WO2012056022A1 - Moteur diesel ayant des propriétés améliorées - Google Patents

Moteur diesel ayant des propriétés améliorées Download PDF

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Publication number
WO2012056022A1
WO2012056022A1 PCT/EP2011/069042 EP2011069042W WO2012056022A1 WO 2012056022 A1 WO2012056022 A1 WO 2012056022A1 EP 2011069042 W EP2011069042 W EP 2011069042W WO 2012056022 A1 WO2012056022 A1 WO 2012056022A1
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WO
WIPO (PCT)
Prior art keywords
weight
meth
polymer
ester
carbon atoms
Prior art date
Application number
PCT/EP2011/069042
Other languages
English (en)
Inventor
Michael Alibert
Thorsten Bartels
Julien Couet
Alexander Dardin
Daniel H Deneen
Brian Hess
Michael Müller
Christian Daniel Georges Neveu
Gerhard Renner
Torsten Stöhr
Christoph Wincierz
Original Assignee
Evonik Rohmax Additives Gmbh
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 Evonik Rohmax Additives Gmbh filed Critical Evonik Rohmax Additives Gmbh
Priority to EP11776785.5A priority Critical patent/EP2633011A1/fr
Priority to CA2816375A priority patent/CA2816375A1/fr
Priority to BR112013010017A priority patent/BR112013010017A2/pt
Priority to RU2013124369/04A priority patent/RU2013124369A/ru
Priority to MX2013004243A priority patent/MX2013004243A/es
Priority to KR1020137013606A priority patent/KR20140066968A/ko
Priority to SG2013031067A priority patent/SG189514A1/en
Priority to JP2013535456A priority patent/JP2013544328A/ja
Priority to US13/881,263 priority patent/US20130219868A1/en
Priority to CN2011800524181A priority patent/CN103201362A/zh
Publication of WO2012056022A1 publication Critical patent/WO2012056022A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
    • F02M37/04—Feeding by means of driven pumps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10N2030/78—Fuel contamination
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • a diesel motor having improved properties having improved properties
  • the present application relates to a diesel motor having improved properties. Furthermore the present invention describes a use of polymers to improve the low temperature performance of a lubricant comprising biodiesel fuel.
  • biodiesel fuel is in many cases understood to mean a mixture of fatty acid esters, usually fatty acid methyl esters (FAMEs), with chain lengths of the fatty acid fraction of 12 to 24 carbon atoms with 0 to 3 double bonds. The higher the carbon number and the fewer double bonds are present, the higher is the melting point of the FAME.
  • FAMEs fatty acid methyl esters
  • Typical raw materials are vegetable oils (i.e. glycerides) such as rapeseed oils (canola oils), sunflower oils, soya oils, palm oils, coconut oils and, in isolated cases, even used vegetable oils.
  • vegetable oils i.e. glycerides
  • canola oils rapeseed oils
  • sunflower oils soya oils
  • palm oils coconut oils
  • coconut oils rapeseed oils
  • Another typical source for Biodiesel is animal fat.
  • the raw materials are converted to the corresponding FAMEs by transesterification, usually with methanol under basic catalysis.
  • their use is accompanied by a number of deficiencies and limitations which must be addressed if they are to become viable alternatives to mineral oil based diesel.
  • the use of pure biodiesel has been an important target in many countries.
  • many issues, ranging from different combustion characteristic to corrosion of seal materials have been reported as
  • the temperature of the particulate filter could be too low to burn the particulate being filtered by the particulate filter. This problem usually occurs if the vehicle is used on short hauls leading to an accumulation of soot in the particulate filter .
  • a computer monitors one or more sensors that measure back pressure and/or temperature, and based on pre- programmed set points the computer makes decisions on when to activate the regeneration cycle. Running the cycle too often while keeping the back pressure in the exhaust system low will use extra fuel. Not running the regeneration cycle soon enough increases the risk of engine damage and/or uncontrolled regeneration (from an excess of accumulated soot) and possible DPF failure. Quality regeneration software is a necessity for longevity of the active DPF system. In order to regenerate additional fuel can be injected into the engine in order to increase the exhaust gas
  • additives for lubricating oils which provide improved cold start and cold run characteristics of biodiesel motors.
  • the additive should improve the life time and the fuel consumption of biodiesel motors.
  • the additives should be producible in a simple and inexpensive manner, and especially commercially
  • the present invention accordingly provides a motor designed for biodiesel compatibility comprising a particulate filter, a motor control unit being able to inject fuel to the engine in order to increase the exhaust temperature, and a lubricant composition, characterized in that the lubricant composition comprises at least one ester group containing polymer.
  • the motor of the present invention shows an enhanced life time and lowered fuel consumption.
  • the motor of the present invention enables extended oil change intervals.
  • the motor provides significant improvements in economic aspects based on lower amounts of motor oil based on a specific mileage.
  • the motor of the present invention does not need complex design in order to regenerate the particulate filter.
  • the regeneration does not decline the run characteristics of the motor.
  • the solution presented by the present invention is not limited to new motor designs and can be applied to existing biodiesel motors having an appropriate motor control unit being able to inject fuel to the engine in order to increase the exhaust temperature.
  • the motor of the present invention can have a very high compression without being detrimental effected regarding the cold start and cold run characteristics and life time and the fuel consumption of biodiesel motors.
  • the additives used in order to obtain a lubricant being able to solve the problems mentioned above can be prepared in a simple and inexpensive manner, and it is possible to use commercially available components in particular. At the same time, production is possible on the industrial scale, without new plants or plants of complex construction being required for that purpose.
  • the polymers for use in accordance with the invention exhibit a particularly favorable profile of properties. For instance, the polymers can be configured so as to be surprisingly shear-stable, such that the
  • the additive for use in accordance with the invention may bring about a multitude of desirable properties in the lubricant.
  • the present polymers comprising ester groups.
  • ester groups are compatible with many additives. This allows the lubricants to be adjusted to a wide variety of different requirements.
  • the additives for use do not exhibit any adverse effects on fuel consumption or the environmental compatibility of the lubricant.
  • present polymers comprising ester groups improve the low temperature performance of lubricants comprising high amounts of biodiesel.
  • lubricant can be improved by using special embodiments of the inventive polymers.
  • some of the biodiesel fuel comprises high amounts of ethylenically unsaturated bonds being sensitive to oxidation. These oxidation products are merely soluble in the motor oil and may cause significant problems. Particulates and sludge formed in motor oil having no biodiesel content have different properties and, furthermore, motor oil having no biodiesel content generates a lower amount of such
  • impurities are one of the reasons for a motor oil change.
  • the present motor comprises a lower corrosion based on the ability of the present motor oil to neutralize the acids being formed on degeneration of the biodiesel fuel .
  • the present invention provides a new motor designed for biodiesel compatibility. These motors are usually part of biodiesel vehicles.
  • a biodiesel vehicle can usually use a mixture of biodiesel and petroleum based diesel.
  • Preferred biodiesel engines are capable of burning any proportion of the resulting blend in the combustion chamber as fuel injection and spark timing are adjusted automatically according to the actual blend detected by electronic sensors.
  • the biodiesel vehicle comprises a particulate filter.
  • a diesel particulate filter sometimes called a DPF, is a device designed to remove diesel particulate matter or soot from the exhaust gas of a diesel engine. Wall-flow diesel particulate filters usually remove 85% or more of the soot, and can at times (heavily loaded condition) attain soot removal efficiencies of close to 100%.
