EP2609180A1 - Engine lubricant - Google Patents
Engine lubricantInfo
- Publication number
- EP2609180A1 EP2609180A1 EP11761140.0A EP11761140A EP2609180A1 EP 2609180 A1 EP2609180 A1 EP 2609180A1 EP 11761140 A EP11761140 A EP 11761140A EP 2609180 A1 EP2609180 A1 EP 2609180A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- lubricating composition
- composition according
- formula
- fatty
- 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.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/04—Metals; Alloys
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/06—Well-defined hydrocarbons aromatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/10—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/10—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M105/14—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms polyhydroxy
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
Definitions
- the present invention relates to lubricating compositions for gasoline engine or diesel vehicle engines, allowing a reduction in the fuel consumption of said vehicles.
- Frictional energy losses between the various engine components occur, depending on the engine parts, either in hydrodynamic, elastohydrodynamic, or limit friction regimes.
- the formulation of a fuel-saving engine lubricant is not limited to the selection of these different components independently of each other.
- the interactions between the different components must be taken into account, and the other lubricant performances, such as the stability of the viscosity, the inhibition of the corrosion, the dispersing power ... must not be altered.
- engine lubricating compositions for achieving fuel economy can be formulated by the combination of GTL-type bases, with organic friction modifiers of fatty acid esters and polyols type, and VI-improving polymers of polybutene type, ethylene propylene copolymers, polyacrylates or polymethacrylates, AB Block copolymers obtained by copolymerization of diene such as butadiene and isoprenes with vinyl aromatics such as styrene.
- compositions are for example disclosed in application WO 2008/124191.
- Such bases have the disadvantage of a high cost and it is desirable to develop an additivation to formulate lubricants fuel savers or fuel eco (FE) with mostly conventional bases.
- Organometallic friction modifiers may also be associated.
- the application EP 2078745 thus discloses a lubricating composition for petrol and diesel engines, associating molybdenum dithiocarbamates and zinc dithiophosphates, and making it possible to obtain fuel savings in vehicles equipped with these engines.
- Eco-fueled motor lubricants comprising a mixture of organo-molybdenum friction modifiers such as molybdenum dithiocarbamates, and organic friction modifiers such as monoesters of fatty acids and polyols are described in application WO 2004/053033.
- WO 93/21288 discloses FE motor lubricants also associating ethoxylated amine friction modifiers with partial esters of fatty acids and polyols, and VI improvers of polyester type, polymethacrylates, polyacrylates, polyolefins.
- Application EP 0955353 also describes fuel-oil engine lubricant formulas combining organomolybdenum friction modifiers (DTCMo) with ethoxylated fatty amine-type organic friction modifiers, optionally in combination with VI-improving polymers of polymethacrylate, polyolefin, styrene type. diene copolymers.
- DTCMo organomolybdenum friction modifiers
- VI-improving polymers of polymethacrylate, polyolefin, styrene type. diene copolymers optionally in combination with VI-improving polymers of polymethacrylate, polyolefin, styrene type. diene copolymers.
- the fuel savings achieved by the engine lubricant must be evaluated globally over an entire standard engine cycle representative of the average conditions of use.
- the lubricant compositions according to the invention make it possible to achieve significant fuel savings, in particular in the urban cold cycle, thanks to a combination of VI improvers and specific friction modifiers.
- the present invention relates to a lubricant composition
- a lubricant composition comprising:
- At least one nitrogen-containing organic friction modifier selected from fatty amines, optionally alkoxylated, fatty amides or imides obtained by condensation of fatty amines and carboxylic acids, alone or as a mixture,
- the hydrocarbon side chains of the comb polymers (b) are obtained by polymerization or copolymerization of olefins, preferably chosen from optionally substituted styrenes, and comprising from 8 to 17 carbon atoms, butadiene, added to 1-4 or in 1-2, or the monomers of formula (I)
- X1 and X2 are independently either hydrogen or alkyl groups having from 1 to 18 carbon atoms.
- the comb polymers (b) are obtained by copolymerization of macromonomers of formula (II)
- each R ' is independently hydrogen or methyl
- RI is an alkyl or aryl residue having from 1 to 6 carbon atoms
- R2 is an alkyl residue having 1 to 26 carbon atoms
- A is formed by the addition of 1,4-butadiene, optionally substituted by alkyl groups comprising 1 to 6 carbon atoms, or by the vinyl addition of styrene, optionally substituted by alkyl groups comprising 1 to 6 carbon atoms ,
- a ' is formed by the addition of 1,2-butadiene optionally substituted by alkyl groups having 1 to 6 carbon atoms, or by the vinyl addition of styrene, optionally substituted with alkyl groups comprising 1 to 6 carbon atoms ,
- n and m are integers greater than or equal to zero, and n + m is an integer between 7 and 3000, preferably between 10 and 3000.
