EP4127113A1 - Use of hydrogenated diene styrene polymer to reduce particulate emissions - Google Patents

Use of hydrogenated diene styrene polymer to reduce particulate emissions

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Publication number
EP4127113A1
EP4127113A1 EP21714145.6A EP21714145A EP4127113A1 EP 4127113 A1 EP4127113 A1 EP 4127113A1 EP 21714145 A EP21714145 A EP 21714145A EP 4127113 A1 EP4127113 A1 EP 4127113A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenated
lubricating composition
particulate emissions
use according
styrene
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.)
Pending
Application number
EP21714145.6A
Other languages
German (de)
French (fr)
Inventor
Gautier BURETTE
François PAOLONI
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.)
TotalEnergies Onetech SAS
Original Assignee
TotalEnergies Onetech SAS
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 TotalEnergies Onetech SAS filed Critical TotalEnergies Onetech SAS
Publication of EP4127113A1 publication Critical patent/EP4127113A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/073—Star shaped polymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/50—Emission or smoke controlling properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation

Definitions

  • TITLE Use of hydrogenated styrene diene polymer to reduce particulate emissions
  • the present invention relates to the use of hydrogenated styrene diene polymer to reduce particulate emissions from motor vehicles.
  • An objective of the present invention is therefore to provide an additive for a lubricating composition having a direct impact on the emissions of particles.
  • Another objective of the present invention is to provide a lubricating composition having a direct impact on the emissions of particles.
  • particles denotes the particles emitted from the exhaust of motor vehicles. This represents a collection of microscopic particles ( ⁇ m or smaller in size). These substances are diverse and are included in vehicle exhaust gases produced by fuel combustion. These substances can be solid or liquid.
  • the term particles includes the term soot, which is formed, oxidized and contains unburned hydrocarbons, oxygenated derivatives (ketones, esters, aldehydes, lactones, ethers, organic acids) and polycyclic aromatic hydrocarbons (the famous PAHs) accompanied by their nitrates, oxygenates, etc. There are also mineral (SO2, sulphates, etc.) and metallic derivatives.
  • the present invention makes it possible to reduce the emissions of particles having a size greater than or equal to 23 nm.
  • particle size is understood to mean particles, or agglomerate of particles, the size of which is between 23 and 100 nm, preferably between 23 and 60 nm, and more preferably between 23 and 40 nm. nm.
  • the size of the particles can in particular be measured by spectrometry, for example using a spectrometer manufactured by the company Cambustion under the trade reference DMS500.
  • reduction in particle emissions is understood to mean in particular the reduction in the number of particles, in particular of particles having a size greater than or equal to 23 nm. This includes reducing the number of particles emitted during a WLTC cycle. This is measured primarily by the number of kilometers traveled.
  • the number of particles can in particular be measured by a particle counting device such as the device existing under the commercial reference AVL APC 489.
  • the present application relates to the reduction of soot emissions.
  • the present invention relates to the reduction of emissions of particles, preferably particles of size greater than or equal to 23 nm, preferably soot, during urban (low speed), peri-urban (moderate speed) and road cycles. (high speed) defined by the WLTC (or WLTP) (globally harmonized test procedure for light vehicles) and throughout the WLTC.
  • the hydrogenated styrene diene polymer (or hydrogenated styrene / isoprene polymer) according to the invention is a copolymer of styrene and hydrogenated diene. It is one of the compounds classified as additives improving the viscosity index.
  • the styrene / hydrogenated diene copolymer according to the invention can be chosen from copolymers in linear or star form, preferably star form.
  • the styrene / hydrogenated diene copolymer can be chosen from block copolymers or random copolymers.
  • the content of hydrogenated diene units is from 50 to 98%, preferably from 60 to 98%, more preferably from 70 to 97%, even more preferably from 75 to 96% by mass, relative to the mass of the copolymer .
  • the content of styrene units is from 2 to 50%, preferably from 2 to 40%, more preferably from 3 to 30%, even more preferably from 4 to 25% by mass, relative to the mass of the copolymer.
  • the styrene / hydrogenated diene copolymer according to the invention has a weight average molecular mass Mw ranging from 100,000 to 800,000 Da, preferably from 200,000 to 700,000 Da, more preferably from 300,000 to 600 000 Da, even more preferably from 400,000 to 500,000 Da.
  • the styrene / hydrogenated diene copolymer according to the invention has a number-average molecular mass Mn ranging from 50,000 to 800,000 Da, preferably from 75,000 to 600,000 Da, more preferably from 100 000 to 500,000 Da, even more preferably 100,000 to 200,000 Da.
  • the styrene / hydrogenated diene copolymer according to the invention has a dispersity index ranging from 1 to 4, preferably from 1.2 to 3.5, more preferably from 1.5 to 3 , 5, even more preferably from 2 to 3.
  • the hydrogenated styrene diene copolymer is used in an amount of 0.1 to 15% by weight relative to the total weight of the lubricating composition.
  • This quantity is understood as a quantity of active polymer material (dry extract).
  • the copolymer of styrene and of hydrogenated diene used in the context of the present invention may be in the form of a dispersion in a mineral or synthetic oil, and more particularly in a group III oil according to the API classification.
  • the hydrogenated diene unit is a hydrogenated butadiene or hydrogenated isoprene unit, this is then referred to as a hydrogenated styrene / butadiene polymer or a hydrogenated styrene / isoprene polymer.
  • the hydrogenated diene unit is a hydrogenated isoprene unit, this is then referred to as a hydrogenated styrene / isoprene polymer.
  • the base oil used in the lubricating compositions of the invention can be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1). or their mixtures.
  • the mineral base oils of the invention include any type of base oil obtained by atomospheric and vacuum distillation of crude petroleum, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization and hydrofinishing.
  • the base oils of the lubricating compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins.
  • the polyalphaolefins used as base oil are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100 ° C is between 1 , 5 and 15 mm2.s-1 according to ASTM D445.
  • Their average molar mass is generally between 250 and 3000 according to the ASTM D5296 standard.
  • the lubricating composition according to the invention can comprise at least 50% by weight of base oil relative to the total weight of the composition. More advantageously, the lubricating composition according to the invention comprises at least 60% by weight, or even at least 70% by weight, of base oils relative to the total weight of the lubricating composition. More preferably, the lubricating composition according to the invention comprises from 75 to 97% by weight of base oils relative to the total weight of the composition.
  • composition of the invention can also include at least one additive.
  • the preferred additives for the lubricating composition according to the invention are chosen from detergent additives, the friction modifying additives differ from the molybdenum compounds defined above, extreme pressure additives, dispersants, pour point activators, anti- mousse, thickeners and mixtures thereof.
  • the lubricating compositions according to the invention comprise at least one extreme pressure additive, or a mixture.
  • Anti-wear additives and extreme pressure additives protect surface friction by forming a protective film adsorbed on its surfaces.
  • the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as the metals alkylthiophosphate, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP.
  • the preferred compounds are of formula Zn ((SP (S) (OR) (OR ')) 2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
  • Amine phosphates are also antiwear additives which can be used in the lubricating compositions of the invention.
  • the phosphorus atoms provided by these additives can act as a poison in automobile catalytic systems since they generate ash. It is possible to minimize these effects by substituting part of the amine phosphates with additives which do not provide phosphorus, such as for example polysulfides, in particular olefins containing sulfur.
