteur.  Preferably, the use of a glycerol mono-ether of formula according to the invention as defined above allows a reduction in fuel consumption at startup and during the operating phase of the engine.
L'invention concerne également une méthode de lubrification d'un moteur, de préférence d'un moteur de véhicule automobile comprenant la mise en œuvre d'une composition lubrifiante selon l'invention. The invention also relates to a method of lubricating an engine, preferably a motor vehicle engine comprising the implementation of a lubricant composition according to the invention.
L'invention concerne également une méthode pour réduire la consommation de carburant d'un moteur, de préférence d'un moteur de véhicule automobile comprenant la mise en œuvre dans ledit moteur d'une composition lubrifiante selon l'invention. Les différents aspects de l'invention sont illustrés par les exemples qui suivent, mais n'y sont pas limités. The invention also relates to a method for reducing the fuel consumption of an engine, preferably a motor vehicle engine comprising the implementation in said engine of a lubricant composition according to the invention. The various aspects of the invention are illustrated by the following examples, but are not limited thereto.
EXEMPLES Composés utilisés : EXAMPLES Compounds used:
Les différents mono-éthers de glycérol testés sont décrits dans le tableau I ci-dessous. La voie de synthèse nécessite que le glycérol et l'alcool gras utilisés soient solubles l'un dans l'autres. Or, tout alcool gras comprenant 8 carbones et plus n'est pas soluble dans le glycérol, les éthers de glycérol correspondants ne peuvent donc pas être synthétisés selon la voie de synthèse décrite. The different glycerol monoethers tested are described in Table I below. The synthetic route requires that the glycerol and fatty alcohol used be soluble one in the other. However, any fatty alcohol comprising 8 or more carbons is not soluble in glycerol, the corresponding glycerol ethers can not be synthesized according to the described synthetic route.
a eau  a water
Les conditions opératoires utilisées pour la préparation de chacun des mono-éthers de glycérol ci-dessus sont présentées dans le tableau II suivant : The operating conditions used for the preparation of each of the above glycerol monoethers are presented in the following Table II:
Nom Réacteur Catalyseur Température Durée Rendement Name Reactor Catalyst Temperature Time Yield
en MEG (%) in MEG (%)
MEG B 2,5%mol 160°C 24h 15 MEG B 2.5% mol 160 ° C 24h 15
C7P APTS  C7P APTS
MEG ROR 2,5%mol 150°C 14h 10  MEG ROR 2.5% mol 150 ° C 14h 10
C7S APTS  C7S APTS
MEG R2L 1 % mol 150°C 24h 25  MEG R2L 1% mol 150 ° C 24h 25
C6P APTS  C6P APTS
MEG ROR 2,5% mol 150°C 7h 33  MEG ROR 2.5% mol 150 ° C 7h 33
C5P APTS  C5P APTS
MEG MP 1 %mol 150°C 24h 15  MEG MP 1% mol 150 ° C 24h 15
C4P APTS MEG ROR 2,5%mol 140°C 5h 8 C4P APTS MEG ROR 2.5% mol 140 ° C 5h 8
C3P APTS  C3P APTS
Ta bleau II  Ta ble II
Les réacteurs utilisés sont les suivants : The reactors used are the following:
- B : Réacteur en verre Buchi plongé dans un bain d'huile,  - B: Buchi glass reactor immersed in an oil bath,
- ROR : Réacteur à ouverture rapide avec une hélice d'agitation de 220m L, - ROR: Fast opening reactor with a stirring propeller of 220mL,
- MP : Multi-réacteurs constitué de six autoclaves de 75 mL, - MP: Multi-reactors consisting of six autoclaves of 75 mL,
- R2L : Réacteur de 2L en inox avec pale d'agitation.  - R2L: 2L stainless steel reactor with stirring blade.
La quantité de catalyseur est une quantité molaire par rapport à la quantité de glycérol utilisée.  The amount of catalyst is a molar amount relative to the amount of glycerol used.
Pour la synthèse de chacun des mono-éthers de glycérol ci-dessus :  For the synthesis of each of the above glycerol monoethers:
- le glycérol, le catalyseur et l'alcool sont mélangés et réagissent ensemble ;  the glycerol, the catalyst and the alcohol are mixed and react together;