- the comb polymers (b) are obtained by copolymerization of macromonomers of formula (IV)
- each R ' is independently hydrogen or methyl
- RI is an alkyl or aryl residue having from 1 to 6 carbon atoms
- R2 is an alkyl residue having 1 to 26 carbon atoms
- X1, X2, X3 are independently either hydrogen or alkyl groups having from 1 to 18 carbon atoms,
- At least one nitrogen-containing organic friction modifier (c) is chosen from fatty amines of formula (V):
- R3, R4, R5 are independently either hydrogen or aliphatic chains comprising from 1 to 150 carbon atoms, preferably from 1 to 32 carbon atoms, and at least one of R3, R4 or R5 chains is an aliphatic chain fat comprising at least 7 carbon atoms,
- n is an integer greater than or equal to 1, preferably between 1 and 2.
- At least one nitrogen-containing organic friction modifier (c) is chosen from alkoxylated amines corresponding to formulas (VI) or (VII) below:
- R6 and R10 are, independently, fatty aliphatic chains, comprising between 7 and 150, preferably between 7 and 32 carbon atoms, preferentially between 12 and 18 carbon atoms,
- R7 and R8 are, independently, hydrocarbon radicals comprising from 2 to 6 carbon atoms, preferentially from 2 to 4, preferably 2 carbon atoms, R 9 is a hydrocarbon radical comprising from 1 to 6 carbon atoms,
- x, y, p, q and z are integers between 0 and 50, satisfying: 0 ⁇ x + y ⁇ (or equal) 50 and 0 ⁇ p + q + z ⁇ (or equal) 50.
- Rl 1 is a fatty aliphatic chain comprising from 7 to 150 carbon atoms, preferably from 7 to 32 carbon atoms, preferably from 12 to 18 carbon atoms.
- At least one nitrogen-containing organic friction modifier (c) is chosen from fatty amides or imides obtained by condensation of a dicarboxylic acid of formula (IX)
- R12 and R13 are independently hydrogen or a hydrocarbon group, or the hydrocarbon groups R12 and R13 form a ring,
- R14 and R15 independently represent hydrogen or an aliphatic chain comprising between 1 and 150 carbon atoms, preferably from 1 to 32 carbon atoms, preferably from 1 to 26 carbon atoms, and at least one of the RI or R2 chains is a fatty aliphatic chain comprising at least 7 carbon atoms.
- the lubricant compositions according to the invention comprise at least one nitrogen-containing organic friction modifier (c) as described above and at least one organometallic friction modifier (d).
- organometallic friction modifiers these are chosen from dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates and thioxanthates of molybdenum.
- the organometallic friction modifier (d) is a molybdenum dithiocarbamate of formula (XI): where R16, R17, R18, R19 are alkyl chains having 8 to 13 carbon atoms.
- the lubricant compositions according to the invention comprise:
- the lubricating compositions according to the invention comprise at least one isoparaffinic mineral base oil (a) obtained by hydroisomerization of an n-paraffinic filler derived from solvent dewaxing or catalytic dewaxing, or at least one oil.
- the lubricant compositions according to the invention are of grade 0W20 or 0W30 according to the SAEJ300 classification.
- the lubricant compositions according to the invention are oils for 4-stroke petrol or diesel engine of motor vehicles, preferably light vehicles, preferably diesel.
- the present invention also relates to the use of lubricating compositions as described above for the lubrication of gasoline or diesel 4-stroke engines of light vehicles, preferably hybrid vehicles.
- this use is made in a diesel engine.
- the lubricant compositions according to the invention make it possible to achieve fuel savings, in particular in the urban cold cycle, thanks to a specific combination of VI improvers and friction modifiers. Improving Polymer VI (b):
- the VI-improving polymers are compounds which make it possible to minimize variations in the viscosity difference with temperature, that is to say to maintain an oil film sufficient to protect the friction parts at high temperature, and preventing an excessive increase in viscosity when cold.