  • a diesel-powered vehicle equipped with functioning filter will emit no visible smoke from its exhaust pipe.
  • the particulate filter has a porosity in the range from 30% to 60%, more preferably in the range of 40% to 50%.
  • the porosity is the ratio of the pore volume to the total volume of the particulate filter.
  • the particulate filter is made of an inorganic material, such as a silicate, a titanate, especially
  • the particulate filter is a wall-flow filter. More preferably, the particulate filter removes of at least 70 %, especially at least 85% and more preferably at least 95% of the particulate.
  • a cordierite wall flow filter Preferably a cordierite wall flow filter, a silicon carbide wall flow filter, a ceramic fiber filter, a metal fiber flow through filters can be used.
  • the filter can be made of cordierite.
  • Cordierite is a special ceramic material known in the art. Cordierite filters provide excellent filtration efficiency and are inexpensive .
  • the filter can be made of silicon carbide (SiC) .
  • Fibrous ceramic filters are made from several different types of ceramic fibers that are mixed together to form a porous media. Fibrous filters have an advantage over wall flow design of producing lower back pressure.
  • Some cores are made from metal fibers - generally the fibers are "woven" into a monolith. Such cores have the advantage that an electrical current can be passed through the monolith to heat the core for regeneration purposes, allowing the filter to regenerate at low exhaust
  • the particulate filters may have a coating being able to lower the burning temperature of the soot, e.g. Additional information and specifications of the
  • the motor of the present invention may be any motor of the present invention. Furthermore, the motor of the present invention may be any motor of the present invention.
  • the motor comprises a motor control unit being able to inject fuel to the engine in order to increase the exhaust temperature.
  • the motor can be based on a common rail system for injecting the fuel into the combustion chamber.
  • common rail refers to the fact that all of the fuel injectors are supplied by a common fuel rail which is nothing more than a pressure accumulator where the fuel is stored at high pressure.
  • This fuel reservoir is supplied by a high pressure pump providing a high pressure up to and above 2,500 bars.
  • the fuel reservoir provides the fuel to multiple fuel injectors. This simplifies the purpose of the high pressure pump in that it only has to maintain a commanded pressure at a target (either mechanically or electronically controlled) .
  • the fuel injectors are typically ECU-controlled . When the fuel injectors are electrically activated a hydraulic valve (consisting of a nozzle and plunger) is mechanically or hydraulically opened and fuel is sprayed into the cylinders at the desired pressure.
  • the injection pressure at the start and end of injection is very near the pressure in the accumulator (rail), thus producing a square injection rate. If the accumulator, pump, and plumbing are sized properly, the injection pressure and rate will be the same for each of the multiple injection events.
  • the diesel fuel can be injected by multiple injection steps during each burning cycle, such that a pre- injection is made into the cylinder to warm the combustion chamber before delivering the main fuel charge.
  • Astonishing improvements can be achieved with a needle valve operating with a solenoid. Furthermore, piezoelectric injectors could be used for improved motor control.
  • the fuel pressure in the common rail system comprises at least 800 bar, especially at least 1,000 bar, more preferably at least 1,500 bar and most preferably at least 1, 800 bar.
  • the motor of the present invention is designed to fuels comprising at least 5%, especially at least 10%, particularly 20%, more especially at least 50% and more preferably at least 80% by volume of biodiesel, e.g. FAME. Furthermore, the motor of the present invention is
  • fuels comprising at least 5%, especially at least 10%, particularly 20%, more especially at least 50% and more preferably at least 80% by volume of mineral diesel.
  • the motor comprises a compression of at least 12, more preferably at least 16.
  • the compression is preferably at most 26, more preferably at most 23.
  • the motor may comprise a fuel injection pump.
  • the motor of the present invention may
  • the exhaust gas recirculation can preferably be cooled.
  • the motor comprises an engine management for optimization of the fuel injection and the spark timing .
  • the motor can preferably comprise a turbocharger and/or a supercharger.
  • the motor may comprise a variable geometry turbocharger (VGT) .
  • Preferred motor of the present invention meet the
  • the motor of the present invention comprises a lubricant composition including at least one ester group containing polymer .
  • the present invention describes polymers which preferably have a high oil solubility.
  • oil-soluble means that a mixture of a base oil and a polymer comprising ester groups is preparable without macroscopic phase formation, which has at least 0.1% by weight, preferably at least 0.5% by weight, of the polymers.
  • the polymer may be present in dispersed and/or dissolved form in this mixture.
  • the polymer may be added to a fresh oil and/or to an aged oil.
  • the polymer may be added to a biodiesel and be introduced into the lubricant oil by dilution of the oil.
  • the oil solubility depends especially on the proportion of the lipophilic side chains and on the base oil. This property is known to those skilled in the art and can be adjusted readily for the particular base oil via the proportion of lipophilic monomers.
  • polymers which comprise ester groups, preferably polyalkyl (meth) acrylates and preferably have a weight-average molecular weight M w in the range from 2000 to 2 000 000 g/mol, especially from 7500 to 1 000 000 g/mol, more preferably 10 000 to
  • the number-average molecular weight M n may preferably be in the range from 2000 to 1 000 000 g/mol, especially from 5000 to 800 000 g/mol, more preferably 7500 to
  • ester group containing polymer preferably a
  • polyalkyl (meth) acrylate may have a weight-average molecular weight M w in the range from 2000 to 1 000 000 g/mol, especially from 20 000 to 800 000 g/mol, more preferably 40 000 to 500 000 g/mol and most preferably 60 000 to
  • ester group containing polymer preferably a
  • polyalkyl (meth) acrylate may have a number average molecular weight M n in the range from 2 000 to 100 000 g/mol,
  • Polymers having a high molecular weight are especially useful as viscosity index improvers.
  • Polymers having a low molecular weight are especially useful as pour point depressants and flow improvers.
  • the polymers which comprise ester groups preferably exhibit a polydispersity, given by the ratio of the weight average molecular weight to the number average molecular weight Mw/Mn, in the range of 1 to 15, more preferably 1.1 to 10, especially preferably 1.2 to 5.
  • the polydispersity may be determined by gel permeation
  • the polymer comprising ester groups may have a variety of structures.
  • the polymer may be present as a diblock, triblock, multiblock, comb and/or star copolymer which has corresponding polar and nonpolar segments.
  • the polymer may especially be present as a graft copolymer .
  • Polymers comprising ester groups are understood in the context of the present invention to mean polymers
  • ester monomers are known per se. They include especially (meth) acrylates , maleates and fumarates, which may have different alcohol radicals.
  • (meth) acrylates encompasses methacrylates and acrylates, and mixtures of the two. These monomers are widely known. Accordingly, these polymers contain ester groups as part of the side chain.
  • the polymer comprising ester groups can be used singly or as a mixture of polymers having different molecular
  • some of the polymers may have properties of pour point depressants while other polymers are viscosity index improvers.
  • a mixture comprising one or more pour point depressants and one or more viscosity index improvers can be used.
  • the polymer comprising ester groups comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 90% by weight of repeat units derived from ester monomers. According to a preferred embodiment of the present
  • the ester group containing polymer may include polyalkyl (meth) acrylates (PAMAs), polyalkyl fumarates and/or polyalkyl maleates. More preferably, the ester group containing polymer is an alkyl (meth) acrylate polymer.