  • the lubricating compositions according to the invention can 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 total weight of lubricating composition, anti-wear and extreme pressure additives.
  • the lubricating compositions according to the invention 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 total weight of composition lubricant, anti-wear additives (or anti-wear compound).
  • compositions according to the invention can comprise at least one friction modifier additive different from the molybdenum compounds of the invention.
  • the friction modifying additives can in particular be chosen from compounds providing metallic elements and ashless compounds.
  • the compounds providing metallic elements mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn for which the ligands may be hydrocarbon compounds comprising oxygen or nitrogen atoms. , sulfur or phosphorus.
  • the ashless friction modifier additives are generally of organic origin or can be chosen from fatty acid monoesters and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty epoxy borates, amines fatty or acid esters of glycerol.
  • fatty compounds comprising at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
  • the lubricating composition according to the invention can comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2 % by weight relative to the total weight of the lubricating composition, of friction modifier additive different from the molybdenum compounds according to the invention.
  • the lubricating composition according to the invention can comprise at least one antioxidant additive.
  • Antioxidant additives generally retard the degradation of the lubricant composition. This degradation is most often expressed by the formation of deposit, by the presence of sludge or by an increase in the viscosity of the lubricating composition.
  • Antioxidant additives generally act as free radical inhibitors or destructive hydroperoxide inhibitors.
  • antioxidants currently used, mention may be made of phenolic-type antioxidants, amine-type antioxidants, and antioxidants containing sulfur and phosphorus. Some of these antioxidants, for example those comprising sulfur and phosphorus can generate ash.
  • the phenolic antioxidant additives can be ash free or in the form of neutral or basic metal salts.
  • the antioxidant additives can in particular be chosen from sterically hindered phenols, esters of sterically hindered phenols, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1 to C12 alkyl group, N, N '-dialkyl-aryl-diamines and mixtures thereof.
  • the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one alkyl group in C1 to C10, preferably a C1 to C6 alkyl group, preferably a C4 alkyl group, preferably a tert-butyl group.
  • Amine compounds are another class of antioxidant additives which can be used, optionally in combination with phenolic antioxidant additives.
  • amine compounds are aromatic amines, for example aromatic amines of formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of formula RdS (0) zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2.
  • Sulfur-containing alkyl phenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
  • antioxidant additives are compounds comprising copper, eg copper thio- or dithiophosphate, copper and carboxylic acid salts, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, salts of succinic acid or succinic anhydride can also be used.
  • the lubricating compositions according to the invention can also comprise any type of antioxidant known to those skilled in the art.
  • the lubricating composition comprises at least one antioxidant additive free of ash.
  • the lubricating composition according to the invention comprises, from 0.1 to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive.
  • the lubricating composition according to the invention can also comprise at least one detergent additive.
  • Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion.
  • detergent additives which can be used in the lubricating compositions according to the invention are generally known to those skilled in the art.
  • Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophobic head.
  • the associated cation can be a metal cation of an alkali or alkaline earth metal.
  • the detergent additives are preferably chosen from alkali or alkaline earth metal salts of carboxylic acid, sulfonates, salicylates, naphthenates, as well as salts of phenates.
  • the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
  • metal salts generally include the metal in a stoichiometric amount or in excess, that is to say in a content greater than the stoichiometric content.
  • overbased detergents the excess metal implying the overbased nature of the detergent additive is generally in the form of an oil insoluble metal salt, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • the lubricating composition according to the invention can comprise from 0.5 to 8% or from 2 to 4% by weight of overbased detergent additive relative to the total weight of the lubricating composition.
  • the lubricating composition according to the invention can also include a pour point depressant additive.
  • the pour point depressant additive By slowing the formation of paraffin crystals, the pour point depressant additive generally improves the cold behavior of the lubricant composition according to the invention.
  • alkyl polymethacrylates there may be mentioned, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalene, alkyl polystyrenes.
  • the lubricating composition according to the invention can also comprise a dispersing agent.
  • the dispersing agents can be chosen from Mannich bases, succinimides and their derivatives. Also advantageously, the lubricating composition according to the invention can comprise from 0.2 to 10% by weight of dispersing agent relative to the total weight of lubricating composition.
  • the lubricating composition according to the invention can also further comprise at least one other additional polymer improving the viscosity index.
  • additional polymer improving the viscosity index there may be mentioned polymeric esters, homopolymers or copolymers, hydrogenated or not, of styrene, butadiene, and isoprene, polymethacrylates (PMA).
  • the lubricating composition according to the invention can comprise from 1 to 15% by weight, relative to the total weight of lubricating composition, of additive improving the viscosity index.
  • the lubricating composition according to the invention can also comprise at least one thickening agent.
  • the lubricating composition according to the invention can also comprise an anti-foaming agent and a demulsifying agent.
  • the lubricating composition of the invention further comprises at least one anti-wear agent, in particular based on Zinc, in particular ZnDTP.
  • the present invention also relates to the use of the lubricating composition according to the invention for reducing the friction of the mechanical parts of an engine, at least one of the parts comprising a coating of amorphous carbon type, preferably hydrogenated amorphous carbon.
  • the present invention also relates to the use of a hydrogenated styrene diene polymer in an engine lubricating composition to reduce particulate emissions.
  • the present invention also relates to a method of reducing the emission of particles in an engine, preferably a gas, gasoline, diesel or even hybrid engine, comprising the use of a lubricating composition comprising a base oil and a hydrogenated styrene diene polymer.
  • the present invention also relates to a method of reducing the emission of particles in an engine, preferably a gas, gasoline, diesel or even hybrid engine, lubricated with a lubricating composition comprising the addition in said lubricating composition of a hydrogenated styrene diene polymer.
  • the hydrogenated styrene diene polymer, the particles, the base oil and the lubricating composition being as defined above.
  • the present invention covers all motorized vehicles, in particular vehicles comprising a 2-stroke or 4-stroke engine, gasoline, diesel, hybrid and gas engines.
  • the present invention covers all motorized vehicles, preferably comprising at least one combustion engine, in particular heavy vehicles or light vehicles.
  • Example 1 Lubricating Compositions The following lubricating compositions were prepared according to Table 2 below.
  • Example 2 Measurement of the number of particles emitted The compositions of Example 1 were subjected to the WLTC test and the quantity of particles per kilometer traveled having a size greater than or equal to 23 nm emitted at the end of each cycle was measured.
  • the engine tests were carried out on 4-cylinder in-line turbocharged engines. The tests are carried out at the same starting temperature of the engine. All other test bench conditions were also held constant. The sampling for the exhaust gas measurements was carried out in the raw exhaust gas before the exhaust system but after the aftertreatment systems. Thus, the effects observed are indeed due to the sole use of the lubricating composition and therefore to the use of the hydrogenated styrene-diene polymer and not to any other criterion such as the presence of a driver, the weight of the vehicle, the temperature. , humidity, etc.
  • the particle size distribution was measured in parallel by a Cambustion differential mobility spectrometer (DMS500). It uses high voltage discharge to charge each particle in proportion to its area. The charged particles are introduced into a classification section with a strong radial electric field. This field causes the particles to drift through a flow in a column towards the electrometer detectors. The particles are detected at different distances in the column, depending on their aerodynamic resistance / load ratio. The outputs of the 22 electrometers are processed in real time at 10 Hz to provide spectral data and other measurements.