- the known viscosity index improvers are typically polyalkyl methacrylates (PMA), polyacrylates, polyolefins, copolymers of olefins (dienes) with vinyl aromatics (styrene).
- a comb polymer is a polymer composed of macromolecules comb, which are macromolecules consisting of a main chain having multiple points degree of branching of three, each of which is starting point of a linear side chain.
- This comb structure distinguishes the polymers of US Pat. Nos. 5,565,130 and 5,597,871 and of Application US2008 / 0194443 from polyacrylates and polymethacrylates (PMA) usually used as VI improvers in lubricant compositions of the prior art, in particular those described in applications EP 0955353 and WO 93/21288.
- PMA polymethacrylates
- the lubricant compositions according to the invention comprise, as VI-improving polymer, such a "comb polymer", or polymer with a comb structure, such as for example described in patents US 5,565,130 and US 5,597,871, and the application US2008 / 0194443 of the present application.
- the lubricating compositions according to the invention thus contain, as VI-improving polymer, comb polyacrylates (comb PA) or comb polymethacrylates (comb PMA) which are comb polymers formed of a main chain polyalkyl (meth) acrylates, and long hydrocarbon side chains having at least 50 carbon atoms.
- these hydrocarbon side chains Preferentially, these hydrocarbon side chains have between 50 and 25,000 carbon atoms, preferably between 80 and 20000 carbon atoms, typically of the order of 10,000 carbon atoms.
- the hydrocarbon side chains are obtained by polymerization or copolymerization of olefins, for example the styrene-type monomers, optionally substituted, and comprising from 8 to 17 carbon atoms, butadiene, added to 1-4 or 1-2, ethylene, propylene, isobutene and more generally monomers of formula (I):
- olefins for example the styrene-type monomers, optionally substituted, and comprising from 8 to 17 carbon atoms, butadiene, added to 1-4 or 1-2, ethylene, propylene, isobutene and more generally monomers of formula (I):
- compositions according to the invention contain a comb polymer obtained by copolymerization of macromonomers of formula (II)
- each R ' is independently hydrogen or methyl
- RI is an alkyl or aryl residue having from 1 to 6 carbon atoms
- R2 is an alkyl residue having 1 to 26 carbon atoms
- A is formed by the addition of 1,4-butadiene, optionally substituted by alkyl groups comprising 1 to 6 carbon atoms, or by the vinyl addition of styrene, optionally substituted by alkyl groups comprising 1 to 6 carbon atoms ,
- a ' is formed by the addition of 1,2-butadiene optionally substituted by alkyl groups having 1 to 6 carbon atoms, or by the vinyl addition of styrene, optionally substituted with alkyl groups comprising 1 to 6 carbon atoms
- n and m are integers greater than or equal to zero
- n + m is an integer between 7 and 3000, preferably between 10 and 3000.
- compositions according to the invention contain a comb polymer obtained by copolymerization of macromonomers of formula (IV)
- each R ' is independently hydrogen or methyl
- RI is an alkyl or aryl residue having from 1 to 6 carbon atoms
- R2 is an alkyl residue having 1 to 26 carbon atoms
- X1, X2, X3 are independently either hydrogen or alkyl groups having from 1 to 18 carbon atoms,
- p, q, r are integers greater than or equal to zero, and p + q + r is an integer between 7 and 3000, preferably between 10 and 3000.
- these comb polymers are advantageously used in combination with other VI improving polymers well known to those skilled in the art.
- These well-known polymers are for example chosen from the category of hydrogenated styrene diene copolymers, for example hydrogenated styrene butadiene copolymers (SBH) or styrene isoprene, which are well known to those skilled in the art, preferably hydrogenated styrene butadiene.
- SBH hydrogenated styrene butadiene copolymers
- styrene isoprene which are well known to those skilled in the art, preferably hydrogenated styrene butadiene.
- the VI (b) improving polymers are typically present at levels of between 2 and 20% by weight relative to the total weight of the composition, or between 2 and 15%, or between 5 and 15% by weight relative to the total weight of the composition.
- the total VI improving polymer is in the same ranges (between 2 and 20%, or between 2 and 15%), or between 5 and 15% by weight of VI improving polymers relative to the total weight of the composition).
- the nitrogen-containing organic friction modifiers of the compositions according to the invention are fatty amines, optionally alkoxylated, or fatty amide derivatives of amide or imide type obtained by condensation of fatty amines with (di) carboxylic acids.