  • PAMAs polyalkyl (meth) acrylates
  • the ester group containing polymer is an alkyl (meth) acrylate polymer.
  • polyalkyl maleates are known per se. They include
  • (meth) acrylates includes methacrylates and acrylates, and mixtures of the two. These monomers are widely known.
  • the alkyl part may be linear, cyclic or branched.
  • the alkyl part may also have known substituents .
  • the term "repeating unit" is widely known in the technical field.
  • the present polymers comprising ester groups can preferably be obtained by means of free-radical
  • the repeat unit is obtained from the monomers used .
  • the polymers comprising ester groups preferably contain repeating units derived from ester monomers having 7 to 4000 carbon atoms in the alcohol part.
  • the polymer comprises at least 40 % by weight, especially at least 60 % by weight and more preferably at least 80 % by weight of repeating units derived from ester monomers having 7 to 4000 carbon atoms, preferably 7 to 300 carbon atoms and more preferably 7 to 30 carbon atoms in the alcohol part.
  • the polymer comprising ester groups may contain 5 to 100% by weight, especially 20 to 98% by weight and more
  • the polymer comprising ester groups may contain 0 to 90% by weight, preferably 5 to 80% by weight and more preferably 40 to 70% by weight of repeat units derived from ester monomers having 16 to 4000, preferably 16 to 30 carbon atoms in the alcohol part.
  • the polymer may comprise repeating units derived from ester monomers having 23 to 4000 carbon atoms, preferably 23 to 400 carbon atoms and more preferably 23 to 300 carbon atoms in the alcohol part.
  • the polymer comprising ester groups may contain 0.1 to 60% by weight, especially 0.5 to 40% by weight, preferably 1 to 30% by weight and more preferably 2 to 20% by weight, of repeat units derived from ester monomers having 1 to 6 carbon atoms in the alcohol part.
  • ester monomers having 23 to 4000 carbon atoms, preferably 23 to 400 carbon atoms and more preferably 23 to 300 carbon atoms in the alcohol part, and repeating units derived from ester monomers having 1 to 6 carbon atoms in the alcohol part.
  • the polymer comprising ester groups comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and very particularly at least 95% by weight of repeat units derived from ester monomers.
  • Mixtures from which the inventive polymers comprising ester groups are obtainable may contain 0 to 40% by weight, especially 0.1 to 30% by weight and more preferably 0.5 to 20% by weight of one or more ethylenically unsaturated ester compounds of the formula (I)
  • R is hydrogen or methyl
  • R is a linear or
  • R 2 and R 3 are each independently hydrogen or a group of the formula -COOR' in which R' is hydrogen or an alkyl group having 1 to 6 carbon atoms .
  • component (I) include
  • (meth) acrylates , fumarates and maleates which derive from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl
  • cycloalkyl (meth) acrylates such as cyclopentyl
  • compositions to be polymerized preferably contain 0 to 100% by weight, particularly 5 to 98% by weight, especially 20 to 90% by weight and more preferably 30 to 60% by weight of one or more ethylenically unsaturated ester compounds of the formula (II)
  • R is hydrogen or methyl
  • R 4 is a linear or
  • R 5 and R 6 are each independently hydrogen or a group of the formula -COOR' ' in which R" is hydrogen or an alkyl group having 7 to 15 carbon atoms.
  • component (II) examples include:
  • (meth) acrylates , fumarates and maleates which derive from saturated alcohols, such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, 2- Propylheptyl (meth) acrylate, undecyl (meth) acrylate,
  • saturated alcohols such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth)
  • (meth) acrylates which derive from unsaturated alcohols, for example oleyl (meth) acrylate ;
  • cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl
  • preferred monomer compositions comprise 0 to 100% by weight, particularly 0.1 to 90% by weight,
  • R is hydrogen or methyl
  • R is a linear or
  • R 8 and R 9 are each independently hydrogen or a group of the formula - COOR' ' ' in which R' ' ' is hydrogen or an alkyl group having 16 to 4000, preferably 16 to 400 and more preferably 16 to 30 carbon atoms.
  • component (III) examples include (meth) acrylates which derive from saturated alcohols, such as hexadecyl
  • cycloalkyl (meth) acrylates such as 2 , 4 , 5-tri-t-butyl- 3-vinylcyclohexyl (meth) acrylate, 2 , 3 , 4 , 5-tetra- t-butylcyclohexyl (meth) acrylate,
  • the C16-C 000 alkyl (meth) acrylate monomers preferably the C16-C 00 alkyl (meth) acrylate monomers include polyolefin-based macromonomers .
  • the polyolefin-based macromonomers comprise at least one group which is derived from polyolefins.
  • Polyolefins are known in the technical field, and can be obtained by polymerizing alkenes and/or alkadienes which consist of the elements carbon and hydrogen, for example C2-Cio-alkenes such as ethylene, propylene, n-butene, isobutene, norbornene, and/or d-Cio-alkadienes such as butadiene, isoprene, norbornadiene .
  • the polyolefin-based macromonomers comprise preferably at least 70% by weight and more preferably at least 80% by weight and most preferably at least 90% by weight of groups which are derived from alkenes and/or alkadienes, based on the weight of the polyolefin-based macromonomers.
  • the polyolefinic groups may in particular also be present in hydrogenated form.
  • the alkyl (meth) acrylate monomers derived from polyolefin- based macromonomers may comprise further groups. These include small proportions of copolymerizable monomers.
  • These monomers are known per se and include, among other monomers, alkyl (meth) acrylates , styrene monomers,
  • monomers is preferably at most 30% by weight, more
  • polyolefin-based macromonomers may comprise start groups and/or end groups which serve for functionalization or are caused by the preparation of the polyolefin-based
  • the proportion of these start groups and/or end groups is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the polyolefin-based macromonomers.
  • the number-average molecular weight of the polyolefin-based macromonomers is preferably in the range from 500 to 50 000 g/mol, more preferably from 700 to 10 000 g/mol, in
  • the polyolefin-based macromonomers preferably have a low melting point, which is measured by means of Differential Scanning Calorimetry (DSC) .
  • the melting point of the polyolefin-based macromonomers is preferably less than or equal to -10°C, especially preferably less than or equal to -20°C, more preferably less than or equal to -40°C. Most preferably, no DSC melting point can be measured for the repeat units which are derived from the polyolefin-based macromonomers in the polyalkyl (meth) acrylate copolymer.
  • components (II) and (III) can be obtained, for example, by reacting (meth) acrylates , fumarates, maleates and/or the corresponding acids with long-chain fatty alcohols, which generally gives rise to a mixture of esters, for example (meth) acrylates with different long- chain hydrocarbons in the alcohol parts.
  • fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alfol® 610, Alfol® 810, Lial® 125 and Nafol® types (Sasol) ; Alphanol® 79 (ICI); Epal® 610 and Epal® 810 (Afton) ; Linevol® 79, Linevol® 911 and Neodol® 25E (Shell) ; Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals); Kalcol® 2465 (Kao
  • the (meth) acrylates are particularly preferred over the
  • R , R , R , R , R and R of the formulae (I), (II) and (III) in particularly preferred embodiments are each hydrogen.
  • the weight ratio of units derived from ester monomers having 7 to 15 carbon atoms, preferably of the formula (II), to the units derived from ester monomers having 16 to 4000 carbon atoms, preferably of the formula (III), may be within a wide range.