- puis le mélange ainsi obtenu est purifié d'abord par décantation sans solvant, puis soumis à une extraction liquide-liquide et enfin soumis à une distillation fractionnée pour récupérer le mono-éther de glycérol.  - Then the mixture thus obtained is first purified by decantation without solvent, then subjected to a liquid-liquid extraction and finally subjected to fractional distillation to recover the glycerol mono-ether.
La quantité de mono-éthers de glycérol obtenu en fin de réaction est mesurée par chromatographie en phase gazeuse.  The amount of glycerol monoethers obtained at the end of the reaction is measured by gas chromatography.
Mesures ATG ATG measurements
L'analyse thermogravimétrique (ATG) donne la perte de masse d'un échantillon en fonction de la température. L'échantillon est chauffé selon des rampes de température programmées. Les pertes de masse sont déterminées à l'aide d'une balance qui mesure en continu la masse de l'échantillon pendant sa montée en température.  Thermogravimetric analysis (TGA) gives the mass loss of a sample as a function of temperature. The sample is heated according to programmed temperature ramps. The mass losses are determined using a scale that continuously measures the mass of the sample during its rise in temperature.
Les résultats de ces mesures ATG sur les différents mono-éthers de glycérol ci-dessus sont décrits dans le tableau III  The results of these ATG measurements on the various glycerol monoethers above are described in Table III.
Tableau I II Ainsi les mono-éthers de glycérol courts (MEG C3P et MEG C4P) présentent une perte de masse de 100% pour des températures plus faibles, et notamment inférieures à 190°C ce qui les rend difficilement utilisables en application moteur voire incompatibles avec une telle application. Table I II Thus short glycerol monoethers (MEG C3P and MEG C4P) have a loss of mass of 100% for lower temperatures, and especially less than 190 ° C which makes them difficult to use in engine application or even incompatible with such application.
A l'inverse les mono-éthers de glycérol selon l'invention (MEG C5P, MEG C6P, MEG C7P et MEG C7S) présentent une perte de masse de 100% pour des températures plus élevées, et notamment pouvant être supérieures à 200°C ce qui les rend tout à fait compatibles avec une utilisation dans une composition lubrifiante pour une application moteur. Conversely, the glycerol monoethers according to the invention (MEG C5P, MEG C6P, MEG C7P and MEG C7S) have a loss of mass of 100% for higher temperatures, and in particular may be greater than 200 ° C. which makes them fully compatible with use in a lubricant composition for engine application.
Tests de caractérisation Characterization tests
Afin de caractériser le comportement des compositions selon l'invention, deux séries de tests ont été menées. Le test HFRR (Machine à Mouvement Alternatif Haute Fréquence, ou High Frequency Reciprocating Rig) permet d'évaluer les performances des carburants et lubrifiants en terme de frottement en régime mixte/limite.  In order to characterize the behavior of the compositions according to the invention, two series of tests were conducted. The HFRR (High Frequency Reciprocating Rig) test is used to evaluate the performance of fuels and lubricants in terms of friction in the mixed / limit regime.
Ce test consite à fixer un plan d'acier sur lequel est disposé la composition lubrifiante à tester dans un bloc chauffant. Une bille d'acier soumise à une certaine charge est alors mise en contact avec la composition lubrifiante et le plan d'acier, avant d'être mise en vibration. La fréquence de vibration et la charge appliquées sur la bille ainsi que la température à laquelle est soumise la composition lubrifiante sont réglables. Cet essai permet d'obtenir une courbe de coefficient de frottement en fonction de la durée du test. En pratique, l'essai dure 30min, la bille parcourt des allers-retours de 2 mm à une fréquence de 20 Hz, soit une vitesse moyenne de cisaillement de 40 mm. s"1 (régime limite). Au point de butée de la bille, la vitesse est nulle ce qui place bien ce test dans un régime de lubrification limite et mixte. Une charge de 200g est appliquée sur la bille, ce qui correspond