- the fatty amines used in the lubricants according to the present invention are primary, secondary or tertiary monoamines, or polyamines, comprising one or more fatty chains.
- Fatty amines are mainly obtained from fatty acids (fatty-chain carboxylic acids), which are generally derived from the hydrolysis of triglycerides present in vegetable and animal oils, such as coconut oil, palm oil, olive, peanut, rapeseed, sunflower, soy, cotton, flax, beef tallow.
- fatty acids fatty-chain carboxylic acids
- vegetable and animal oils such as coconut oil, palm oil, olive, peanut, rapeseed, sunflower, soy, cotton, flax, beef tallow.
- the fatty acids making it possible to obtain the fatty amines of the compositions according to the invention generally comprise from 7 to 32 carbon atoms, preferably from 8 to 24 carbon atoms, preferably from 10 to 20, and preferably from 12 to 18 carbon atoms.
- These acids such as palmi
- the fatty amines used as compound (c) in the lubricant compositions according to the invention correspond to the general formula (V):
- R3, R4, R5 are independently either hydrogen or aliphatic chains comprising from 1 to 150 carbon atoms, preferably from 1 to 32 carbon atoms, and at least one of the R3, R4 or R5 chains is a fatty aliphatic chain comprising at least 7 carbon atoms,
- n is an integer greater than or equal to 1, preferably between 1 and 2.
- the fatty amines used in the lubricants according to the invention are preferably obtained from natural resources, plant or animal. Treatments that result in fatty amines from natural oils can result in mixtures of secondary primary and tertiary monoamines and polyamines.
- mono or polyalkoxylated fatty amines for example mono or polyethoxylated, obtained from the fatty amines described above can be used.
- alkoxylated amines used in the lubricant compositions according to the invention correspond for example to formulas (VI) and (VII) below:
- R6 and R10 are, independently, fatty aliphatic chains, comprising between 7 and 150, preferably between 7 and 32 carbon atoms, preferentially between 12 and 18 carbon atoms,
- R7 and R8 are, independently, hydrocarbon radicals comprising from 2 to 6 carbon atoms, preferentially from 2 to 4, preferably 2 carbon atoms, R 9 is a hydrocarbon radical comprising from 1 to 6 carbon atoms,
- x, y, p, q and z are integers between 0 and 50, satisfying: 0 ⁇ x + y ⁇ (or equal) 50 and 0 ⁇ p + q + z ⁇ (or equal) 50.
- R5 and R9 are aliphatic fatty chains, optionally substituted with aryl groups. In a particularly preferred manner, they comprise between 7 and 30 carbon atoms, preferentially between 10 and 20, preferably between 12 and 18 carbon atoms.
- R6 and R7 are aliphatic chains, preferably alkyl, containing from 2 to 6 carbon atoms, preferably from 2 to 4, preferably 2 carbon atoms.
- R8 is an aliphatic chain, preferably an alkyl chain, containing from 1 to 6 carbon atoms, preferably from 2 to 4, preferably 3 carbon atoms.
- Particularly preferred compounds are diethanolamines of the formula
- R 1 is an aliphatic chain comprising from 7 to 150 carbon atoms, preferentially from 7 to 32 carbon atoms, preferably from 12 to 18 carbon atoms
- the nitrogen-containing organic friction modifiers (c) of the lubricant compositions according to the invention may be amides or imides obtained by condensation of the fatty amines described above and of carboxylic acids, such as, for example, oleylamides, in particular primary oleylamides.
- the organic friction modifiers (c) are amides or imides obtained by condensation of fatty amines and acids. dicarboxylic, aliphatic or aromatic, optionally hydroxylated, such as, for example, malonic acid, succinic acid, malic acid, tartaric acid, phthalic acid, isophthalic acid, preferentially tartaric acid.
- the organic friction modifiers (c) are fatty amides or imides obtained by condensation of a dicarboxylic acid of formula (IX)
- R12 and R13 are independently hydrogen or a hydrocarbon group, or the hydrocarbon groups R12 and R13 form a ring,
- R14 and R15 independently represent hydrogen or an aliphatic chain comprising between 1 and 150 carbon atoms, preferably from 1 to 32 carbon atoms, preferably from 1 to 26 carbon atoms, and at least one of the RI or R2 chains is a fatty aliphatic chain comprising at least 7 carbon atoms.
- the lubricating compositions according to the invention may contain one or more organomolybdenum compound as a friction modifier.