  • monomers having 16 to 4000 carbon atoms in the alcohol part is preferably in the range from 30:1 to 1:30, more
  • the weight ratio of repeat units derived from ester monomers having 7 to 15 carbon atoms in the alcohol part to repeat units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol part is preferably in the range from 4:1 to 1:4, more preferably in the range from 3:1 to 1:3, especially preferably 2.4:1 to 1.1:1.
  • the polymer may contain units derived from comonomers as an optional component. These comonomers include
  • aryl (meth) acrylates like benzyl (meth) acrylate or phenyl (meth) acrylate, where the acryl residue in each case can be unsubstituted or substituted up to four times;
  • (meth) acrylates of halogenated alcohols like 2,3- dibromopropyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 1 , 3-dichloro-2-propyl (meth) acrylate, 2-bromoethyl
  • (meth) acrylate vinyl halides such as, for example, vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; vinyl esters like vinyl acetate; vinyl monomers containing aromatic groups like styrene, substituted styrenes with an alkyl substituent in the side chain, such as -methylstyrene and -ethylstyrene, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes , dichlorostyrenes , tribromostyrenes and tetrabromostyrenes ; vinyl and isoprenyl ethers; maleic acid and maleic acid derivatives such as mono- and diesters of maleic acid, maleic anhydride, methylmaleic anhydride, maleinimide, methylmaleinimide ;
  • Dispersing monomers are understood to mean especially monomers with functional groups, for which it can be assumed that polymers with these functional groups can keep particles, especially soot particles, in solution (cf. R.M. Mortier, S.T. Orszulik (eds.) : “Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2 nd ed. 1997) .
  • These include especially monomers which have boron-, phosphorus-, silicon-, sulfur-, oxygen- and
  • nitrogen-containing groups preference being given to oxygen- and nitrogen-functionalized monomers.
  • R is hydrogen or methyl
  • X is oxygen, sulfur or an amino group of the formula -NH- or -NR a - in which R a is an alkyl radical having 1 to 40 and preferably 1 to 4 carbon
  • R is a radical which comprises 2 to 1000
  • R 11 and R 12 are each independently hydrogen or
  • R is a radical comprising 1 to 100, preferably 1 to 30 and more preferably 1 to 15 carbon atoms, as dispersing monomers.
  • radical comprising 2 to 1000 carbon denotes radicals of organic compounds having 2 to 1000 carbon atoms. Similar definitions apply for corresponding terms. It encompasses aromatic and heteroaromatic groups, and alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups, and also heteroaliphatic groups. The groups mentioned may be branched or unbranched. In addition, these groups may have customary substituents . Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl;
  • cycloalkyl groups for example cyclopentyl and cyclohexyl; aromatic groups such as phenyl or naphthyl; amino groups, hydroxyl groups, ether groups, ester groups and halides.
  • aromatic groups denote radicals of mono- or polycyclic aromatic compounds having preferably 6 to 20 and especially 6 to 12 carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and/or at least two adjacent CH groups have been replaced by S, NH or 0, heteroaromatic groups having 3 to 19 carbon atoms.
  • Aromatic or heteroaromatic groups preferred in accordance with the invention derive from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane,
  • diphenyldimethylmethane bisphenone, diphenyl sulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3, 4-oxadiazole,
  • benzotriazole dibenzofuran, dibenzothiophene, carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1, 3, 5-triazine, 1 , 2 , 4-triazine,
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl , tert- butyl radical, pentyl, 2-methylbutyl , 1 , 1-dimethylpropyl , hexyl, heptyl, octyl, 1 , 1 , 3 , 3-tetramethylbutyl , nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
  • the preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the cyclooctyl group, each of which is optionally substituted with branched or unbranched alkyl groups.
  • the preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl , butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and the dodecanoyl group.
  • the preferred alkoxycarbonyl groups include the
  • the preferred alkoxy groups include alkoxy groups whose hydrocarbon radical is one of the aforementioned preferred alkyl groups.
  • the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the aforementioned preferred cycloalkyl groups.
  • the preferred heteroatoms which are present m the R radical include oxygen, nitrogen, sulfur, boron, silicon and phosphorus, preference being given to oxygen and nitrogen .
  • the R radical comprises at least one, preferably at least two, preferentially at least three, heteroatoms.
  • the R radical m ester compounds of the formula (IV) preferably has at least 2 different heteroatoms.
  • compounds of the formula (IV) may comprise at least one nitrogen atom and at least one oxygen atom.
  • (meth) acrylates aminoalkyl (meth) acrylamides , hydroxyalkyl (meth) acrylates , (meth) acrylates of ether alcohols, heterocyclic (meth) acrylates and/or carbonyl-containing
  • the hydroxyalkyl (meth) acrylates include
  • (meth) acrylate ethoxylated (meth) acrylates , 1-ethoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-ethoxy-2- ethoxy-2-ethoxyethyl (meth) acrylate, esters of
  • heterocyclic (meth) acrylates include
  • diethylphosphatoethyl (meth) acrylate diethylphosphatoethyl (meth) acrylate.
  • the preferred heterocyclic vinyl compounds include
  • N-vinylpyrrolidone 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactarn,
  • the monomers detailed above can be used individually or as a mixture .
  • polymers which comprise ester groups and are obtained using 2- hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, mono-2-methacryloyloxyethyl succinate,
  • ester groups comprise polymers being obtained using N-vinyl-2- pyrrolidine and/or N-vinyl-2-pyrrolidone .
  • the dispersing and non-dispersing monomers can be any dispersing and non-dispersing monomers.
  • the proportion of dispersing repeat units in a statistical polymer is preferably in the range from 0 % by weight to 20% by weight, more preferably in the range from 1% by weight to 15% by weight and most preferably in the range from 2.5% by weight to 10% by weight.
  • the dispersing repeating unit can be selected from dimethylaminopropylmethacrylamide (DMAPMA) and/or dimethylaminoethylmethacrylate (DMAEMA) and the amount of dispersing repeating based on the weight of the polymers comprising ester groups, is preferably in the range from 0.5 % by weight to 10% by weight, more
  • DMAPMA dimethylaminopropylmethacrylamide
  • DMAEMA dimethylaminoethylmethacrylate
  • the dispersing repeating unit can be selected from 2- ( 4-morpholinyl ) ethylmethacrylate (MOEMA) , 2-hydroxyethyl (meth) acrylate (HEMA) and/or
  • HPMA hydroxypropylmethacrylate
  • dispersing repeating based on the weight of the polymers comprising ester groups is preferably in the range from 2 % by weight to 20% by weight, more preferably in the range from 5 % by weight to 10% by weight.
  • the ester group containing polymer may comprise only a low amount of dispersing repeating units. According such aspect, the proportion of the dispersing repeat units is preferably at most 5 %, more preferably at most 2 % and most preferably at most 0.5 %, based on the weight of the polymers comprising ester groups.
  • the lubricant used in the motor may preferably comprise a mixture of polymers and at least one of the polymers comprises a considerable amount of dispersing repeating units and at least one of the polymers comprises a low amount of dispersing repeating units as mentioned above.
  • the ester group containing polymer is a graft copolymer having an non-dispersing alkyl (meth) acrylate polymer as graft base and an dispersing monomer as graft layer.
  • non-dispersing alkyl (meth) acrylate polymer essentially comprises (meth) acrylate monomer units according formulae (I), (II) and (III) as defined above and below.