  • DMS500 Cambustion differential mobility spectrometer

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

Abstract

The application relates to the use of a lubricant composition containing a base oil and a hydrogenated diene styrene polymer, for reducing engine particulate emissions.

Description

TITRE : Utilisation de polymère styrène diène hydrogéné pour réduire les émissions de particules TITLE: Use of hydrogenated styrene diene polymer to reduce particulate emissions
La présente invention concerne l’utilisation de polymère styrène diène hydrogéné pour réduire les émissions de particules des véhicules motorisés. The present invention relates to the use of hydrogenated styrene diene polymer to reduce particulate emissions from motor vehicles.
En 1992, la première norme européenne sur les émissions des véhicules à moteurs à combustion a été introduite. Entrée en vigueur le 1er septembre 2014 pour les véhicules nouvellement homologués et applicable à tous les véhicules neufs à partir du 1er septembre 2015, la norme antipollution Euro 6 (norme EC 715/2007, amendement 692/2008) concerne tant les moteurs essence que diesel. Cette norme vise notamment quatre polluants : le monoxyde de carbone (CO), les hydrocarbures imbrûlés (HC), les oxydes d’azote (NOx), la masse (PM) et le nombre (PN) des particules, parmi lesquelles les suies, les deux derniers restant les plus problématiques pour le système de dépollution des motorisations modernes. In 1992, the first European standard on vehicle emissions with combustion engines was introduced. Coming into force on September 1, 2014 for newly approved vehicles and applicable to all new vehicles from September 1, 2015, the Euro 6 antipollution standard (EC standard 715/2007, amendment 692/2008) concerns both petrol and diesel engines. . This standard targets four pollutants in particular: carbon monoxide (CO), unburnt hydrocarbons (HC), nitrogen oxides (NOx), the mass (PM) and the number (PN) of particles, including soot, the last two remaining the most problematic for the pollution control system of modern engines.
La chasse au CO2 a incité les constructeurs à augmenter leur rendement pour en abaisser les consommations. Pour cela, il a souvent été opté pour un fonctionnement en mélange pauvre (excès d’air par rapport à la masse de carburant). Malheureusement, ce procédé engendre une augmentation significative des émissions d’oxyde d’azote et de particules. The hunt for CO2 has prompted manufacturers to increase their efficiency in order to lower consumption. For this, it has often been opted for lean-mixture operation (excess air relative to the mass of fuel). Unfortunately, this process results in a significant increase in nitrogen oxide and particulate emissions.
Les constructeurs ont également opté par le passé pour l’introduction de systèmes de filtre à particules dans le souci de faire diminuer le nombre et la masse des particules émises dans l’atmosphère. Le fonctionnement de ces systèmes réside dans la plupart des cas en une combustion des suies par une élévation de la température des gaz d'échappement à l'entrée du filtre. Cette opération nécessite la présence d'une catalyse. Manufacturers have also opted in the past to introduce particulate filter systems in an effort to reduce the number and mass of particles emitted into the atmosphere. The operation of these systems lies in most cases in a combustion of soot by an increase in the temperature of the exhaust gases at the inlet of the filter. This operation requires the presence of catalysis.
Il existe un intérêt à pouvoir également trouver des additifs pour compositions lubrifiantes et des compositions lubrifiantes ayant un impact direct sur l’émission des particules. There is an interest in also being able to find additives for lubricating compositions and lubricating compositions having a direct impact on the emission of particles.
Un objectif de la présente invention est donc de fournir un additif pour composition lubrifiante ayant un impact direct sur les émissions de particules. An objective of the present invention is therefore to provide an additive for a lubricating composition having a direct impact on the emissions of particles.
Un autre objectif de la présente invention est de fournir une composition lubrifiante ayant un impact direct sur les émissions de particules. Another objective of the present invention is to provide a lubricating composition having a direct impact on the emissions of particles.
D’autres objectifs encore apparaîtront à la lecture de la description de l’invention qui suit. Ces objectifs sont remplis par la présente demande qui concerne l’utilisation d’une composition lubrifiante comprenant une huile de base et un polymère styrène diène hydrogéné, pour réduire les émissions de particules d’un moteur. Still other objectives will become apparent on reading the description of the invention which follows. These objectives are met by the present application which relates to the use of a lubricating composition comprising a base oil and a hydrogenated styrene diene polymer, to reduce the emissions of particles from an engine.
Dans le cadre de la présente invention, on désigne par « particules » les particules émises à l’échappement des véhicules motorisés. Cela représente un ensemble de particules microscopiques (de taille de l’ordre du pm ou inférieure). Ces substances sont variées et sont comprises dans les gaz d’échappement des véhicules issus de la combustion du carburant. Ces substances peuvent être solides ou liquides. Le terme de particules comprend le terme de suies, qui se forment, s’oxydent et renferment des hydrocarbures imbrûlés, des dérivés oxygénés (cétones, esters, aldéhydes, lactones, éthers, acides organiques) et des hydrocarbures aromatiques polycycliques (les fameux HAP) accompagnés de leurs dérivés nitrés, oxygénés, etc. Se trouvent également des dérivés minéraux (S02, sulfates...) et métalliques. In the context of the present invention, the term "particles" denotes the particles emitted from the exhaust of motor vehicles. This represents a collection of microscopic particles (µm or smaller in size). These substances are diverse and are included in vehicle exhaust gases produced by fuel combustion. These substances can be solid or liquid. The term particles includes the term soot, which is formed, oxidized and contains unburned hydrocarbons, oxygenated derivatives (ketones, esters, aldehydes, lactones, ethers, organic acids) and polycyclic aromatic hydrocarbons (the famous PAHs) accompanied by their nitrates, oxygenates, etc. There are also mineral (SO2, sulphates, etc.) and metallic derivatives.
De façon particulièrement avantageuse, la présente invention permet la réduction des émissions de particules présentant une taille supérieure ou égale à 23 nm. Particularly advantageously, the present invention makes it possible to reduce the emissions of particles having a size greater than or equal to 23 nm.
Dans le cadre de la présente invention, on entend par « taille des particules » des particules, ou agglomérat de particules dont la taille est comprise entre 23 et 100 nm, de préférence entre 23 et 60 nm, et de préférence encore entre 23 et 40 nm. In the context of the present invention, the term “particle size” is understood to mean particles, or agglomerate of particles, the size of which is between 23 and 100 nm, preferably between 23 and 60 nm, and more preferably between 23 and 40 nm. nm.
La taille des particules peut notamment être mesurée par spectrométrie, par exemple à l’aide d’un spectromètre fabriqué par la société Cambustion sous la référence commerciale DMS500. The size of the particles can in particular be measured by spectrometry, for example using a spectrometer manufactured by the company Cambustion under the trade reference DMS500.
Par réduction des émissions de particules, on entend notamment la réduction du nombre de particules, notamment de particules présentant une taille supérieure ou égale à 23 nm. Il est notamment question de la réduction du nombre de particules émises lors d’un cycle WLTC. Cela est mesuré principalement en fonction d’un nombre de kilomètres parcourus. The term “reduction in particle emissions” is understood to mean in particular the reduction in the number of particles, in particular of particles having a size greater than or equal to 23 nm. This includes reducing the number of particles emitted during a WLTC cycle. This is measured primarily by the number of kilometers traveled.
La nombre des particules peut notamment être mesurée par un dispositif de comptage des particules tel que le dispositif existant sous la référence commerciale AVL APC 489. The number of particles can in particular be measured by a particle counting device such as the device existing under the commercial reference AVL APC 489.
