JP2013544328A - Diesel engine with improved characteristics - Google Patents

Abstract

  The present invention is a motor designed for biodiesel compatibility, comprising a particulate filter, a motor control unit capable of raising the exhaust temperature by injecting fuel into the engine, and a lubricant composition. The motor is characterized in that the lubricant composition contains a polymer having at least one ester group.

Description

  The present application relates to diesel engines having improved characteristics. The present invention further describes the use of polymers to improve the low temperature performance of lubricants including biodiesel fuel.

  Today, fuel is mostly obtained from fossil sources. However, these resources are limited and therefore alternatives are sought. Accordingly, there is a growing interest in renewable raw materials that can be used to produce fuel. A very interesting alternative is in particular biodiesel fuel.

  The term biodiesel often means a mixture of fatty acid esters, usually fatty acid methyl esters (FAME), having a chain length of 12 to 24 carbon atoms with 0 to 3 double bonds. Then it is understood. The higher the carbon number, as well as the fewer double bonds present, the higher the melting point of FAME. Typical raw materials are vegetable oils (ie glycerides), such as rapeseed oil (canola oil), sunflower oil, soybean oil, palm oil, coconut oil, and in rare cases used vegetable oil. Another typical source of biodiesel is animal fat. The raw material is usually converted to the corresponding FAME by transesterification with methanol under a basic catalyst. However, its use entails a number of deficiencies and limitations that must be addressed in order to make them a viable alternative to mineral oil based diesel.

  In many countries, the use of pure biodiesel is an important goal in view of the degradation of environmental quality and global crude oil reserves. However, many problems ranging from various combustion properties to corrosion of sealing materials have been reported as obstacles to using biodiesel as an alternative to fossil diesel. Another critical challenge is the regeneration of the diesel particulate removal filter. Regeneration is the process of removing accumulated soot from the filter. If the temperature of the particulate filter becomes too low due to the use of an automobile, the particulates captured by the particulate filter will not be able to burn. This problem usually occurs when an automobile is used at a short distance, and causes accumulation of soot in the particulate filter.

  Typically, a computer monitors one or more sensors that measure back pressure and / or temperature and makes a decision when to activate a regeneration cycle based on preprogrammed settings. If the cycle is run too often while keeping the back pressure in the exhaust system low, excess fuel will be used. Failure to perform the regeneration cycle immediately increases the risk of engine damage and / or loss of regeneration control and possibly DPF failure (if the accumulated soot is excessive). For the long life of an effective DPF system, quality reproduction software is required.

  It can be regenerated by injecting additional fuel into the engine to increase the exhaust gas temperature. Such type of regeneration does not require technical effort and is therefore relatively inexpensive.

  However, such a cycle can lead to oil dilution. On the other hand, it is also possible to use a vaporizer. However, such devices are expensive and can cause failures. Therefore, most vehicles include a motor control unit that can inject fuel into the engine to raise the exhaust gas temperature.

  The problems mentioned above depend on the type of passenger car used. The use of a car in a very short cycle creates a very serious problem that causes the replacement of the lubricant in a short period of time. Moreover, the problem is more acute in engines with high performance exhaust control systems and additional technical approaches for fuel saving. The higher the performance of the engine, the more likely it is to be affected by lubricant degradation based on excessive biodiesel content and the like.

  Lubricant degradation, particularly high biodiesel content and poor low temperature performance, has a detrimental effect on various properties of the engine. These are particularly acute for engines with biodiesel compatibility. Insufficient cold performance can usually cause problems related to characteristics such as cold start and cold run of the engine. In addition, motor life and fuel consumption are adversely affected by the poor low temperature performance of the lubricant.

  To date, many attempts have been made to improve the characteristics of the engine, such as cold start and cold running, through engineering technology and new equipment. However, these additional features suffer from the high cost and usually that only the latest cars can benefit from such improvements. Thus, further opportunities to improve characteristics such as cold start and cold run of the engine, lifetime, and fuel consumption would be useful.

  Therefore, in view of the prior art, the object of the present invention is to provide a solution that can be applied to existing biodiesel engines as well, not limited to new engine designs. In particular, the characteristics of biodiesel engines such as cold start and cold running should be improved. Furthermore, a further object of the present invention is an improvement in lifetime and fuel consumption. This improvement should be achieved without burdening the environment.

  A further object of the present invention is to provide an additive for lubricating oils that improves the properties of biodiesel engines such as cold start and cold running. In addition, the additive should improve the life and fuel consumption of the biodiesel engine.