  • the proportion of dispersing repeat units in a graft or block copolymer, based on the weight of the polymers comprising ester groups, is preferably in the range from 0 % by weight to 20% by weight, more preferably in the range from 1% by weight to 15% by weight and most preferably in the range from 2.5% by weight to 10% by weight.
  • the dispersing monomer preferably is a heterocyclic vinyl compound as mentioned above and below.
  • the ester group containing polymer is an alkyl (meth) acrylate polymer having at least one polar block and at least one hydrophobic block.
  • the polar block comprises at least three units derived from monomers of the formula (IV) and/or from heterocyclic vinyl compounds, which are bonded directly to one another.
  • Preferred polymers comprise at least one hydrophobic block and at least one polar block, said polar block having at least eight repeat units and the proportion by weight of dispersing repeat units in the polar block being at least 30%, based on the weight of the polar block.
  • Preferred inventive polymers may have polar and hydrophobic blocks.
  • the term "block" in this context denotes a section of the polymer.
  • the blocks may have an essentially constant composition composed of one or more monomer units.
  • the blocks may have a gradient, in which case the concentration of different monomer units (repeat units) varies over the segment length.
  • the polar blocks differ from the hydrophobic block via the proportion of dispersing monomers.
  • the hydrophobic blocks may have at most a small proportion of dispersing repeat units (monomer units), whereas the polar block comprise a high proportion of dispersing repeat units (monomer units) .
  • the polar block may preferably comprise at least 8, especially preferably at least 12 and most preferably at least 15 repeat units.
  • the polar block comprise at least 30% by weight, preferably at least 40% by weight, of dispersing repeat units, based on the weight of the polar block.
  • the polar block may also have repeat units which do not have any dispersing effect.
  • the polar block may have a random structure, such that the different repeat units have a random distribution over the segment length.
  • the polar block may have a block structure or a structure in the form of a gradient, such that the non-dispersing repeat units and the dispersing repeat units within the polar block have an inhomogeneous distribution.
  • the hydrophobic block may comprise a small proportion of dispersing repeat units, which is preferably less than 20% by weight, more preferably less than 10% by weight and most preferably less than 5% by weight, based on the weight of the hydrophobic block.
  • the hydrophobic block comprises essentially no dispersing repeat units.
  • the hydrophobic block of the polymer comprising ester groups may have 5 to 100% by weight, especially 20 to 98% by weight, preferably 30 to 95 and most preferably 70 to 92% by weight of repeat units derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical.
  • the hydrophobic block of the polymer comprising ester groups may have 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of repeat units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol radical.
  • the hydrophobic block of the polymer may have 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of repeat units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol radical.
  • the hydrophobic block of the polymer may have 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight of repeat units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol radical.
  • the hydrophobic block of the polymer may have 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight
  • ester groups may have 0 to 40% by weight, preferably 0.1 to 30% by weight and more preferably 0.5 to 20% by weight of repeat units derived from ester monomers having 1 to 6 carbon atoms in the alcohol radical.
  • the hydrophobic block of the polymer comprising ester groups comprises preferably at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 90% by weight of repeat units derived from ester monomers.
  • the length of the hydrophobic and hydrophobic blocks may vary within wide ranges.
  • the hydrophobic block preferably possess a weight-average degree of polymerization of at least 10, especially at least 40.
  • the weight-average degree of polymerization of the hydrophobic block is preferably in the range from 20 to 5000, especially from 50 to 2000.
  • the proportion of dispersing repeat units, based on the weight of the polymers comprising ester groups, is
  • these repeat units preferably form a segment-like structure within the polymer comprising ester groups, such that preferably at least 70% by weight, more preferably at least 80% by weight, based on the total weight of the dispersing repeat units, are part of a polar block.
  • the weight ratio of said hydrophobic block and said polar block is in the range from 100:1 to 1:1, more preferably in the range from 30:1 to 2:1 and most
  • ester group containing polymers from the above-described compositions is known per se.
  • a polymerization initiator and a chain transfer agent are used for this purpose.
  • the usable initiators include the azo initiators widely known in the technical field, such as AIBN and 1 , 1-azobiscyclohexane- carbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate,
  • Suitable chain transfer agents are in particular oil- soluble mercaptans, for example n-dodecyl mercaptan or 2- mercaptoethanol , or else chain transfer agents from the class of the terpenes, for example terpinolene.
  • the ATRP process is known per se. It is assumed that it is a "living" free-radical polymerization, without any
  • a transition metal compound is reacted with a compound which has a transferable atom group. This transfers the transferable atom group to the transition metal compound, which oxidizes the metal. This reaction forms a radical which adds onto ethylenic groups.
  • the transfer of the atom group to the transition metal compound is reversible, so that the atom group is transferred back to the growing polymer chain, which forms a controlled polymerization system.
  • the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled
  • inventive polymers may be obtained, for example, also via RAFT methods. This process is presented in detail, for example, in WO 98/01478 and WO 2004/083169, to which reference is made explicitly for the purposes of disclosure .
  • inventive polymers are obtainable by NMP processes (nitroxide-mediated polymerization) , which are described, inter alia, in US 4581429. These methods are described comprehensively, in particular with further references, inter alia, in K. Maty aszewski, T.P. Davis, Handbook of Radical Polymerization, Wiley
  • the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
  • the polymerization temperature is generally in the range of -20° - 200°C, preferably 0° - 160°C and more preferably 60° - 140°C.
  • the polymerization may be carried out with or without solvent.
  • solvent is to be understood here in a broad sense.
  • the polymerization is preferably carried out in a nonpolar solvent.
  • hydrocarbon solvents for example aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons, for example cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be present in branched form.
  • solvents may be used individually and as a mixture.
  • Particularly preferred solvents are mineral oils, diesel fuels of mineral origin, natural vegetable and animal oils, biodiesel fuels and synthetic oils (e.g.
  • ester oils such as dinonyl adipate
  • mineral oils and mineral diesel fuels.
  • polymers based on ethyl vinyl acetate can be used as an ester group containing polymer.
  • Preferred polymers based on ethyl vinyl acetate are described in EP 0 739 971 Bl, EP 0 721 492 B2 and EP 0 741 181 Bl .
  • Acetate (EVA) based polymers can be used in order to improve the properties of the lubricating oil comprising biodiesel impurities.
  • the first EVA based polymer may comprise ethylene, vinyl acetate and a alkyl ester of a (meth) acrylate, a fumarate and/or a maleate.
  • the alkyl ester preferably contains 6 to 20, more preferably 7 to 12 carbon atoms in the alkyl residue.
  • the diesters are preferred.
  • the first EVA polymer preferably has an ethylene content in the range of 50 to 90 mol% and a vinyl acetate content in the range of 10 to 40 mol%.
  • the amount of alkyl ester being derived from a (meth) acrylate, a fumarate and/or a maleate is preferably in the range of 1 to 20 mol%, more preferably in the range of 2 to 10 mol%.
  • the weight average molecular weight Mw of the first EVA polymer can preferably be situated in the range of 10000 to 50000 g/mol.
  • polydispersity Mw/Mn of the first EVA polymer is preferably in the range of 1.1 to 5, more preferably 1.5 to 3.
  • the second EVA polymer preferably has an ethylene content in the range of 60 to 95 mol% and a vinyl acetate content in the range of 5 to 40 mol%.