De préférence, la présente demande concerne la réduction des émissions de suies. De préférence, la présente invention concerne la réduction des émissions de particules, de préférence de particules de taille supérieure ou égale à 23 nm, de préférence de suies, pendant les cycles urbain (faible vitesse), péri-urbain (vitesse modérée) et routier (grande vitesse) définis par le WLTC (ou WLTP) (procédure mondiale harmonisée de tests pour les véhicules légers) et sur l’ensemble du WLTC. Preferably, the present application relates to the reduction of soot emissions. Preferably, the present invention relates to the reduction of emissions of particles, preferably particles of size greater than or equal to 23 nm, preferably soot, during urban (low speed), peri-urban (moderate speed) and road cycles. (high speed) defined by the WLTC (or WLTP) (globally harmonized test procedure for light vehicles) and throughout the WLTC.
Le polymère styrène diène hydrogéné (ou polymère styrène/isoprène hydrogéné) selon l’invention est un copolymère de styrène et de diène hydrogéné. Il fait partie des composés classés dans les additifs améliorant l’indice de viscosité. The hydrogenated styrene diene polymer (or hydrogenated styrene / isoprene polymer) according to the invention is a copolymer of styrene and hydrogenated diene. It is one of the compounds classified as additives improving the viscosity index.
Le copolymère styrène/diène hydrogéné selon l’invention peut être choisi parmi les copolymères sous forme linéaire ou étoilé, de préférence étoilé. The styrene / hydrogenated diene copolymer according to the invention can be chosen from copolymers in linear or star form, preferably star form.
Le copolymère styrène/diène hydrogéné peut être choisi parmi les copolymères blocs ou les copolymères statistiques. The styrene / hydrogenated diene copolymer can be chosen from block copolymers or random copolymers.
De préférence, la teneur en motifs diène hydrogéné est de 50 à 98%, de préférence de 60 à 98%, plus préférentiellement de 70 à 97%, encore plus préférentiellement de 75 à 96% en masse, par rapport à la masse du copolymère. Preferably, the content of hydrogenated diene units is from 50 to 98%, preferably from 60 to 98%, more preferably from 70 to 97%, even more preferably from 75 to 96% by mass, relative to the mass of the copolymer .
De préférence, la teneur en motifs styrène est de 2 à 50%, de préférence de 2 à 40%, plus préférentiellement de 3 à 30%, encore plus préférentiellement de 4 à 25% en masse, par rapport à la masse du copolymère. Preferably, the content of styrene units is from 2 to 50%, preferably from 2 to 40%, more preferably from 3 to 30%, even more preferably from 4 to 25% by mass, relative to the mass of the copolymer.
Dans un mode de réalisation, le copolymère styrène/diène hydrogéné selon l’invention possède une masse moléculaire moyenne en poids Mw allant de 100 000 à 800 000 Da, de préférence de 200 000 à 700 000 Da, plus préférentiellement de 300 000 à 600 000 Da, encore plus préférentiellement de 400 000 à 500 000 Da. In one embodiment, the styrene / hydrogenated diene copolymer according to the invention has a weight average molecular mass Mw ranging from 100,000 to 800,000 Da, preferably from 200,000 to 700,000 Da, more preferably from 300,000 to 600 000 Da, even more preferably from 400,000 to 500,000 Da.
Dans un mode de réalisation de l’invention, le copolymère styrène/diène hydrogéné selon l’invention possède une masse moléculaire moyenne en nombre Mn allant de 50000 à 800 000 Da, de préférence de 75 000 à 600 000 Da, plus préférentiellement de 100 000 à 500 000 Da, encore plus préférentiellement de 100 000 à 200 000 Da. In one embodiment of the invention, the styrene / hydrogenated diene copolymer according to the invention has a number-average molecular mass Mn ranging from 50,000 to 800,000 Da, preferably from 75,000 to 600,000 Da, more preferably from 100 000 to 500,000 Da, even more preferably 100,000 to 200,000 Da.
La mesure des masses moléculaires moyennes en nombre et en poids (Mn et Mw) est réalisée par chromatographie par perméation de gel (GPC). The measurement of the number and weight average molecular masses (Mn and Mw) is carried out by gel permeation chromatography (GPC).
Dans un mode de réalisation de l’invention, le copolymère styrène/diène hydrogéné selon l’invention possède un indice de dispersité allant de 1 à 4, de préférence de 1 ,2 à 3,5, plus préférentiellement de 1 ,5 à 3,5, encore plus préférentiellement de 2 à 3. In one embodiment of the invention, the styrene / hydrogenated diene copolymer according to the invention has a dispersity index ranging from 1 to 4, preferably from 1.2 to 3.5, more preferably from 1.5 to 3 , 5, even more preferably from 2 to 3.
De préférence, le copolymère styrène diène hydrogéné est mis en œuvre en une quantité de 0,1 à 15% en poids par rapport au poids totale de la composition lubrifiante. Cette quantité s’entend en quantité de matière active de polymère (extrait sec). En effet le copolymère de styrène et de diène hydrogéné utilisé dans le cadre de la présente invention peut se présenter sous la forme d’une dispersion dans une huile minérale ou synthétique, et plus particulièrement dans une huile de groupe III selon la classification API. Preferably, the hydrogenated styrene diene copolymer is used in an amount of 0.1 to 15% by weight relative to the total weight of the lubricating composition. This quantity is understood as a quantity of active polymer material (dry extract). In fact, the copolymer of styrene and of hydrogenated diene used in the context of the present invention may be in the form of a dispersion in a mineral or synthetic oil, and more particularly in a group III oil according to the API classification.
De préférence, le motif diène hydrogéné est un motif butadiène hydrogéné ou isoprène hydrogéné, on parle alors de polymère styrène/butadiène hydrogéné ou de polymère styrène/isoprène hydrogéné. Preferably, the hydrogenated diene unit is a hydrogenated butadiene or hydrogenated isoprene unit, this is then referred to as a hydrogenated styrene / butadiene polymer or a hydrogenated styrene / isoprene polymer.
De préférence, le motif diène hydrogéné est un motif isoprène hydrogéné, on parle alors de polymère styrène/isoprène hydrogéné. Preferably, the hydrogenated diene unit is a hydrogenated isoprene unit, this is then referred to as a hydrogenated styrene / isoprene polymer.
L’huile de base utilisée dans les compositions lubrifiantes de l’invention peuvent être des huiles d’origine minérale ou synthétique appartenant aux groupes I à V selon les classes définies par la classification API (ou leurs équivalents selon la classification ATIEL (Tableau 1) ou leurs mélanges. The base oil used in the lubricating compositions of the invention can be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined by the API classification (or their equivalents according to the ATIEL classification (Table 1). or their mixtures.
[Table 1] [Table 1]
Tableau 1 Table 1
Les huiles de base minérales de l’invention incluent tout type d’huile de base obtenue par distillation atomosphérique et sous vide de pétrole brute, suivi par des operations de rafinage telle que l’extraction par solvant, désasphaltage, déparaffinage au solvant, hydrotraitement, hydrocraquage, hydroisomérisation et hydrofinissage. The mineral base oils of the invention include any type of base oil obtained by atomospheric and vacuum distillation of crude petroleum, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization and hydrofinishing.