  Moreover, the additive should be manufacturable in a simple and inexpensive way, in particular commercially available components should be used. In this context, they should be manufacturable on an industrial scale without the use of new plants or complex structures required for this purpose.

  It is a further object of the present invention to provide additives that produce a number of desirable properties in lubricants. Thereby, the kind of additive can be minimized.

  Moreover, the additive should not show any adverse effects on fuel consumption or the environmental compatibility of the lubricant.

  Furthermore, the additive should improve the properties of lubricating oils that contain large amounts of biodiesel.

  These objectives as well as further objectives that are not explicitly stated but can be readily derived or inferred from the relevance described herein in an introductory manner are achieved by a motor having all the features of claim 1. Is done. Appropriate modifications to the inventive mover are protected in the claims referring to claim 1.

  Accordingly, the present invention is a motor designed for biodiesel compatibility having a particulate filter, a motor control unit that can inject fuel into the engine to raise the exhaust temperature, and a lubricant composition. Thus, the present invention provides a motor, wherein the lubricant composition includes a polymer having at least one ester group.

  Thus, it is possible to provide a motor designed for biodiesel compatibility with characteristics such as improved cold start and cold running in an unexpected manner. In addition, the engine of the present invention exhibits long life and reduced fuel consumption.

  In addition, the engine of the present invention can increase the interval between oil changes. Therefore, the engine runs on a specific distance with a smaller amount of motor oil, greatly improving the economy.

  The engine of the present invention does not require a complicated design to regenerate the particulate filter. In addition, the regeneration does not degrade the running characteristics of the engine.

  Furthermore, the solution presented by the present invention is not limited to new engine designs, but to existing biodiesel engines that have a suitable engine control unit that can inject fuel into the engine to increase the exhaust temperature. Can also be applied.

  Moreover, the engine of the present invention can have a very high compression without adversely affecting the characteristics, life and fuel consumption of the biodiesel engine, such as cold start and cold travel.

  Moreover, the additives used to obtain a lubricant that can solve the problems mentioned above can be produced in a simple and inexpensive way, in particular using commercially available components. it can. At the same time, production on an industrial scale is possible without the need for a new plant or the complex structure required for this purpose.

  Moreover, the polymers for use according to the invention exhibit a particularly preferred property profile. For example, the polymer can be configured to be surprisingly shear stable so that the lubricant has a very long service life. Furthermore, additives for use according to the present invention can produce a number of desirable properties in lubricants. For example, it is possible to produce a lubricant having very good low temperature or viscosity characteristics, including the present polymer having ester groups. Thereby, the kind of additive can be minimized. Moreover, the present polymers having ester groups are compatible with many additives. This makes it possible to adapt the additive to various requirements.

  Moreover, the use of the additive does not show any adverse effects on fuel consumption or the environmental compatibility of the lubricant.

  Surprisingly, the present polymer with ester groups improves the low temperature performance of lubricating oils containing large amounts of biodiesel.

  In addition, the dispersing ability of the lubricant can be improved by using certain embodiments of the polymers of the present invention. When considering these aspects, some biodiesel fuels have large amounts of ethylenically unsaturated bonds that are susceptible to oxidation. These oxidation products are only soluble in motor oils, but can cause serious problems. The fine particles and sludge formed in the motor oil not containing biodiesel have various characteristics, and the motor oil not containing biodiesel is less likely to generate such impurities. These impurities are one reason for replacing motor oil.

  In addition, the motor has a lower corrosivity based on the motor oil's ability to neutralize the acid formed in biodiesel degradation.

  The present invention provides a novel engine designed for biodiesel compatibility. These engines are usually part of a biodiesel vehicle.

  Biodiesel vehicles can typically use a mixture of biodiesel and petroleum-based diesel. In the preferred biodiesel engine, fuel injection and spark timing are automatically adjusted according to the actual blend sensed by the electronic sensor, so that any resulting proportion of the blend can be burned in the combustion chamber.

  Biodiesel vehicles are equipped with a particulate filter. A diesel particulate filter, sometimes called a DPF, is a device designed to remove diesel particulate or soot from diesel engine exhaust. Wall flow diesel particulate filters usually remove more than 85% of soot and sometimes (high load conditions) can achieve soot removal efficiency close to 100%. No visible smoke will be emitted from the exhaust pipe of the diesel vehicle where the filter is functioning.

  Preferably, the particulate filter has a porosity of 30% to 60%, more preferably 40% to 50%. The porosity is the ratio of the pore volume to the total volume of the particulate filter.