- organomolybdenum compounds are well known to those skilled in the art. These are, for example compounds also containing sulfur or phosphorus, such as dithiophosphates, dithiocarbamates, dithiophosphinates, xanthates, thioxanthates of molybdenum molybdenum.
- Organomolybdenum compounds which are suitable for the lubricant compositions according to the present invention are for example described in the application EP 2,078,745, [0036] to [062].
- the nitrogen-containing organic friction modifiers (c) are typically present at contents of between 0.01 and 2% by weight relative to the total weight of the composition, or between 0.1 and 1 %, or between 0.3 and 0.8% by weight relative to the total weight of the composition.
- the nitrogen organic friction modifiers (c) are used in combination with other friction modifiers, organometallic (d)
- the total content of friction modifiers is in the same ranges (between 0.01 and 2%, or between 0.1 and 1%, or between 0.5 and 0.8% by weight of the friction modifiers relative to the total weight of the composition).
- Lubricating compositions according to the present invention comprise one or more base oils, generally representing at least 60% by weight of the lubricating compositions, generally at least 65% by weight, and up to 90% or more.
- the base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized herein. below, alone or mixed.
- oils may be oils of vegetable, animal or mineral origin.
- the mineral base oils according to the invention include all types of bases obtained by atmospheric distillation and vacuum of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydro-treatment, hydrocracking and hydroisomerization. , hydrofinishing.
- the base oils of the compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
- the polyo-olefins used as base oils for example, are obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and have a viscosity at 100 ° C of between 1.5 and 15 Cst. Their weight average molecular weight is typically between 250 and 3000. Mixtures of synthetic and mineral oils can also be used.
- the lubricant compositions according to the invention are formulated with Group III and / or IV bases.
- the lubricating compositions according to the invention comprise at least one isoparaffinic mineral base oil, obtained by hydroisomerization of an n-paraffinic charge, resulting from solvent dewaxing or catalytic dewaxing operations.
- Such bases are Group III mineral bases referred to as Group III + bases.
- the lubricant compositions according to the invention comprise at least one isoparaffinic synthetic base oil, obtained by hydroisomerization of an n-paraffinic filler such as a Fisher Tropsh wax.
- the lubricant compositions according to the invention contain 65 to 90% by weight of such isoparaffinic bases.
- the lubricant compositions according to the invention exclusively contain so-called Group III + mineral bases or bases obtained by hydroisomerization of a Fisher Tropsh wax as a base oil, in a proportion of between 65 and 90%. in mass.
- the compositions according to the present invention have a kinematic viscosity at 100 ° C. of between 5.6 and 16.3 Cst, measured by the ASTM D445 standard (grade SAE 20, 30 and 40), preferably between 9.3 and 12.5 Cst (grade 30).
- the compositions according to the present invention are multigrade oils of grade 0W30 or 0W20 according to the SAEJ300 classification.
- compositions according to the present invention also preferably have a VI viscosity index greater than 130, preferably greater than 150, preferably greater than 160.
- the lubricant compositions according to the invention are motor oils for petrol or diesel vehicles, preferably for diesel vehicles, preferably in accordance with the specifications ACE A C2 or JASO DL1 well known to those skilled in the art.
- the lubricant compositions according to the invention may also contain any type of additive adapted to their use. These additives can be added individually, or in the form of packets of additives, guaranteeing a certain level of performance to the lubricating compositions, as required, for example for a Diesel ACEA (European car manufacturers) or JASO (Japan Automobile Standards Organization) lubricant. These are for example and not limited to: Dispersants, generally representing between 5 and 8% by weight of the lubricating compositions. Dispersants such as succinimides, PIB (polyisobutene) succinimides, Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
- Dispersants such as succinimides, PIB (polyisobutene) succinimides, Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
- Antioxidants generally represent between 0.5 and 2% by weight of the lubricating compositions.
- Antioxidants delay the degradation of oils in service, which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides.
- antioxidants include phenolic antioxidants, sterically hindered amines.
- Another class of antioxidants is that of oil-soluble copper compounds, for example copper thio or dithiophosphate, copper and carboxylic acid salts, copper dithiocarbamates, sulphonates, phenates, acetylacetonates.
- the copper salts I and II, succinic acid or anhydride are used.
- Antiwear additives generally representing between 1 and 2% by weight of the lubricating compositions.