à une pression de 800 MPa. L'huile est chauffée à 100°C. Le test MTM (Machine de traction ou Mini Traction Machine) permet d'évaluer les performances de lubrifiants en terme de frottement en régime mixte/hydrodynamique. Ce test consiste à mettre en mouvement relatif une bille d'acier et un plan en acier, à des vitesses différentes, permettant de définir le %SSR (Ratio vitesse de glissement/vitesse d'entraînement ou Slide-to-Roll Ratio) qui correspond à la vitesse de glissement/vitesse d'entraînement. Les essais réalisés consistent en une période d'accumulation de 120 min où la bille tourne à 100 mm. s"1 (régime hydrodynamique) avec un %SSR de 50%, pour une charge de 1 ,1 GPa et une température d'huile de 100°C. This test involves fixing a steel plane on which the lubricant composition to be tested is placed in a heating block. A steel ball subjected to a certain load is then brought into contact with the lubricant composition and the steel plane before being vibrated. The vibration frequency and the load applied to the ball as well as the temperature at which the lubricant composition is subjected are adjustable. This test makes it possible to obtain a coefficient of friction curve as a function of the duration of the test. In practice, the test lasts 30min, the ball travels back and forth 2 mm at a frequency of 20 Hz, an average shear rate of 40 mm. s "1 (limit speed). In the abutment point of the ball, the speed is zero which puts out this test in a lubrication system limits and mixed. A load of 200g is applied to the ball, which corresponds to a The oil is heated to 100 ° C. The MTM (Traction Machine or Mini Traction Machine) test is used to evaluate the lubricant performance in terms of friction in the mixed / hydrodynamic regime. in relative motion a steel ball and a steel plane, at different speeds, to define the% SSR (Ratio speed of slip / speed of drive or Slide-to-Roll Ratio) which corresponds to the speed of slip / training speed. The tests carried out consist of a accumulation period of 120 min where the ball rotates at 100 mm. s "1 (hydrodynamic regime) with a% SSR of 50%, for a load of 1, 1 GPa and an oil temperature of 100 ° C.
Un modificateur de frottement est considéré comme efficace s'il permet d'abaisser le coefficient de frottement.  A friction modifier is considered effective if it lowers the coefficient of friction.
Les différents mono-éthers de glycérol sont testés dans une composition lubrifiante de référence dont la composition est donnée dans le tableau IV ci-dessous.  The different glycerol monoethers are tested in a reference lubricant composition whose composition is given in Table IV below.
Tableau IV  Table IV
Chaque mono-éther de glycérol est ajouté à une teneur de 1 % en masse par rapport au poids total de la composition lubrifiante de référence. Les différentes compositions lubrifiantes testées sont décrites dans le tableau V ci-dessous.  Each glycerol mono-ether is added at a content of 1% by weight relative to the total weight of the reference lubricating composition. The various lubricating compositions tested are described in Table V below.
CM c LO CD CM c LO CD
g g g g g O o  g o o o
'ω 'ω 'ω 'ω 'ω CO co ' ω ' ω ' ω ' ω ' ω CO CO
o o o o o o o  o o o o o o o
CL CL CL CL CL CL CL CL CL CL CL CL CL CL
E E E E E E E E E E E E
o o o o o o o  o o o o o o o
O O O O O O O Composition 99 99 99 99 99 99 99 de OOOOOOO Composition 99 99 99 99 99 99 99 of
référence  reference
MEG C3P 1  MEG C3P 1
MEG C4P 1  MEG C4P 1
MEG C5P 1  MEG C5P 1
MEG C6P 1  MEG C6P 1
MEG C7P 1  MEG C7P 1
MEG C7S 1  MEG C7S 1
Mono-oléate 1 de glycérol  Mono-oleate 1 of glycerol
Tableau V  Table V
Exemple 1 : tests HFRR  Example 1: HFRR tests
Le tableau VI ci-dessous représente les coefficients de frottement de la composition de référence et des compositions 3, 4, 5 et 6 ; les valeurs ont été prises après 900 secondes d'essai. Table VI below represents the coefficients of friction of the reference composition and compositions 3, 4, 5 and 6; the values were taken after 900 seconds of testing.