Preferably, the particulate filter is made of an inorganic material such as silicate, titanate, especially tialite (Al ₂ TiO ₅ ), carbide, ceramic, or metallic material.

  According to a preferred embodiment, the particulate filter is a wall flow filter. More preferably, the particulate filter removes at least 70%, especially at least 85%, more preferably at least 95% of the particulates.

  Preferably, a cordierite wall flow type filter, a silicon carbide wall flow type filter, a ceramic fiber filter, and a metal fiber flow through type filter can be used.

  Preferably, the filter can be made of cordierite. Cordierite is a special ceramic material known in the art. Cordierite filters have high filtration efficiency and are inexpensive.

  According to a further aspect, the filter can be made of silicon carbide (SiC).

  Fibrous ceramic filters are made from various types of ceramic fibers mixed together to form a porous body. Fibrous filters have advantages over wall flow designs that produce lower back pressure.

  Some cores are made from metal fibers and generally the fibers are “woven” into the monolith. Such a core has the advantage that, for regeneration, current can be passed through the monolith to heat the core, thereby allowing the filter to be regenerated at low exhaust temperatures and / or low exhaust flow rates. Have

  The particulate filter may have, for example, a coating that can lower the combustion temperature of soot.

  Additional information and specifications for the particulate filter can be found in Engineer Bench and Vehicle Durability Test of Si bonded SiC Particulate Filters: A. Schaefer-Sindlinger et al. . SAE 2004-01-0952. The disclosure of this document is incorporated herein by reference.

Furthermore, movers of the present invention may comprise a catalyst for removing NO _x and other harmful components of exhaust gases.

  In addition, the engine includes an engine control unit that can inject fuel into the engine to raise the exhaust gas temperature.

  According to a highly preferred embodiment, the engine can be based on a common rail system for injecting fuel into the combustion chamber.

  The term “common rail” refers to the fact that all fuel injectors are supplied by a common fuel rail which is only a pressure accumulator where the fuel is stored at high pressure. This fuel storage container is supplied by a high-pressure pump that provides high pressures up to 2,500 bar. The fuel storage container supplies fuel to a plurality of fuel injection devices. This simplifies the purpose of the high-pressure pump so that the commanded pressure need only be maintained at the target value (mechanically or electronically controlled). The fuel injection device is typically ECU-controlled. When the fuel injector is electrically actuated, a hydraulic valve (consisting of a nozzle and a plunger) is opened mechanically or hydraulically, and fuel is sprayed into the cylinder at the desired pressure. Since the fuel pressure energy is held remotely and the injector is operated electrically, the injection pressure at the start and end of the injection is very close to the accumulator (rail) pressure and therefore sufficient injection Rate occurs. If the accumulator, pump, and piping are appropriately sized, the injection pressure and injection rate will be the same for each of the multiple injections.

  Preferably, the diesel fuel can be pre-injected into the cylinder to warm the combustion chamber and then injected by multiple injection steps during each combustion cycle so that the main fuel charge is made.

  A surprising improvement can be achieved with a needle valve actuated by a solenoid. Moreover, the piezoelectric injector could be used for improved motor control.

  Preferably, the fuel pressure in the common rail system is at least 800 bar, in particular at least 1,000 bar, more preferably at least 1,500 bar, most preferably at least 1,800 bar.

  Technically, biodiesel engines can run on any mixture of petroleum-based diesel and biodiesel (from pure gasoline to 100% biodiesel (B100)), but in North America and Europe Biodiesel vehicles are optimized to run on a maximum blend of 80% mineral diesel and 20% biodiesel (referred to as B20 fuel). This limit on biodiesel content is set to avoid cold start problems during cold periods below 11 ° C. (52 ° F.).

  Preferably, the engine according to the invention comprises a fuel comprising at least 5% by volume, in particular at least 10% by volume, in particular 20% by volume, more especially at least 50% by volume, more preferably at least 80% by volume of biodiesel, such as FAME. Designed against. Furthermore, the motor of the present invention is preferably based on a fuel comprising at least 5% by volume, in particular at least 10% by volume, in particular 20% by volume, more especially at least 50% by volume, more preferably at least 80% by volume of mineral diesel. Designed.

  Preferably, the mover has at least 12, more preferably at least 16 compressions. According to a preferred embodiment, the compression is preferably at most 26, more preferably at most 23.

  In accordance with certain aspects of the present invention, the engine may include a fuel injection pump.

  Unexpected benefits can be achieved with engines with multi-valve technology.