Des mélanges d’huiles synthétiques et minérales peuvent aussi être utilisés. Les huiles de base des compositions lubrifiantes selon l’invention peuvent aussi être choisies parmi les huiles synthétiques, tels que certains esters d’acides carboxyliques et d’alcools, et les polyalphaoléfines. Les polyalphaoléfines utilsées en tant qu’huile de base sont par exemple obtenues à partir de monomères comprenant de 4 à 32 atomes de carbone, par exemple à partir d’octène ou décène, et pour lesquels la viscosité à 100°C est comprise entre 1 ,5 et 15 mm2.s-1 selon la norme ASTM D445. Leur masse molaire moyenne est généralement comprise entre 250 et 3000 selon la norme ASTM D5296. Mixtures of synthetic and mineral oils can also be used. The base oils of the lubricating compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, and polyalphaolefins. The polyalphaolefins used as base oil are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and for which the viscosity at 100 ° C is between 1 , 5 and 15 mm2.s-1 according to ASTM D445. Their average molar mass is generally between 250 and 3000 according to the ASTM D5296 standard.
La composition lubrifiante selon l’invention peut comprendre au moins 50% en poids d’huile de base par rapport au poids total de la composition. De manière plus avantageuse, la composition lubrifiante selon l’invention comprend au moins 60% en poids, ou même au moins 70% en poids, d’huiles de base par rapport au poids total de la composition lubrifiante. De manière plus préférée, la composition lubrifiante selon l’invention comprend de 75 à 97% en poids d’huiles de base par rapport au poids total de la composition. The lubricating composition according to the invention can comprise at least 50% by weight of base oil relative to the total weight of the composition. More advantageously, the lubricating composition according to the invention comprises at least 60% by weight, or even at least 70% by weight, of base oils relative to the total weight of the lubricating composition. More preferably, the lubricating composition according to the invention comprises from 75 to 97% by weight of base oils relative to the total weight of the composition.
La composition de l’invention peut également comprendre au moins un additif.The composition of the invention can also include at least one additive.
De nombreux additifs peuvent être utilisés dans les compositions lubrifiantes selon l’invention. Many additives can be used in the lubricating compositions according to the invention.
Les additifs préférés pour la composition lubrifiante selon l’invention sont choisis parmi les additifs détergents, les additifs modificateurs de frottement diffèrent des composés molybdène définis ci-dessus, des additifs extrême pression, des dispersants, activateurs du point d'écoulement, agents anti-mousse, épaississants et leurs mélanges. The preferred additives for the lubricating composition according to the invention are chosen from detergent additives, the friction modifying additives differ from the molybdenum compounds defined above, extreme pressure additives, dispersants, pour point activators, anti- mousse, thickeners and mixtures thereof.
De préférence, les compositions lubrifiantes selon l’invention, comprennent au moins un additif extrême pression, ou un mélange. Preferably, the lubricating compositions according to the invention comprise at least one extreme pressure additive, or a mixture.
Les additifs anti-usure et les additifs extrême pression protègent les frictions des surfaces en formant un film de protection adsorbé sur ses surfaces. Anti-wear additives and extreme pressure additives protect surface friction by forming a protective film adsorbed on its surfaces.
Il existe une grande variété d’additifs anti-usure. De préférence, pour les compositions lubrifiantes de l’invention, les additifs anti-usure sont choisis parmi les additifs comprenant du phosphore et du soufre tels que les métaux alkylthiophosphate, en particulier zinc alkylthiophosphate, et plus précisément le zinc dialkyldithiophosphate ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR)(OR'))2, dans laquelle R et R', identique ou différent, représente indépendamment un groupe alkyle, de préférence un groupe alkyle comprenant de 1 à 18 atomes de carbone. There is a wide variety of antiwear additives. Preferably, for the lubricating compositions of the invention, the anti-wear additives are chosen from additives comprising phosphorus and sulfur such as the metals alkylthiophosphate, in particular zinc alkylthiophosphate, and more precisely zinc dialkyldithiophosphate or ZnDTP. The preferred compounds are of formula Zn ((SP (S) (OR) (OR ')) 2, in which R and R', identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
Les phosphates d’amine sont également des additifs anti-usure qui peuvent être utilisés dans les compositions lubrifiantes de l’invention. Cependant, les atomes de phosphore apportés par ces additifs peuvent agir comme poison des systèmes catalytiques des automobiles puisqu’ils génèrent des cendres. Il est possible de minimiser ces effets en substituant une partie des phosphates d’amine avec des additifs n’apportant pas de phosphore, tels que par exemple les polysulfides, notamment les oléfines contenant du soufre. Amine phosphates are also antiwear additives which can be used in the lubricating compositions of the invention. However, the phosphorus atoms provided by these additives can act as a poison in automobile catalytic systems since they generate ash. It is possible to minimize these effects by substituting part of the amine phosphates with additives which do not provide phosphorus, such as for example polysulfides, in particular olefins containing sulfur.
Avantageusement, les compositions lubrifiantes selon l’invention peuvent comprendre de 0,01 à 6% en poids, de préférence de 0,05 à 4% en poids, plus préférentiellement de 0,1 à 2% en poids par rapport au poids total de composition lubrifiante, d’additifs anti-usure et extrême pression. Advantageously, the lubricating compositions according to the invention can 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 total weight of lubricating composition, anti-wear and extreme pressure additives.
Avantageusement, les compositions lubrifiantes selon l’invention comprennent de 0,01 à 6% en poids, de préférence de 0,05 à 4% en poids, plus préférentiellement de 0,1 à 2% en poids par rapport au poids total de composition lubrifiante, d’additifs anti-usure (ou composé anti-usure). Advantageously, the lubricating compositions according to the invention 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 total weight of composition lubricant, anti-wear additives (or anti-wear compound).
Avantageusement, les compositions selon l’invention peuvent comprendre au moins un additif modificateur de friction différents des composés molybdène de l’invention. Les additifs modificateurs de friction peuvent notamment être choisis parmi les composes apportant des éléments métalliques et des composes sans cendres. Parmi les composes apportant des éléments métalliques il peut être fait mention des complexes de métaux de transition tels que Mo, Sb, Sn, Fe, Cu, Zn pour lesquels les ligands peuvent être des composés hydrocarbonés comprenant des atomes d’oxygène, d’azote, de soufre ou de phosphore. Les additifs modificateurs de friction sans cendres sont généralement d’origine organique ou peuvent être choisis parmi les monoester d’acide gras et de polyols, les amines alcoxylées, les amines grasses alcoxylées, les époxydes gras, les borates d’époxydes gras, les amines grasses ou les esters d’acide de glycérol. Selon l’invention, les composes gras comprenant au moins un groupe hydrocarboné comprenant de 10 à 24 atomes de carbone. Advantageously, the compositions according to the invention can comprise at least one friction modifier additive different from the molybdenum compounds of the invention. The friction modifying additives can in particular be chosen from compounds providing metallic elements and ashless compounds. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn for which the ligands may be hydrocarbon compounds comprising oxygen or nitrogen atoms. , sulfur or phosphorus. The ashless friction modifier additives are generally of organic origin or can be chosen from fatty acid monoesters and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty epoxy borates, amines fatty or acid esters of glycerol. According to the invention, fatty compounds comprising at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
Avantageusement la composition lubrifiante selon l’invention peut comprendre de 0,01 à 2% en poids ou de 0,01 à 5% en poids, de préférence de 0,1 à 1 ,5% en poids ou de 0,1 à 2% en poids par rapport au poids total de la composition lubrifiante, d’additif modificateur de friction différent des composés molybdène selon l’invention. Advantageously, the lubricating composition according to the invention can comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2 % by weight relative to the total weight of the lubricating composition, of friction modifier additive different from the molybdenum compounds according to the invention.