  • the weight average molecular weight Mw of the second EVA polymer can preferably be situated in the range of 1000 to 10000 g/mol.
  • the lubricant comprises a mixture of at least two polymers comprising ester groups. More preferably, the lubricant comprises an alkyl (meth) acrylate polymer and a ethylene vinyl acetate polymer as mentioned above and below .
  • the lubricant of the inventive motor preferably comprises an ester group containing polymer and a olefinic polymer which preferably have a viscosity index-improving or thickening effect.
  • Such polyolefins have long been known and are described in the documents mentioned in the prior art.
  • polyolefins include in particular polyolefin
  • OCP ethylene glycol dimethacrylate copolymers
  • HSD hydrogenated styrene/diene copolymers
  • the polyolefin copolymers (OCP) to be used according to the invention are known per se. They are primarily polymers synthesized from ethylene-, propylene-, isoprene-,
  • Systems which have been grafted with small amounts of oxygen- or nitrogen-containing monomers (e.g. from 0.05 to 5% by weight of maleic anhydride) may also be used.
  • the copolymers which contain diene components are generally hydrogenated in order to reduce the oxidation sensitivity and the crosslinking tendency of the viscosity index improvers .
  • the molecular weight Mw is in general from 10 000 to
  • Ethylene/propylene copolymers are particularly useful and terpolymers having the known ternary components, such as ethylidene-norbornene (cf. Macromolecular Reviews, Vol. 10 (1975)) are also possible, but their tendency to crosslink must also be taken into account in the aging process.
  • the distribution may be substantially random, but sequential polymers comprising ethylene blocks can also advantageously be used.
  • the ratio of the monomers ethylene/propylene is variable within certain limits, which can be set to about 75% for ethylene and about 80% for propylene as an upper limit. Owing to its reduced tendency to dissolve in oil, polypropylene is less suitable than ethylene/propylene copolymers.
  • polymers having a predominantly atactic propylene incorporation those having a more pronounced isotactic or syndiotactic propylene
  • HSD hydrogenated styrene/diene copolymers
  • DE 21 56 122 They are in general hydrogenated isoprene/styrene or butadiene/styrene copolymers.
  • the ratio of diene to styrene is preferably in the range from 2:1 to 1:2, particularly preferably about 55:45.
  • the molecular weight Mw is in general from 10 000 to 300 000, preferably between 50 00 and 150 000.
  • the proportion of double bonds after the hydrogenation is not more than 15%, particularly preferably not more than 5%, based on the number of double bonds before the hydrogenation.
  • Hydrogenated styrene/diene copolymers can be commercially obtained under the trade name SHELLVIS ® 50, 150, 200, 250 or 260.
  • the ester group containing polymer is a block copolymer comprising a block of ester group containing units and an olefinic block.
  • the olefinic block is derived from HSD polymers and/or OCP polymers.
  • Block copolymer comprising a block of ester group
  • the lubricant used in the motor of the present invention includes base oil.
  • Preferred base oils include especially mineral oils, synthetic oils and natural oils.
  • Mineral oils are known per se and commercially available. They are generally obtained from mineral oil or crude oil by distillation and/or refining and optionally further purification and finishing processes, the term mineral oil including in particular the higher-boiling fractions of crude or mineral oil. In general, the boiling point of mineral oil is higher than 200°C, preferably higher than 300°C, at 5000 Pa. The production by low-temperature carbonization of shale oil, coking of bituminous coal, distillation of brown coal with exclusion of air, and also hydrogenation of bituminous or brown coal is likewise possible. Accordingly, mineral oils have, depending on their origin, different proportions of aromatic, cyclic, branched and linear hydrocarbons.
  • paraffin-base fraction represents longer-chain or highly branched isoalkanes
  • naphthenic fraction represents cycloalkanes
  • mineral oils depending on their origin and finishing, have different fractions of n-alkanes, isoalkanes having a low degree of branching, known as mono-methyl-branched
  • paraffins and compounds having heteroatoms, in particular 0, N and/or S, to which a degree of polar properties are attributed.
  • the assignment is difficult, since individual alkane molecules may have both long-chain branched groups and cycloalkane radicals, and aromatic parts.
  • the assignment can be effected to DIN 51 378, for example.
  • Polar fractions can also be determined to ASTM D 2007.
  • the proportion of n-alkanes in preferred mineral oils is less than 3% by weight, the fraction of 0-, N- and/or
  • S-containing compounds less than 6% by weight.
  • the fraction of the aromatics and of the mono-methyl-branched paraffins is generally in each case in the range from 0 to 40% by weight.
  • mineral oil comprises mainly naphthenic and paraffin-base alkanes which have generally more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
  • the fraction of these compounds is generally > 60% by weight, preferably > 80% by weight, without any intention that this should impose a restriction.
  • a preferred mineral oil contains 0.5 to 30% by weight of aromatic fractions, 15 to 40% by weight of naphthenic fractions, 35 to 80% by weight of paraffin-base fractions, up to 3% by weight of n-alkanes and 0.05 to 5% by weight of polar compounds, based in each case on the total weight of the mineral oil.
  • n-alkanes having approx. 18 to 31 carbon atoms having approx. 18 to 31 carbon atoms:
  • An improved class of mineral oils results from hydrogen treatment of the mineral oils (hydroisomerization r hydrocracking, hydrotreatment , hydrofinishing) . In the presence of hydrogen, this
  • Dresel eds.: "Lubricants and Lubrication", Wiley-VCH, Weinheim 2001; R.M. Mortier, S.T. Orszulik (eds.) :
  • the mineral oil can be selected from group I, group II and/oder group III oil, wherein group II and group III oil are preferred.
  • Synthetic oils include organic esters, for example diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, among which
  • PAOs polyalphaolefins
  • silicone oils silicone oils
  • perfluoroalkyl ethers preference is given to polyalphaolefins (PAOs), silicone oils and perfluoroalkyl ethers.
  • synthetic base oils originating from gas to liquid (GTL) , coal to liquid (CTL) or biomass to liquid (BTL) processes. They are usually somewhat more expensive than the mineral oils, but have advantages with regard to their performance .
  • Natural oils are animal or vegetable oils, for example neatsfoot oils or jojoba oils.
  • Base oils for lubricant oil formulations are divided into groups according to API (American Petroleum Institute) .
  • Mineral oils are divided into group I (non-hydrogen-treated) and, depending on the degree of saturation, sulfur content and viscosity index, into groups II and III (both hydrogen-treated) .
  • PAOs correspond to group IV. All other base oils are encompassed in group V.
  • lubricant oils may also be used as mixtures and are in many cases commercially available.
  • the concentration of the polymers comprising ester groups in the lubricant oil composition is preferably in the range of 0.01 to 30% by weight, more preferably in the range of 0.1-20% by weight and most preferably in the range of 0.5- 10% by weight, based on the total weight of the composi ⁇ tion .
  • the polymers comprising ester groups can be mixed with the lubricant oil. Furthermore, the polymers can be prepared in the lubricant oils as mentioned above. In addition thereto, the polymers comprising ester groups can be used as a concentrate or as component of an additive package. The polymer comprising ester groups may be added to a fresh oil and/or to an aged oil. Furthermore, polymer comprising ester groups can be added directly in the engine oil or indirectly through dilution effect using a diesel mixture comprising these polymers.