  Moreover, the engine of the present invention can be provided with exhaust gas recirculation. The exhaust gas recirculation can preferably be cooled.

  Preferably, the engine includes engine management for fuel injection and spark timing optimization.

  Furthermore, the engine may preferably comprise a turbocharger and / or a supercharger. According to a preferred embodiment of the present invention, the engine may comprise a variable capacity turbocharger (VGT).

  A preferred engine of the present invention is a command No. It meets the requirements of Euro 5, more preferably Euro 6, which is an exhaust emission standard as defined in 715/2007 / EC. The mover may also meet other requirements to comply with national or local standards such as TIER II in the United States.

  Additional information and specifications of the specific components referred to above of the diesel engine of the present invention can be found in Handbuch Dieselmotoren: Mollenhauer, Tshoeke; Springer Verlag; 2007 and Oto-und Dieselmotoren: Grohe, Vs; Is mentioned. The disclosure of this document is incorporated herein by reference.

  The engine of the present invention has a lubricant composition comprising a polymer having at least one ester group.

  The present invention describes polymers that preferably have high oil solubility. The term “oil-soluble” means that a mixture of a base oil and a polymer having ester groups can be produced without forming a macrophase, which is at least 0.1% by weight, preferably at least 0%. .5% by weight of polymer. The polymer may be present in the mixture in a dispersed and / or dissolved state. The polymer can be added to virgin oil and / or aging oil. Moreover, the polymer may be added to biodiesel or diluted with oil and introduced into the lubricating oil. Oil solubility depends inter alia on the proportion of lipophilic side chains and base oil. This property is known to those skilled in the art and can be easily adjusted for a particular base oil by the proportion of lipophilic monomer.

Among them, a polymer having an ester group, preferably a polyalkyl (meth) acrylate, preferably 2000 to 2,000,000 g / mol, particularly 7500 to 1,000,000 g / mol, more preferably 10 Of particular interest are polymers having a weight average molecular weight M _{w of} from 5,000 to 600,000 g / mol, most preferably from 15,000 to 80,000 g / mol.

The number average molecular weight _Mn is preferably 2000 to 1,000,000 g / mol, especially 5000 to 800,000 g / mol, more preferably 7500 to 500,000 g / mol, most preferably 10,000 to 80,000 g. / Mol.

According to a particular embodiment of the present invention, the polymer having an ester group, preferably a polyalkyl (meth) acrylate, is 2000 to 1,000,000 g / mol, especially 20,000 to 800,000 g / mol, more preferably 40 May have a weight average molecular weight _{Mw of} from 50,000 to 500,000 g / mol, most preferably from 60,000 to 250,000 g / mol.

According to a further aspect of the invention, the polymer having an ester group, preferably a polyalkyl (meth) acrylate, is 2,000-100,000 g / mol, especially 4,000-60,000 g / mol, most preferably 5,000. It may have a number average molecular weight M _n of ˜30,000 g / mol.

  High molecular weight polymers are particularly useful as viscosity index improvers. Low molecular weight polymers are particularly useful as pour point depressants and flow improvers.

Although no limitation is intended by the following description, the polymer having an ester group is preferably a number average molecular weight of 1-15, more preferably 1.1-10, particularly preferably 1.2-5. The polydispersity given by the ratio M _w / M _n of the mass average molecular weight to The polydispersity can be specified by gel permeation chromatography (GPC).

  The polymer having the ester group may have various structures. For example, the polymer can exist as a diblock, triblock, multiblock, comb, and / or star copolymer with corresponding polar and nonpolar segments. In addition, the polymer can exist in particular as a graft copolymer.

  In the context of the present invention, a polymer having an ester group is a polymer obtained by polymerizing a monomer composition comprising an ethylenically unsaturated compound having at least one ester group (hereinafter referred to as an ester monomer). Is understood to mean. Ester monomers are known per se. These monomers include (meth) acrylates, maleates, and fumarate, among others, which can have different alcohol groups. The expression “(meth) acrylate” includes methacrylates and acrylates, and mixtures of the two. These monomers are widely known.

  Thus, these polymers have ester groups as part of the side chain.

  The polymers having ester groups can be used alone or as a mixture of polymers having, for example, different molecular weights, different compositions in repeating units, and / or different ester group-containing monomers. For example, some of the polymers may have pour point depressant properties while other polymers are viscosity index improvers. Preferably, a mixture containing one or more pour point depressants and one or more viscosity index improvers can be used.

  The polymer having ester groups preferably comprises at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight and most preferably at least 90% by weight of repeating units derived from ester monomers.