Avantageusement, la composition lubrifiante selon l’invention peut comprendre au moins un additif antioxydant. Advantageously, the lubricating composition according to the invention can comprise at least one antioxidant additive.
Les additifs antioxydant généralement retardent la dégradation de la composition lubrifiante. Cette dégradation s’exprime le plus souvent par la formation de dépôt, par la présence de boues ou par une augmentation de la viscosité de la composition lubrifiante. Antioxidant additives generally retard the degradation of the lubricant composition. This degradation is most often expressed by the formation of deposit, by the presence of sludge or by an increase in the viscosity of the lubricating composition.
Les additifs antioxydants agissent généralement comme inhibiteurs radicalaires ou inhibiteurs destructeurs de l'hydroperoxyde. Parmi les antioxydants couramment utilisés on peut citer les antioxydants de type phénolique, les antioxydants de type amine, les antioxydants contenant du soufre et du phosphore. Certains de ces antioxydants, par exemple ceux comprenant du soufre et du phosphore peuvent générer des cendres. Les additifs antioxydants phénoliques peuvent être exempt de cendres ou bien être sous la forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, des esters de phénols stériquement encombrés, des phénols stériquement encombrés comprenant un pont thioéther, des diphénylamines, des diphénylamines substituées avec au moins un groupe alkyl en C1 à C12, des N,N’-dialkyl-aryl-diamines et leurs mélanges. Antioxidant additives generally act as free radical inhibitors or destructive hydroperoxide inhibitors. Among the antioxidants currently used, mention may be made of phenolic-type antioxidants, amine-type antioxidants, and antioxidants containing sulfur and phosphorus. Some of these antioxidants, for example those comprising sulfur and phosphorus can generate ash. The phenolic antioxidant additives can be ash free or in the form of neutral or basic metal salts. The antioxidant additives can in particular be chosen from sterically hindered phenols, esters of sterically hindered phenols, sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C1 to C12 alkyl group, N, N '-dialkyl-aryl-diamines and mixtures thereof.
De préférence selon l’invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupe phénol pour lequel au moins un des atomes de carbone au voisinage de l’atome de carbone portant la fonction alcool est substitué par au moins un groupe alkyle en C1 à C10, de préférence un groupe alkyle en C1 à C6, de préférence un groupe alkyle en C4, de préférence un groupe ter-butyle. Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group for which at least one of the carbon atoms in the vicinity of the carbon atom carrying the alcohol function is substituted by at least one alkyl group in C1 to C10, preferably a C1 to C6 alkyl group, preferably a C4 alkyl group, preferably a tert-butyl group.
Les composés amines sont une autre classe d’additifs antioxydants qui peuvent être utilises, optionnellement en combinaison avec des additifs antioxydants phénoliques. Des exemples de composes amines sont les amines aromatiques, par exemple les amines aromatiques de formule NRaRbRc dans laquelle Ra représente un groupe aliphatique ou un groupe aromatique, optionnellement substitué, Rb représente un groupe aromatique, optionnellement substitué, Rc représente un atome d’hydrogène, un groupe alkyle, un groupe aryle group ou un groupe de formule RdS(0)zRe dans lequel Rd représente un groupe alkylène ou alkenylène, Re représente un groupe alkyle, un groupe alkényle ou un groupe aryle et z représente 0, 1 ou 2. Amine compounds are another class of antioxidant additives which can be used, optionally in combination with phenolic antioxidant additives. Examples of amine compounds are aromatic amines, for example aromatic amines of formula NRaRbRc in which Ra represents an aliphatic group or an aromatic group, optionally substituted, Rb represents an aromatic group, optionally substituted, Rc represents a hydrogen atom, an alkyl group, an aryl group or a group of formula RdS (0) zRe in which Rd represents an alkylene or alkenylene group, Re represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2.
Les alkyl-phénols contenant du soufre ou leurs sels de métaux alcalins ou alcalino- terreux peuvent aussi être utilisés comme additifs antioxydants. Sulfur-containing alkyl phenols or their alkali or alkaline earth metal salts can also be used as antioxidant additives.
D’autres classes d’additifs antioxydants sont les composés comprenant du cuivre, par exemple thio- ou dithio-phosphate de cuivre, des sels de cuivre et d’acides carboxylique, des dithiocarbamates, des sulfonates, des phénates, des acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d’acide ou d’anhydride succinique peuvent également être utilisés. Other classes of antioxidant additives are compounds comprising copper, eg copper thio- or dithiophosphate, copper and carboxylic acid salts, dithiocarbamates, sulfonates, phenates, copper acetylacetonates. Copper I and II salts, salts of succinic acid or succinic anhydride can also be used.
Les compositions lubrifiantes selon l’invention peuvent également comprendre tout type d’antioxydant connu de l’homme du métier. The lubricating compositions according to the invention can also comprise any type of antioxidant known to those skilled in the art.
Avantageusement, la composition lubrifiante comprend au moins un additif antioxydant exempt de cendres. Advantageously, the lubricating composition comprises at least one antioxidant additive free of ash.
Également avantageusement la composition lubrifiante selon l’invention comprend de 0,1 à 2% en poids par rapport au poids total de la composition, d’au moins un additif antioxydant. La composition lubrifiante selon l’invention peut également comprendre au moins un additif détergent. Also advantageously, the lubricating composition according to the invention comprises, from 0.1 to 2% by weight relative to the total weight of the composition, of at least one antioxidant additive. The lubricating composition according to the invention can also comprise at least one detergent additive.
Les additifs détergents permettent généralement de réduire la formation de dépôts à la surface des parties métalliques par dissolution des produits secondaires d’oxydation et de combustion. Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion.
Les additifs détergents pouvant être utilisés dans les compositions lubrifiantes selon l’invention sont généralement connus de l’homme du métier. Les additifs détergents peuvent être des composés anioniques comprenant une longue chaîne hydrocarbonée lipophilique et une tête hydrophobe. Le cation associé peut être un cation métallique d’un métal alcalin ou alcalino-terreux. The detergent additives which can be used in the lubricating compositions according to the invention are generally known to those skilled in the art. Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophobic head. The associated cation can be a metal cation of an alkali or alkaline earth metal.
Les additifs détergents sont de préférence choisis parmi les sels de métaux alcalins ou alcalino-terreux d’acide carboxylique, les sulfonates, les salicylates, les naphténates, ainsi que les sels de phénates. Les métaux alcalins et alcalino-terreux sont de préférence le calcium, le magnésium, le sodium ou le baryum. The detergent additives are preferably chosen from alkali or alkaline earth metal salts of carboxylic acid, sulfonates, salicylates, naphthenates, as well as salts of phenates. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
Ces sels métalliques comprennent généralement le métal en quantité stoechiométrique ou en excès, c’est-à-dire dans une teneur supérieure à la teneur stoechiométrique. Ceux-ci sont alors des détergents surbasés; l’excès de métal impliquant la nature surbasée de l’additif détergent est généralement sous la forme d’un sel métallique insoluble dans l’huile, par exemple carbonate, hydroxyde, oxalate, acétate, glutamate, de préférence carbonate. These metal salts generally include the metal in a stoichiometric amount or in excess, that is to say in a content greater than the stoichiometric content. These are then overbased detergents; the excess metal implying the overbased nature of the detergent additive is generally in the form of an oil insoluble metal salt, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
Avantageusement, la composition lubrifiante selon l’invention peut comprendre de 0,5 à 8% ou de 2 à 4% en poids d’additif détergents surbasés par rapport au poids total de la composition lubrifiante. Advantageously, the lubricating composition according to the invention can comprise from 0.5 to 8% or from 2 to 4% by weight of overbased detergent additive relative to the total weight of the lubricating composition.