  • the lubricant oil in addition to the polymers comprising ester groups for use in accordance with the invention, the lubricant oil
  • compositions detailed here may also comprise further additives.
  • additives include viscosity index
  • the additionally usable VI improvers include
  • styrene-maleate copolymers hydrogenated styrene-diene copolymers (HSD) and olefin copolymers (OCP) .
  • Appropriate dispersants include poly ( isobutylene ) deri- vatives, e.g. poly ( isobutylene ) succinimides (PIBSIs);
  • the preferred detergents include metal-containing
  • these compounds for example phenoxides; salicylates; thio- phosphonates , especially thiopyrophosphonates, thio- phosphonates and phosphonates ; sulfonates and carbonates.
  • these compounds may comprise especially calcium, magnesium and barium.
  • defoamers which are in many cases divided into silicone-containing and silicone-free defoamers.
  • the silicone-containing defoamers include linear poly (dimethylsiloxane) and cyclic
  • silicone-free defoamers which may be used are in many cases polyethers, for example poly ( ethylene glycol) or tributyl phosphate.
  • inventive lubricant oil compositions may comprise corrosion inhibitors. These are in many cases divided into antirust additives and metal passivators/deactivators .
  • the antirust additives used may, inter alia, be sulfonates, for example petroleumsulfonates or (in many cases overbased) synthetic
  • alkylbenzenesulfonates e.g. dinonylnaphthenesulfonates ; carboxylic acid derivatives, for example lanolin (wool fat) , oxidized paraffins, zinc naphthenates , alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine- neutralized mono- and dialkyl phosphates; morpholine, dicyclohexylamine or diethanolamine.
  • carboxylic acid derivatives for example lanolin (wool fat) , oxidized paraffins, zinc naphthenates , alkylated succinic acids, 4-nonylphenoxy-acetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); amine- neutralized mono- and dialkyl phosphates; morpholine, dicyclohexylamine
  • passivators/deactivators include benzotriazole,
  • tolyltriazole 2-mercaptobenzothiazole, dialkyl- 2, 5-dimercapto-l , 3, 4-thiadiazole ;
  • a further preferred group of additives is that of
  • antioxidants include, for example, phenols, for example 2 , 6-di-tert-butylphenol (2,6-DTB), butylated hydroxytoluene (BHT) , 2 , 6-di-tert-butyl- 4-methylphenol , 4,4' -methylenebis ( 2 , 6-di-tert-butylphenol ) ; aromatic amines, especially alkylated diphenylamines ,
  • N-phenyl-l-naphthylamine (PNA) polymeric
  • TMQ 4-trimethyldihydroquinone
  • organosulfur compounds for example dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates,
  • thioglycols, thioaldehydes sulfur-containing carboxylic acids; heterocyclic sulfur/nitrogen compounds, especially dialkyldimercaptothiadiazoles , 2-mercaptobenzimidazoles ; zinc and methylene bis (dialkyldithiocarbamate) ; organophos- phorus compounds, for example triaryl and trialkyl
  • phosphites organocopper compounds and overbased calcium- and magnesium-based phenolates and salicylates.
  • the preferred antiwear (AW) and extreme pressure (EP) additives include phosphorus compounds, for example
  • trialkyl phosphates triaryl phosphates, e.g. tricresyl phosphate, amine-neutralized mono- and dialkyl phosphates, ethoxylated mono- and dialkyl phosphates, phosphites, phosphonates , phosphines; compounds containing sulfur and phosphorus, for example metal dithiophosphates , e.g. zinc C3-i 2 dialkyldithiophosphates (ZnDTPs), ammonium
  • ZnDTPs zinc C3-i 2 dialkyldithiophosphates
  • dialkyldithiophosphates antimony dialkyldithiophosphates , molybdenum dialkyldithiophosphates, lead
  • dithiocarbamate sulfur compounds containing elemental sulfur and 3 ⁇ 4S-sulfurized hydrocarbons (diisobutylene, terpene) ; sulfurized glycerides and fatty acid esters;
  • overbased sulfonates chlorine compounds or solids such as graphite or molybdenum disulfide.
  • the antiwear additive and/or extreme pressure additive is selected from phosphorous compounds, compounds comprising sulfur and phosphorous, compounds comprising sulfur and nitrogen, sulfur compounds comprising elemental sulfur and 3 ⁇ 4S-sulfurized hydrocarbons,
  • sulfurized glycerides and fatty acid esters overbased sulfonates, chlorine compounds, graphite or molybdenum disulfide .
  • a further preferred group of additives is that of friction modifiers.
  • the friction modifiers used may include
  • mechanically active compounds for example molybdenum disulfide, graphite (including fluorinated graphite), poly ( trifluoroethylene) , polyamide, polyimide; compounds which form adsorption layers, for example long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds which form layers through tribochemical reactions, for example saturated fatty acids, phosphoric acid and thiophosphoric esters, xanthogenates , sulfurized fatty acids; compounds which form polymer-like layers, for example ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates , unsaturated fatty acids, sulfurized olefins or organometallic
  • molybdenum compounds for example molybdenum compounds (molybdenum dithiophosphates and molybdenum dithiocarbamates MoDTC) and their combinations with ZnDTPs, copper-containing organic compounds .
  • ZnDTP is primarily an antiwear additive and extreme pressure additive, but also has the character of an antioxidant and corrosion inhibitor (here: metal passivator/deactivator ) .
  • Preferred lubricant oil compositions have a viscosity, measured at 40°C to ASTM D 445, in the range of 10 to
  • the kinematic viscosity KVioo measured at 100°C is
  • preferred lubricant oil compositions have a viscosity index
  • lubricant compositions for the use in the motor of the present invention may preferably comprise a High Temperature High Shear (HTHS) viscosity of at least 2.4 mPas, more preferably at least 2.6 mPas as measured at 150°C according to ASTM D4683.
  • HTHS High Temperature High Shear
  • HTHS High Temperature High Shear
  • HTHSioo High Temperature High Shear
  • HTHSiso High Temperature High Shear
  • HTHSioo/HTHSi5o preferably comprises at most at most 2.0 mPas, especially at most 1.9 mPas .
  • High Temperature High Shear (HTHS) viscosity can be determined according to D4683.
  • the lubricant useful as component of the present motor may comprises a high shear stability index (SSI) .
  • SSI shear stability index
  • the shear stability index (SSI) as measured according to ASTM D2603 Ref. B (12.5 minutes sonic treatment) could preferably amount to 35 or less, more preferably to 20 or less.
  • lubricants comprising a shear stability index (SSI) as measured according to DIN 51381 (30 cycles Bosch-pump) of at most 5, especially at most 2 and more preferably at most 1 could be used.
  • the lubricant useful for the present invention can be any suitable lubricant useful for the present invention.
  • the lubricant of the present invention may contain at least about 1 %, especially at least 5 %, particularly at least 10 %, more particularly at least 20 % by volume of biodiesel. Astonishingly, such high amounts of water do not impart unduly high lowering of the motor characteristics such as life time, cold run performance and fuel consumption. Astonishingly, the fuel dilution of the motor oil does only have an acceptable influence on properties such as
  • the additives do have a high compatibility with the biodiesel fuel impurities in the motor oils, such that the efficiency of these additives is not unduly declined. Furthermore, particulates and sludge formed by the biodiesel fuel can be dispersed in the lubricant in an astonishing manner, especially if polymers having dispersing groups are used.