  According to a preferred embodiment of the present invention, the polymer having an ester group may comprise polyalkyl (meth) acrylate (PAMA), polyalkyl fumarate, and / or polyalkyl maleate. More preferably, the polymer having an ester group is an alkyl (meth) acrylate polymer.

  Ester monomers for the production of polyalkyl (meth) acrylates (PAMA), polyalkyl fumarate and / or polyalkyl maleates are known per se. They include, among others, (meth) acrylates, maleates, and fumarate, which can have different alcohol moieties. The expression “(meth) acrylate” includes methacrylates and acrylates, and mixtures of the two. These monomers are widely known. In this context, the alkyl moiety can be linear, cyclic, or branched. The alkyl moiety can also have a known substituent.

  The term “repeat unit” is widely known in the art. The polymer having ester groups is preferably obtained by free radical polymerization of monomers, ATRP, RAFT, and NMP controlled radical process techniques (discussed later), which are counted in the context of the present invention as free radical processes. And is not intended to impose any restrictions. In these processes, double bonds are opened and covalent bonds are formed. The repeat unit is thus obtained from the monomers used.

  The polymer having an ester group preferably contains a repeating unit derived from an ester monomer having 7 to 4000 carbon atoms in the alcohol moiety. Preferably, the polymer is at least 40% by weight, in particular at least 60% by weight, more preferably at least 80% by weight, 7 to 4000 carbon atoms, preferably 7 to 300 carbon atoms, more preferably at least 80% by weight. Contains repeating units derived from ester monomers having 7 to 30 carbon atoms.

  According to a preferred embodiment, the polymer comprises a repeating unit derived from an ester monomer having 16 to 4000 carbon atoms, preferably 16 to 300 carbon atoms, more preferably 16 to 30 carbon atoms in the alcohol moiety. , And repeating units derived from ester monomers having from 7 to 15 carbon atoms in the alcohol moiety.

  The polymer having an ester group contains 5 to 100% by weight, particularly 20 to 98% by weight, more preferably 30 to 60% by weight, containing repeating units derived from an ester monomer having 7 to 15 carbon atoms in the alcohol part. Can do.

  In a particular embodiment, the ester group-containing polymer is 0 to 90% by weight, preferably 5 to 80% by weight, more preferably 40 to 70% by weight, 16 to 4000, preferably 16 to 30% in the alcohol moiety. It may contain repeating units derived from ester monomers having 1 carbon atom.

  Preferably, the polymer may comprise repeating units derived from ester monomers having 23-4000 carbon atoms, preferably 23-400 carbon atoms, more preferably 23-300 carbon atoms in the alcohol moiety. .

  Furthermore, the polymer having an ester group is 0.1 to 60% by weight, in particular 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight, in the alcohol part. It may contain repeating units derived from ester monomers having ˜6 carbon atoms.

  According to a preferred embodiment, the polymer comprises a repeating unit derived from an ester monomer having 23 to 4000 carbon atoms, preferably 23 to 400 carbon atoms, more preferably 23 to 300 carbon atoms in the alcohol moiety. , And repeating units derived from ester monomers having 1 to 6 carbon atoms in the alcohol moiety.

  The polymer having ester groups preferably comprises at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight, very particularly at least 95% by weight, of repeating units derived from ester monomers.

［式中、Ｒは、水素またはメチルであり、Ｒ¹は、１〜６個の炭素原子を有する直鎖状または分岐鎖状のアルキル基であり、Ｒ²およびＲ³は、それぞれ独立して、水素または式−ＣＯＯＲ’の基である（ここで、Ｒ’は、水素または、１〜６個の炭素原子を有するアルキル基である）］の１種以上のエチレン性不飽和エステル化合物を含有し得る。 The mixture from which the polymers according to the invention having ester groups are obtained is 0 to 40% by weight, in particular 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, of the formula (I):

Wherein R is hydrogen or methyl, R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently , Hydrogen or a group of formula —COOR ′, wherein R ′ is hydrogen or an alkyl group having 1 to 6 carbon atoms]] containing one or more ethylenically unsaturated ester compounds Can do.

Examples of component (I) include
(Meth) acrylates, fumarate and maleates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate;
Examples thereof include cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate.