Également de manière avantageuse, la composition lubrifiante selon l’invention peut aussi comprendre un additif abaisseur du point d’écoulement. Also advantageously, the lubricating composition according to the invention can also include a pour point depressant additive.
En ralentissant la formation de cristaux de paraffine, l’additif abaisseur du point d’écoulement améliore généralement le comportement à froid de la composition lubrifiante selon l’invention. By slowing the formation of paraffin crystals, the pour point depressant additive generally improves the cold behavior of the lubricant composition according to the invention.
Comme exemple d’additif abaisseurs du point d’écoulement on peut mentionner, les alkyles polyméthacrylates, polyacrylates, polyarylamides, polyalkylphénols, polyalkylnaphtalène, les alkyls polystyrènes. As an example of a pour point depressant additive, there may be mentioned, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalene, alkyl polystyrenes.
Avantageusement, la composition lubrifiante selon l’invention peut aussi comprendre un agent dispersant. Advantageously, the lubricating composition according to the invention can also comprise a dispersing agent.
Les agents dispersants peuvent être choisis parmi les bases de Mannich bases, les succinimides et leurs dérivés. Également de manière avantageuse, la composition lubrifiante selon l’invention peut comprendre de 0,2 à 10% en poids d’agent dispersant par rapport au poids total de composition lubrifiante. The dispersing agents can be chosen from Mannich bases, succinimides and their derivatives. Also advantageously, the lubricating composition according to the invention can comprise from 0.2 to 10% by weight of dispersing agent relative to the total weight of lubricating composition.
Avantageusement, la composition lubrifiante selon l’invention peut également comprendre en outre au moins un autre polymère additionnel améliorant l’indice de viscosité. Comme exemple de polymère additionnel améliorant l’indice de viscosité, on peut citer les esters polymériques, homopolymères ou copolymères, hydrogénés ou non, de styrène, de butadiène, et d’isoprène, les polyméthacrylates (PMA). Également avantageusement, la composition lubrifiante selon l’invention peut comprendre de 1 à 15% en poids par rapport au poids total de composition lubrifiante, d’additif améliorant l’indice de viscosité. Advantageously, the lubricating composition according to the invention can also further comprise at least one other additional polymer improving the viscosity index. As an example of an additional polymer improving the viscosity index, there may be mentioned polymeric esters, homopolymers or copolymers, hydrogenated or not, of styrene, butadiene, and isoprene, polymethacrylates (PMA). Also advantageously, the lubricating composition according to the invention can comprise from 1 to 15% by weight, relative to the total weight of lubricating composition, of additive improving the viscosity index.
La composition lubrifiante selon l’invention peut également comprendre au moins un agent épaississant. The lubricating composition according to the invention can also comprise at least one thickening agent.
La composition lubrifiante selon l’invention peut également comprendre un agent antimousse et un agent démulsifiant. The lubricating composition according to the invention can also comprise an anti-foaming agent and a demulsifying agent.
De préférence, la composition lubrifiante de l’invention comprend en outre au moins un agent anti-usure, notamment à base de Zinc, notamment ZnDTP. Preferably, the lubricating composition of the invention further comprises at least one anti-wear agent, in particular based on Zinc, in particular ZnDTP.
La présente invention concerne également l’utilisation de la composition lubrifiante selon l’invention pour réduire les frottements des pièces mécaniques d’un moteur, au moins une des pièces comprenant un revêtement de type carbone amorphe, de préférence carbone amorphe hydrogéné. The present invention also relates to the use of the lubricating composition according to the invention for reducing the friction of the mechanical parts of an engine, at least one of the parts comprising a coating of amorphous carbon type, preferably hydrogenated amorphous carbon.
La présente invention concerne également l’utilisation d’un polymère styrène diène hydrogéné dans une composition lubrifiante pour moteur pour réduire les émissions de particules. The present invention also relates to the use of a hydrogenated styrene diene polymer in an engine lubricating composition to reduce particulate emissions.
La présente invention concerne également une méthode de réduction de l’émission de particules dans un moteur, de préférence un moteur à gaz, à essence, diesel ou encore hybride, comprenant l’utilisation d’une composition lubrifiante comprenant une huile de base et un polymère styrène diène hydrogéné. The present invention also relates to a method of reducing the emission of particles in an engine, preferably a gas, gasoline, diesel or even hybrid engine, comprising the use of a lubricating composition comprising a base oil and a hydrogenated styrene diene polymer.
La présente invention concerne également une méthode de réduction de l’émission de particules dans un moteur, de préférence un moteur à gaz, à essence, diesel ou encore hybride, lubrifié par une composition lubrifiante comprenant l’ajout dans ladite composition lubrifiante d’un polymère styrène diène hydrogéné. Le polymère styrène diène hydrogéné, les particules, l’huile de base et la composition lubrifiante étant tels que définis ci-dessus. La présente invention couvre tous les véhicules motorisés, notamment les véhicules comprenant un moteur 2-temps ou 4-temps, les moteurs essence, diesel, hybride, gaz. The present invention also relates to a method of reducing the emission of particles in an engine, preferably a gas, gasoline, diesel or even hybrid engine, lubricated with a lubricating composition comprising the addition in said lubricating composition of a hydrogenated styrene diene polymer. The hydrogenated styrene diene polymer, the particles, the base oil and the lubricating composition being as defined above. The present invention covers all motorized vehicles, in particular vehicles comprising a 2-stroke or 4-stroke engine, gasoline, diesel, hybrid and gas engines.
La présente invention couvre tous les véhicules motorisés, de préférence comprenant au moins un moteur à combustion, notamment les véhicules lourds ou véhicules légers. The present invention covers all motorized vehicles, preferably comprising at least one combustion engine, in particular heavy vehicles or light vehicles.
La présente invention va maintenant être décrite à l’aide d’exemples non limitatifs. The present invention will now be described with the aid of non-limiting examples.
Exemple 1 : Compositions lubrifiantes Les compositions lubrifiantes suivants ont été préparées selon le tableau 2 suivant. Example 1: Lubricating Compositions The following lubricating compositions were prepared according to Table 2 below.
[Table 2] [Table 2]
Les caractéristiques des compositions lubrifiantes sont rassemblées dans le tableauThe characteristics of the lubricating compositions are collated in the table
3 ci-dessous : [Table 3] 3 below: [Table 3]
Exemple 2 : Mesure du nombre de particules émises Les compositions de l’exemple 1 ont subi le test WLTC et la quantité de particules par kilomètres parcourus présentant une taille supérieure ou égale à 23 nm émises à la fin de chaque cycle a été mesurée. Example 2: Measurement of the number of particles emitted The compositions of Example 1 were subjected to the WLTC test and the quantity of particles per kilometer traveled having a size greater than or equal to 23 nm emitted at the end of each cycle was measured.