Ainsi, l'ensemble des compositions lubrifiantes selon l'invention (compositions 3 à 6) abaisse le coefficient de frottement de manière significative, sur cet essai HFRR dans des conditions sévérisées.  Thus, all of the lubricant compositions according to the invention (compositions 3 to 6) significantly lower the coefficient of friction on this HFRR test under severe conditions.
Exemple 2 : tests MTM Example 2: MTM tests
Comme décrit précédemment, les tests MTM vont sonder les performances des modificateurs de frottement dans des conditions moins sévères que l'essai HFRR mais néanmoins représentatives de points de fonctionnement de certains organes moteurs. Le tableau VI I ci-dessous indique les valeurs des coefficients de frottements des compositions 1 , 2, 4, 5, 6 et 7 ; les valeurs ont été prises après 6120 secondes d'essai. As previously described, the MTM tests will probe the performance of the friction modifiers under less severe conditions than the HFRR test but nevertheless representative of operating points of certain driving members. Table VI I below gives the values of the coefficients of friction of compositions 1, 2, 4, 5, 6 and 7; the values were taken after 6120 seconds of testing.
Tableau VII Ainsi, les compositions lubrifiantes 4 à 6 selon l'invention abaissent le coefficient de frottement de manière significative, sur cet essai MTM en comparaison des compositions comparatives 1 et 2 (comprenant respectivement un mono-éther de glycérol en C3 et en C4) ou de la composition comparative 7 (comprenant du mono-oléate de glycérol)) Exemple 3 : essais moteurs  Thus, the lubricant compositions 4 to 6 according to the invention significantly lower the coefficient of friction on this MTM test in comparison with the comparative compositions 1 and 2 (comprising respectively a C 3 and C 4 glycerol mono-ether). or comparative composition 7 (comprising glycerol mono-oleate)) Example 3: Motor Tests
Afin de confirmer les bons résultats exprimés sur essais tribologiques, la composition 3 et la composition 6 ont été évaluées comparativement par la mise en œuvre de l'essai moteur décrit ci-après : In order to confirm the good results expressed on tribological tests, the composition 3 and the composition 6 have been evaluated comparatively by the implementation of the motor test described below:
Lors de l'essai, la température des fluides (eau/huile) est régulée. Le moteur est ensuite positionné à un point de fonctionnement choisi (régime/couple) et la consommation de carburant est ensuite mesurée sur ce même point. Une cartographie de consommation est ainsi réalisée par ce moyen. Le moteur d'essai est un moteur Renault R9M. During the test, the fluid temperature (water / oil) is regulated. The engine is then positioned at a selected operating point (rpm / torque) and the fuel consumption is then measured at this point. A consumption map is thus produced by this means. The test engine is a Renault R9M engine.
Le tableau VIII représente les gains en termes de % de consommation carburant par rapport à la composition de référence à une température (eau/huile) fixée à 90°C. Le seuil de significativité de l'essai est égal 0.15%. Table VIII shows the gains in terms of% fuel consumption compared to the reference composition at a temperature (water / oil) set at 90 ° C. The threshold of significance of the test is equal to 0.15%.
Régime Couple Composition 6 Composition 3Couple Diet Composition 6 Composition 3
2500 160 0,14 0,31 2500 160 0.14 0.31
2000 160 0,24 0,44 1500 160 0,19 0,352000 160 0.24 0.44 1500 160 0.19 0.35
2500 90 0,37 0,61 2500 90 0.37 0.61
2000 90 0,06 0,50  2000 90 0.06 0.50
1500 90 0,28 0,60  1500 90 0.28 0.60
2500 40 0,42 0,88  2500 40 0.42 0.88
2000 40 0,58 0,82  2000 40 0.58 0.82
1500 40 0,71 0,79  1500 40 0.71 0.79
849 2 1 ,96 0,95  849 2 1, 96 0.95
Gain moyen  Average gain
0,49 0,62  0.49 0.62
chaud  hot
Tableau VIII  Table VIII
Ainsi les compositions lubrifiantes selon l'invention améliorent de manière significative la consommation de carburant, notamment à chaud.  Thus the lubricant compositions according to the invention significantly improve the fuel consumption, especially when hot.