［式中、Ｒは、水素またはメチルであり、Ｒ⁴は、７〜１５個の炭素原子を有する直鎖状または分岐鎖状のアルキル基であり、Ｒ⁵およびＲ⁶は、それぞれ独立して、水素または式−ＣＯＯＲ’’の基である（ここで、Ｒ’’は、水素または、７〜１５個の炭素原子を有するアルキル基である）］の１種以上のエチレン性の不飽和エステル化合物を含有する。 The composition to be polymerized is preferably from 0 to 100% by weight, in particular from 5 to 98% by weight, in particular from 20 to 90% by weight, more preferably from 30 to 60% by weight, of formula (II):

Wherein R is hydrogen or methyl, R ⁴ is a linear or branched alkyl group having 7 to 15 carbon atoms, and R ⁵ and R ⁶ are each independently , Hydrogen or a group of formula —COOR ″, where R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms]] Contains compounds.

Examples of component (II) include
(Meth) acrylate, fumarate, and maleate derived from saturated alcohols, such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3- Isopropyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, 2-propylheptyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate;
(Meth) acrylates derived from unsaturated alcohols, such as oleyl (meth) acrylate;
Examples include cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate; and the corresponding fumarate and maleate.

［式中、Ｒは、水素またはメチルであり、Ｒ⁷は、１６〜４０００個、好ましくは１６〜４００個、より好ましくは１６〜３０個の炭素原子を有する直鎖状または分岐鎖状アルキル基であり、Ｒ⁸およびＲ⁹は、それぞれ独立して、水素または式−ＣＯＯＲ’’’の基である（ここで、Ｒ’’’は、水素または、１６〜４０００個、好ましくは１６〜４００個、より好ましくは１６〜３０個の炭素原子を有するアルキル基である）］の１種以上のエチレン性不飽和エステル化合物を含む。 Moreover, the preferred monomer composition is 0-100% by weight, in particular 0.1-90% by weight, preferably 5-80% by weight, more preferably 40-70% by weight, of formula (III):

[Wherein R is hydrogen or methyl, and R ⁷ is a linear or branched alkyl group having 16 to 4000, preferably 16 to 400, more preferably 16 to 30 carbon atoms. R ⁸ and R ⁹ are each independently hydrogen or a group of the formula —COOR ′ ″ (where R ′ ″ is hydrogen or 16 to 4000, preferably 16 to 400, Or more preferably an alkyl group having 16 to 30 carbon atoms)].

Examples of component (III) include
(Meth) acrylate derived from saturated alcohol, for example, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (Meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyl eicosyl (meth) acrylate, stearyl Eicosyl (meth) acrylate, docosyl (meth) acrylate, and / or eicosyl tetratriacontyl (meth) acrylate;
Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate;
As well as the corresponding fumarate and maleate.

  In addition, monomers according to formula (III) include, among others, US Pat. No. 6,746,993, filed August 7, 2002, to the United States Patent Office (USPTO), application number 10 / 212,784. Long chain branching (meta) as disclosed in U.S. Patent Application Publication No. 2004/075509, filed August 1, 2003, to the United States Patent Office (USPTO) with application number 10 / 632,108. ) Acrylates. The disclosures of these documents, in particular (meth) acrylate monomers having at least 16, preferably at least 23 carbon atoms, are hereby incorporated by reference.

In addition, C ₁₆ -C ₄₀₀₀ alkyl (meth) acrylate monomers, preferably C ₁₆ -C ₄₀₀ alkyl (meth) acrylate monomers, include polyolefin-based macromonomers. The polyolefin-based macromonomer has at least one group derived from a polyolefin. Polyolefins are known in the art, alkenes and / or alkadienes of carbon elements and hydrogen elements, for example, C ₂ -C ₁₀ - alkenes such as ethylene, propylene, n- butene, isobutene, norbornene, and / Alternatively, it is obtained by polymerizing C ₄ -C ₁₀ -alkadiene, such as butadiene, isoprene, norbornadiene. The polyolefin-based macromonomer is preferably at least 70%, more preferably at least 80%, and most preferably at least 90% by weight of alkene and / or based on the weight of the polyolefin-based macromonomer. It has a group derived from alkadiene. The polyolefinic group can also be present, especially in hydrogenated form. In addition to groups derived from alkenes and / or alkadienes, alkyl (meth) acrylate monomers derived from polyolefin-based macromonomers can also have further groups. These contain small amounts of copolymerizable monomers. These monomers, which are known per se, include, among other monomers, alkyl (meth) acrylates, styrene monomers, fumarate, maleates, vinyl esters, and / or vinyl ethers. The proportion of these groups relative to the copolymerizable monomer is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the polyolefin-based macromonomer. Moreover, the polyolefin-based macromonomer can have starting and / or terminating groups that are utilized for functionalization or that result from the production of a polyolefin-based macromonomer. The proportion of these starting and / or terminating groups is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the polyolefin-based macromonomer.