- the anti-wear additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
- the most commonly used is zinc di-thiophosphate or DTPZn. This category also contains various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
- Detergents generally representing between 2 and 4% by weight of the lubricating compositions
- Detergents are typically alkali metal or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts. They typically have a BN according to ASTM D2896 greater than 40, or 80 mg KOH / gram of detergent, and are most often overbased, with BN values typically of the order of 150 and more, or even 250 or 400 or more. (expressed as mg KOH per gram of detergent).
- 0W30 grade diesel engine oils have been prepared from a diesel engine performance additive package to meet ACEA C2 / JASO DLl specifications, including antioxidants, corrosion inhibitors, dispersants, detergents, antiwear, pour point depressants, corrosion inhibitors.
- compositions (in% by weight) of these oils are given in Table 1 below:
- a 5W30 oil comprising an ACEA Cl / JASO DLl performance level additive package, a hydrogenated polyisoprene-type VI-improving polymer formulated from Group III base oils, serves as a reference for the test.
- a vehicle Toyota Corolla Verso D4D Clean Power equipped with an engine common rail injection 2AD, a post processing system DPNR (Diesel Particulate-NOx Reduction) with 5th regeneration injector lure, placed in a B7 environment, is subject to a NEDC (New European Driving Cycle) standard driving cycle, also known as the Motor Vehicle Emissions Group (MVEG) cycle.
- DPNR Diesel Particulate-NOx Reduction
- 5th regeneration injector lure placed in a B7 environment
- NEDC New European Driving Cycle
- MVEG Motor Vehicle Emissions Group
- this cycle (velocity as a function of time) is given in figure 1. It includes a cold phase or cold urban phase (from 0 to 200 seconds), an intermediate phase or hot urban phase (from 200 to 725 seconds), a phase hot or extra urban phase (from 725 to 1200 seconds).
- the vehicle is placed on a E4-standard two-roller bench allowing the resistance encountered on the road to be simulated in a reproducible manner due to the aerodynamic drag and the mass of the vehicle.
- the tests are carried out with an ambient air temperature of 20 ° C, a hygrometry of 50%, a pressure of 1000 mbar.
- the calculation of consumption is done by a carbon balance after analysis of the exhaust gases.
- the fuel used for all tests is an EN590-B7 diesel.
- Absolute fuel consumption is measured (in liters / 100 km), on the global cycle and per phase.
- the consumption differences (in%) with the reference passed immediately before the oil sample to be analyzed are also calculated. The results are given in Table 2.
- the oil A is according to the invention. It contains as a friction modifier a mixture of amides and fatty imides of tartaric acid. It contains as an improvement polymer of VI PMA comb, and a smaller amount of SBH, intended to provide the viscosity necessary to obtain a grade 30 oil.
- oils B to F contain friction modifiers identical to the oils according to the invention, at comparable contents, but are formulated without a comb polymer.
- the amounts of VI improving polymer are adjusted to obtain the desired viscosimetric grade.
- the oil A according to the invention makes it possible to achieve fuel savings with respect to oils B, C, D, E and F over the entire engine cycle and in particular in the cold phase and in the intermediate phase.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1056832A FR2964115B1 (en) | 2010-08-27 | 2010-08-27 | ENGINE LUBRICANT |
PCT/IB2011/053738 WO2012025901A1 (en) | 2010-08-27 | 2011-08-25 | Engine lubricant |
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EP2609180A1 true EP2609180A1 (en) | 2013-07-03 |
EP2609180B1 EP2609180B1 (en) | 2017-01-11 |
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US (1) | US20130196888A1 (en) |
EP (1) | EP2609180B1 (en) |
JP (1) | JP5914482B2 (en) |
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CN (1) | CN103097503B (en) |
BR (1) | BR112013004089A2 (en) |
CA (1) | CA2807756A1 (en) |
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FR (1) | FR2964115B1 (en) |
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- 2011-08-25 WO PCT/IB2011/053738 patent/WO2012025901A1/en active Application Filing
- 2011-08-25 JP JP2013525410A patent/JP5914482B2/en not_active Expired - Fee Related
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- 2011-08-25 ES ES11761140.0T patent/ES2621907T3/en active Active
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JP5914482B2 (en) | 2016-05-11 |
BR112013004089A2 (en) | 2016-06-14 |
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WO2012025901A1 (en) | 2012-03-01 |
CN103097503B (en) | 2015-09-16 |
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US20130196888A1 (en) | 2013-08-01 |
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