  • canola oil methyl ester RME
  • canola oil methyl ester PME
  • PME palm oil methyl ester
  • yield stress (recorded in pascals); the target value for yield stress is "zero" pascals, although any value less than 35 pascals (limit of sensitivity of equipment) is recorded as "zero" yield stress. Yield stress values greater than 35 pascals signify increasing degrees of less desirable performance.
  • Aged samples could be either prepared by following the test method procedure as reported by the CEC (Coordinating European Council), or by GFC (Groupement Francais de Coordination) method A or B, or by ROBO (Romaszewski Oil Bench Oxidation) Test or by standard oxidation tests for engine oils.
  • Fresh motor oil has been used over a long period of time in a diesel motor.
  • the content of biodiesel in this aged motor oil had been determined to at least 5.5 % by weight
  • the aged motor oil has been modified by adding 0.1 % by weight of a pour point depressant being based on a polyalkyl
  • (meth) acrylate composition comprising about 67.8 % by weight LMA, 32.0% by weight SMA and 0.2 % by weight DPMA example 1 ) .
  • LMA lauryl-myristyl methacrylate
  • DPMA dodecyl-pentadecyl methacrylate
  • SMA cetyl-stearyl methacrylate
  • the polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG under the trademark VISCOPLEX ® .
  • (meth) acrylate improves the cold start performance of an aged oil to the features of a fresh oil.
  • the aged oil is within the specification of a SAE J300 5W-30 oil. Comparative Examples 2 and 3
  • a commercially available 15W-40 motor oil has been oxidized according to a modified GFC specification at 170°C for 72 h on a larger volume.
  • a mixture of 10 % by weight of biodiesel (B100, rapeseed oil methyl ester) and 90 % by weight of the same SAE 15W-40 motor oil has been prepared and oxidized in the same manner.
  • the low temperature performance has been evaluated using MRV-TPl measurements according to ASTM D-4684-08 at a temperature of -25°C.
  • Oil mixtures comprising about 90 % by weight of a
  • An oil mixture comprising about 90 % by weight of a commercially available 15W-40 motor oil, about 10 % by weight of biodiesel (B100) as mentioned in Comparative
  • Example 3 has been treated with 0.3 % by weight of a pour point depressant being based on a polyalkyl (meth) acrylate composition comprising about 57.5 % by weight LMA and
  • the pour point depressant being based on a polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG.
  • SAE 15W-40 motor oil mixture comprising about 85.8 % by weight of a base oil mixture, 8.7 % by weight of a DI- package and 5.5 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point.
  • This composition comprises about 82.6 % by weight IDMA, about 5.2 % by weight MMA, about 5.6 % by weight SMA, about
  • IDMA isodecyl methacrylate
  • MMA is methyl methacrylate and NVP is N-vinyl-2- pyrrolidone .
  • the polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG.
  • the oil mixture comprising 5.5 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point as mentioned above has been treated with
  • the oil mixtures have been oxidized according to the modified GFC specification at 170°C for 72 h.
  • the amount of biodiesel given in % by weight given in % by weight and the results achieved are mentioned in table 4.
  • Viscosity Viscosity B100 wt.% stress stress
  • the oil mixture comprising 5.5 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point as mentioned above has been treated with
  • Examples 14 to 22 An SAE 5W-30 motor oil mixture comprising about 83.4 % by weight of a base oil mixture, 13.3 % by weight of a DI- package and 3.3 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point.
  • This composition comprises about 82.6 % by weight IDMA, about 5.2 % by weight MMA, about 5.6 % by weight SMA, about 3.8 % by weight NVP and about 2.73 % by weight LMA.
  • the polyalkyl (meth) acrylate composition improving
  • viscosity index and pour point comprises about 3.7 % by weight of the pour point depressant and 96.3 % by weight of the VI improver.
  • the polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG.
  • the oil mixture comprising 3.3 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point as mentioned above has been treated with
  • the oil mixtures have been oxidized according to the modified GFC specification at 170°C for 72 h.
  • the amount of biodiesel given in % by weight given in % by weight and the results achieved are mentioned in table 6.
  • the oil mixture comprising 3.3 % by weight of a polyalkyl (meth) acrylate composition improving viscosity index and pour point as mentioned above has been treated with
  • ester group containing polymers especially polyalkyl (meth) acrylate compositions improving viscosity index and pour point, retain the cold start performance of oils.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur un moteur conçu pour une compatibilité avec le biodiesel, lequel moteur comprend un filtre à particules, une unité de commande de moteur apte à injecter du carburant dans le moteur de façon à augmenter la température des gaz d'échappement, et une composition lubrifiante, caractérisé en ce que la composition lubrifiante comprend au moins un groupe ester contenant un polymère.
PCT/EP2011/069042 2010-10-29 2011-10-28 Moteur diesel ayant des propriétés améliorées WO2012056022A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP11776785.5A EP2633011A1 (fr) 2010-10-29 2011-10-28 Moteur diesel ayant des propriétés améliorées
CA2816375A CA2816375A1 (fr) 2010-10-29 2011-10-28 Moteur diesel ayant des proprietes ameliorees
BR112013010017A BR112013010017A2 (pt) 2010-10-29 2011-10-28 motor a diesel tendo propriedades aprimoradas
RU2013124369/04A RU2013124369A (ru) 2010-10-29 2011-10-28 Дизельный двигатель, обладающий улучшенными свойствами
MX2013004243A MX2013004243A (es) 2010-10-29 2011-10-28 Un motor diesel que tiene propiedades mejoradas.
KR1020137013606A KR20140066968A (ko) 2010-10-29 2011-10-28 개선된 특성을 갖는 디젤 모터
SG2013031067A SG189514A1 (en) 2010-10-29 2011-10-28 A diesel motor having improved properties
JP2013535456A JP2013544328A (ja) 2010-10-29 2011-10-28 改良された特性を有するディーゼル発動機
US13/881,263 US20130219868A1 (en) 2010-10-29 2011-10-28 Diesel motor having improved properties
CN2011800524181A CN103201362A (zh) 2010-10-29 2011-10-28 具有改进的性能的柴油发动机

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CN (1) CN103201362A (fr)
BR (1) BR112013010017A2 (fr)
CA (1) CA2816375A1 (fr)
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EP3778839B1 (fr) * 2019-08-13 2021-08-04 Evonik Operations GmbH Agent améliorant l'indice de viscosité présentant une meilleure résistance au cisaillement
CN111763555A (zh) * 2020-07-22 2020-10-13 南宁广壮润滑油有限公司 一种耐高温且低温流动性能优异的柴油机油制备方法
EP4060009B1 (fr) * 2021-03-19 2023-05-03 Evonik Operations GmbH Un agent améliorant l'indice de viscosité et composition lubrifiante
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JP2023151684A (ja) * 2022-03-31 2023-10-16 出光興産株式会社 組成物、潤滑油組成物、及びグリース組成物

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EP2633011A1 (fr) 2013-09-04
BR112013010017A2 (pt) 2016-08-02
MX2013004243A (es) 2013-06-03
JP2013544328A (ja) 2013-12-12
SG189514A1 (en) 2013-05-31
CN103201362A (zh) 2013-07-10
KR20140066968A (ko) 2014-06-03
RU2013124369A (ru) 2014-12-10
CA2816375A1 (fr) 2012-05-03
US20130219868A1 (en) 2013-08-29

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