  The number average molecular weight of the polyolefin-based macromonomer is preferably 500 to 50,000 g / mol, more preferably 700 to 10,000 g / mol, especially 1500 to 8000 g / mol, most preferably 2000 to 6000 g / mol. is there.

  When a comb polymer is produced by copolymerization of a low molecular weight monomer and a high molecular monomer, these values are caused by the characteristics of the high molecular monomer. In the case of polymer-analogous reactions, this property arises, for example, from macroalcohols and / or macroamines that are used in view of converted repeating units in the main chain. In the case of graft copolymerization, the proportion of polyolefin formed without being incorporated into the backbone can be used to conclude the molecular weight distribution of the polyolefin.

  Polyolefin-based macromonomers preferably have a low melting point, which is measured by differential scanning calorimetry (DSC). The melting point of the polyolefin-based macromonomer is preferably −10 ° C. or less, particularly preferably −20 ° C. or less, more preferably −40 ° C. or less. Most preferably, no DSC melting point is measured for repeating units derived from polyolefin-based macromonomers in the polyalkyl (meth) acrylate copolymer.

  Polyolefin-based macromonomers are published in German Patent Application No. 102007032120 (A1) filed with the German Patent Office on July 9, 2007, publication number DE102007032120.3, and German Patent Application Publication No. 102007046223 (A1), filed with the German Patent Office on September 26, 2007, application number DE1020070462223.0, which is hereby incorporated by reference. Incorporated in the specification.

  Ester compounds having a long-chain alcohol moiety, in particular components (II) and (III), can be obtained, for example, by reacting a long-chain fatty alcohol with (meth) acrylate, fumarate, maleate and / or the corresponding acid. This generally results in a mixture of esters, for example (meth) acrylates with various long chain hydrocarbons in the alcohol moiety. These fatty alcohols include Oxo Alcohol (R) 7911, Oxo Alcohol (R) 7900, Oxo Alcohol (R) 1100; Alfol (R) 610, Alfol (R) 810, Lial (R). 125, and Nafol (R) type (Sasol); Alphanol (R) 79 (ICI); Epal (R) 610 and Epal (R) 810 (Afton); Linevol (R) 79, Linevol (R) Trademark) 911, and Neodol <(R)> 25E (Shell); Dehydad <(R)>, Hydrenol <(R)>, and Lorol <(R)> Type (Cognis); Acropol <(R)> Mark) 35 and Exxal (R) 10 (Exxon Chemicals); Kalcol (R) 2465 (Kao Chemicals) and the like.

Of the ethylenically unsaturated ester compounds, (meth) acrylates are particularly preferred over maleates and fumarate, ie R ² , R ³ , R ⁵ , R ^{6 of} formulas (I), (II), and (III). , R ⁸ , and R ⁹ are each hydrogen in certain preferred embodiments.

  A unit derived from an ester monomer having 7 to 15 carbon atoms, preferably an ester monomer of formula (II), and an ester monomer having 16 to 4000 carbon atoms, preferably an ester monomer of formula (III) The mass ratio with the originating unit can be within a wide range. The mass ratio of the repeating unit derived from an ester monomer having 7 to 15 carbon atoms in the alcohol part and the repeating unit derived from an ester monomer having 16 to 4000 carbon atoms in the alcohol part is preferably 30: The ratio is 1-1: 30, more preferably 5: 1 to 1: 5, and particularly preferably 3: 1 to 1.1: 1. According to a further preferred embodiment, the mass ratio of repeating units derived from ester monomers having 7 to 15 carbon atoms in the alcohol moiety and repeating units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol moiety. Is preferably 4: 1 to 1: 4, more preferably 3: 1 to 1: 3, and particularly preferably 2.4: 1 to 1.1: 1.