Les tests moteurs ont été effectués sur des moteurs 4 cylindres en ligne turbocompressé. Les tests sont faits à la même température de départ du moteur. Toutes les autres conditions du banc d'essai ont également été maintenues constantes. L'échantillonnage pour les mesures des gaz d'échappement a été effectué dans les gaz d'échappement bruts avant le système d'échappement mais après les systèmes de traitement. Ainsi, les effets observés sont bien dus à la seule utilisation de la composition lubrifiante et donc à l’utilisation du polymère styrène-diène hydrogéné et non à un autre critère quelconque comme la présence d’un conducteur, le poids du véhicule, la température, l’humidité, etc. The engine tests were carried out on 4-cylinder in-line turbocharged engines. The tests are carried out at the same starting temperature of the engine. All other test bench conditions were also held constant. The sampling for the exhaust gas measurements was carried out in the raw exhaust gas before the exhaust system but after the aftertreatment systems. Thus, the effects observed are indeed due to the sole use of the lubricating composition and therefore to the use of the hydrogenated styrene-diene polymer and not to any other criterion such as the presence of a driver, the weight of the vehicle, the temperature. , humidity, etc.
La distribution granulométrique a été mesurée en parallèle par un spectromètre à mobilité différentielle Cambustion (DMS500). Il utilise une décharge haute tension pour charger chaque particule proportionnellement à sa surface. Les particules chargées sont introduites dans une section de classification avec un fort champ électrique radial. Ce champ provoque la dérive des particules à travers un flux dans une colonne vers les détecteurs d'électromètre. Les particules sont détectées à différentes distances dans la colonne, en fonction de leur rapport résistance aérodynamique / charge. Les sorties des 22 électromètres sont traitées en temps réel à 10 Hz pour fournir des données spectrales et d'autres mesures. The particle size distribution was measured in parallel by a Cambustion differential mobility spectrometer (DMS500). It uses high voltage discharge to charge each particle in proportion to its area. The charged particles are introduced into a classification section with a strong radial electric field. This field causes the particles to drift through a flow in a column towards the electrometer detectors. The particles are detected at different distances in the column, depending on their aerodynamic resistance / load ratio. The outputs of the 22 electrometers are processed in real time at 10 Hz to provide spectral data and other measurements.
[Table 4] [Table 4]
Ces résultats montrent que l’ajout d’un polymère styrène isoprène hydrogéné dans une composition lubrifiante permet de réduire la quantité de particules, présentant une taille supérieure ou égale à 23 nm, relarguée à l’échappement. These results show that the addition of a hydrogenated styrene isoprene polymer in a lubricating composition makes it possible to reduce the quantity of particles, having a size greater than or equal to 23 nm, released in the exhaust.

Claims

REVENDICATIONS
1. Utilisation d’une composition lubrifiante comprenant une huile de base et un polymère styrène diène hydrogéné, pour réduire les émissions de particules d’un moteur. 1. Use of a lubricating composition comprising a base oil and a hydrogenated styrene diene polymer, to reduce particulate emissions from an engine.
2. Utilisation selon la revendication 1 , dans laquelle le motif diène hydrogéné est un motif butadiène hydrogéné ou isoprène hydrogéné. 2. Use according to claim 1, wherein the hydrogenated diene unit is a hydrogenated butadiene or hydrogenated isoprene unit.
3. Utilisation selon la revendication 1 ou 2, dans laquelle le motif diène hydrogéné est un motif isoprène hydrogéné. 3. Use according to claim 1 or 2, wherein the hydrogenated diene unit is a hydrogenated isoprene unit.
4. Utilisation selon l’une quelconque des revendications 1 à 3, dans laquelle le polymère styrène/diène hydrogéné selon l’invention peut être choisi parmi les copolymères sous forme linéaire ou étoilé, de préférence étoilé. 4. Use according to any one of claims 1 to 3, wherein the styrene / hydrogenated diene polymer according to the invention can be chosen from copolymers in linear or star form, preferably star.
5. Utilisation selon l’une quelconque des revendications 1 à 4, dans laquelle la teneur en motifs diène hydrogéné est de 50 à 98%, de préférence de 60 à 98%, plus préférentiellement de 70 à 97%, encore plus préférentiellement de 75 à 96% en masse, par rapport à la masse du polymère. 5. Use according to any one of claims 1 to 4, in which the content of hydrogenated diene units is from 50 to 98%, preferably from 60 to 98%, more preferably from 70 to 97%, even more preferably from 75. at 96% by mass, relative to the mass of the polymer.
6. Utilisation selon l’une quelconque des revendications 1 à 5, dans laquelle la teneur en motifs styrène est de 2 à 50%, de préférence de 2 à 40%, plus préférentiellement de 3 à 30%, encore plus préférentiellement de 4 à 25% en masse, par rapport à la masse du polymère. 6. Use according to any one of claims 1 to 5, in which the content of styrene units is from 2 to 50%, preferably from 2 to 40%, more preferably from 3 to 30%, even more preferably from 4 to 25% by mass, relative to the mass of the polymer.
7. Utilisation selon l’une quelconque des revendications 1 à 6, dans laquelle le polymère styrène diène hydrogéné est mis en œuvre en une quantité de 0,1 à 15% en poids par rapport au poids total de la composition lubrifiante. 7. Use according to any one of claims 1 to 6, in which the hydrogenated styrene diene polymer is used in an amount of 0.1 to 15% by weight relative to the total weight of the lubricating composition.
8. Utilisation d’un polymère styrène diène hydrogéné dans une composition lubrifiante pour moteur pour réduire les émissions de particules. 8. Use of a hydrogenated styrene diene polymer in an engine lubricating composition to reduce particulate emissions.
9. Méthode de réduction de l’émission de particules dans un moteur comprenant l’utilisation d’une composition lubrifiante comprenant une huile de base et un polymère styrène diène hydrogéné. 9. A method of reducing particulate emissions in an engine comprising the use of a lubricating composition comprising a base oil and a hydrogenated styrene diene polymer.
10. Méthode de réduction de l’émission de particules dans un moteur lubrifié par une composition lubrifiante comprenant l’ajout dans ladite composition lubrifiante d’un polymère styrène diène hydrogéné. 10. A method of reducing particulate emissions in an engine lubricated with a lubricating composition comprising adding to said lubricating composition a hydrogenated styrene diene polymer.
11. Utilisation selon l’une quelconque des revendications 1 à 8 ou méthode selon l’une des revendications 9 ou 10, dans laquelle les particules présentent une taille supérieure ou égale à 23 nm. 11. Use according to any one of claims 1 to 8 or method according to one of claims 9 or 10, wherein the particles have a size greater than or equal to 23 nm.
12. Utilisation selon l’une quelconque des revendications 1 à 8 ou 11 ou méthode selon l’une des revendications 9 à 10, dans laquelle la réduction des émissions de particules concerne les cycles de type urbain, péri-urbain et routier définis par le WLTC et/ou le WLTC entier. 12. Use according to any one of claims 1 to 8 or 11 or method according to one of claims 9 to 10, in which the reduction of particulate emissions relates to cycles of urban, peri-urban and road type defined by the WLTC and / or the entire WLTC.
EP21714145.6A 2020-03-25 2021-03-23 Use of hydrogenated diene styrene polymer to reduce particulate emissions Pending EP4127113A1 (en)

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