Claims

REVENDICATIONS
1 . Composition lubrifiante comprenant : 1. A lubricating composition comprising:
- au moins une huile de base ; et  at least one base oil; and
- au moins un mono-éther de glycérol caractérisé en ce que l'une des fonctions alcool du glycérol forme une fonction éther avec un groupe R alkyle ou alkylène, linéaire ou ramifié, comprenant 6 ou 7 atomes de carbone,  at least one glycerol mono-ether, characterized in that one of the alcohol functions of glycerol forms an ether function with a linear or branched alkyl or alkylene group R comprising 6 or 7 carbon atoms,
ladite composition étant un lubrifiant moteur.  said composition being a motor lubricant.
2. Composition lubrifiante selon la revendication 1 comprenant : The lubricating composition of claim 1 comprising:
- au moins une huile de base ; et  at least one base oil; and
- au moins un mono-éther de glycérol de formule (I) ou (II), pris seul ou en mélange at least one glycerol mono-ether of formula (I) or (II), taken alone or as a mixture
(l) (II) dans lequel R représente un groupe alkyle ou alkylène, linéaire ou ramifié, comprenant 6 ou 7 atomes de carbone.  (I) (II) wherein R represents a linear or branched alkyl or alkylene group comprising 6 or 7 carbon atoms.
3. Composition lubrifiante selon l'une quelconque des revendications 1 ou 2 dans laquelle R représente un groupe alkyle ou alkylène, linéaire ou ramifié comprenant 6 atomes de carbone. 3. Lubricating composition according to any one of claims 1 or 2 wherein R represents a linear or branched alkyl or alkylene group comprising 6 carbon atoms.
4. Composition lubrifiante selon l'une quelconque des revendications 1 à 3 comprenant de 0,01 % à 5% en masse, de préférence de 0,01 % à 2% en masse, de préférence de 0,1 à 1 ,5% en masse de mono-éther de glycérol défini selon les revendications 1 à 3. 4. Lubricating composition according to any one of claims 1 to 3 comprising from 0.01% to 5% by weight, preferably from 0.01% to 2% by weight, preferably from 0.1 to 1.5% by weight. in weight of glycerol mono-ether defined according to claims 1 to 3.
5. Utilisation d'une composition lubrifiante selon l'une quelconque des revendications 1 à 4 pour lubrifier un moteur, de préférence un moteur de véhicule automobile. 5. Use of a lubricant composition according to any one of claims 1 to 4 for lubricating an engine, preferably a motor vehicle engine.
6. Utilisation d'une composition lubrifiante selon l'une quelconque des revendications 1 à 4 pour diminuer le frottement dans un moteur, de préférence un moteur de véhicule automobile. 6. Use of a lubricant composition according to any one of claims 1 to 4 for reducing the friction in an engine, preferably a motor vehicle engine.
7. Utilisation d'une composition lubrifiante selon l'une quelconque des revendications 1 à 4 pour réduire la consommation de carburant d'un moteur, de préférence un moteur de véhicule automobile. 7. Use of a lubricant composition according to any one of claims 1 to 4 for reducing the fuel consumption of an engine, preferably a motor vehicle engine.
8. Utilisation d'un mono-éther de glycérol tel que défini selon l'une quelconque des revendications 1 à 3 dans une composition lubrifiante pour diminuer le frottement dans un moteur ou pour réduire la consommation de carburant d'un moteur, de préférence un moteur de véhicule automobile . 8. Use of a glycerol mono-ether as defined in any one of claims 1 to 3 in a lubricant composition to reduce friction in an engine or to reduce the fuel consumption of an engine, preferably a motor vehicle engine.
9. Méthode de lubrification d'un moteur de véhicule automobile comprenant la mise en œuvre d'une composition lubrifiante selon l'une quelconque des revendications 1 à 4. 9. A method of lubricating a motor vehicle engine comprising the implementation of a lubricant composition according to any one of claims 1 to 4.
EP17816626.0A 2016-12-07 2017-12-06 Lubricating composition comprising glycerol monoethers Withdrawn EP3551734A1 (en)

Applications Claiming Priority (2)

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FR1662075A FR3059677B1 (en) 2016-12-07 2016-12-07 LUBRICATING COMPOSITION INCLUDING GLYCEROL MONO-ETHERS
PCT/EP2017/081746 WO2018104408A1 (en) 2016-12-07 2017-12-06 Lubricating composition comprising glycerol monoethers

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EP (1) EP3551734A1 (en)
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WO (1) WO2018104408A1 (en)

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CA3141132A1 (en) * 2019-06-19 2020-12-24 Exxonmobil Chemical Patents Inc. Compositions comprising oligomerized reaction products and methods for downhole use thereof

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GB1029610A (en) * 1965-04-08 1966-05-18 Shell Int Research Improvements in or relating to ethers
JPS5925890A (en) * 1982-08-05 1984-02-09 Mitsubishi Oil Co Ltd Common lubricating oil composition
JPS6356814A (en) * 1986-08-27 1988-03-11 Ishihara Sangyo Kaisha Ltd Magnetic recording medium
JP2000273481A (en) 1999-03-23 2000-10-03 New Japan Chem Co Ltd Lubricating oil composition
JP2001064286A (en) * 1999-08-25 2001-03-13 New Japan Chem Co Ltd Lubricant composition
JP2001214186A (en) * 2000-01-31 2001-08-07 Asahi Denka Kogyo Kk Lubricating composition
US20060183652A1 (en) * 2004-12-10 2006-08-17 Takashi Fujitsu Lubricating oil composition
KR20120099065A (en) * 2009-12-03 2012-09-06 이데미쓰 고산 가부시키가이샤 Lubricating oil composition
FR2969146B1 (en) * 2010-12-17 2013-01-11 Fonds De Dev Des Filieres Des Oleagineux Et Proteagineux Fidop PROCESS FOR THE PREPARATION OF POLYOL ETHER

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FR3059677A1 (en) 2018-06-08
US20190300809A1 (en) 2019-10-03
WO2018104408A1 (en) 2018-06-14
FR3059677B1 (en) 2020-10-23

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