The polymer may contain a unit derived from a comonomer as an optional component. These comonomers include:
Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate (in which case the acrylic residue is in each case unsubstituted or optionally substituted up to 4 times);
2,3-dibromopropyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 1,3-dichloro-2-propyl (meth) acrylate, 2-bromoethyl (meth) acrylate, 2-iodoethyl (meth) acrylate, (Meth) acrylates of halogenated alcohols, such as chloromethyl (meth) acrylate;
(Meth) acrylic acid such as N- (methacryloyloxyethyl) diisobutylketimine, N- (methacryloyloxyethyl) dihexadecylketimine, (meth) acryloylamide acetonitrile, 2-methacryloyloxyethylmethyl cyanamide, cyanomethyl (meth) acrylate And other nitrogen-containing (meth) acrylate nitriles;
Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
Vinyl esters such as vinyl acetate;
Vinyl monomers having an aromatic group such as styrene, substituted styrenes having an alkyl substituent in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrene, such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene;
Vinyl and isoprenyl ethers;
Maleic acid and maleic acid derivatives such as maleic acid, maleic anhydride, methylmaleic anhydride, maleimide, monoesters and diesters of methylmaleimide;
Fumaric acid and fumaric acid derivatives, such as mono- and diesters of fumaric acid;
Examples include methacrylic acid and acrylic acid.

  According to a particular embodiment of the invention, the polymer having an ester group comprises a dispersible monomer.

Dispersible monomers are understood to mean, inter alia, monomers having functional groups, and polymers having these functional groups can be envisaged to maintain particles, especially soot particles, in solution (RM Mortier). , S.T.Orszulik (eds.): " Chemistry and Technology of Lubricants", Blackie Academic & Professional, see ^London, 2 nd ^ed.1997). These include, among other things, monomers having boron-containing groups, phosphorus-containing groups, silicon-containing groups, sulfur-containing groups, oxygen-containing groups, and nitrogen-containing groups. Functionalized monomers and nitrogen functionalized monomers are preferred.

［式中、Ｒは、水素またはメチルであり、Ｘは、酸素、硫黄、または式−ＮＨ−もしくは−ＮＲ^a−のアミノ基であり（ここで、Ｒ^aは、１〜４０個、好ましくは１〜４個の炭素原子を有するアルキル基である）、Ｒ¹⁰は、２〜１０００個、とりわけ２〜１００個、好ましくは２〜２０個の炭素原子を有する基であり、少なくとも１個のヘテロ原子、好ましくは少なくとも２個のヘテロ原子を有し、Ｒ¹¹およびＲ¹²は、それぞれ独立して、水素または、式−ＣＯＸ’Ｒ^10’の基である（ここで、Ｘ’は、酸素または、式−ＮＨ−もしくは−ＮＲ^a’−のアミノ基であり、式中、Ｒ^a’は、１〜４０個、好ましくは１〜４個の炭素原子を有するアルキル基であり、Ｒ^10’は、１〜１００個、好ましくは１〜３０個、より好ましくは１〜１５個の炭素原子を有する基である）］のエチレン性不飽和極性エステル化合物を使用することができる。 Suitably as dispersible monomers, inter alia heterocyclic vinyl compounds and / or formula (IV):

[Wherein, R is hydrogen or methyl, X is oxygen, sulfur, or an amino group of the formula —NH— or —NR ^a — (wherein R ^a is 1 to 40, preferably R ¹⁰ is a group having 2 to 1000, especially 2 to 100, preferably 2 to 20 carbon atoms, and at least one hetero Having atoms, preferably at least two heteroatoms, R ¹¹ and R ¹² are each independently hydrogen or a group of formula —COX′R ^{10 ′} (where X ′ is oxygen or An amino group of the formula —NH— or —NR ^{a ′} —, wherein R ^{a ′} is an alkyl group having 1 to 40, preferably 1 to 4 carbon atoms, and R ^{10 ′} is 1-100, preferably 1-30, more preferably 1-15 carbon atoms. The ethylenically unsaturated polar ester compound can be used.

  The expression “group having 2 to 1000 carbons” means an organic compound group having 2 to 1000 carbon atoms. Similar definitions apply to the corresponding terms. It includes aromatic and heteroaromatic groups, as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups, and heteroaliphatic groups. The mentioned groups may be branched or unbranched. Furthermore, these groups may have a normal substituent. Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl, or hexyl; cycloalkyl groups, such as , Cyclopentyl and cyclohexyl; aromatic groups such as phenyl or naphthyl; amino groups, hydroxyl groups, ether groups, ester groups, and halides.

  According to the invention, an aromatic group preferably means a group of monocyclic or polycyclic aromatic compounds having 6-20, in particular 6-12, carbon atoms. A heteroaromatic group means an aryl group in which at least one CH group is substituted with N and / or an aryl group in which at least two adjacent CH groups are substituted with S, NH, or O, Group groups have from 3 to 19 carbon atoms.

  Preferred aromatic or heteroaromatic groups according to the invention are benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole. , Pyrazole, 1,3,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 1,3,4-thiadiazol, 1,3,4-triazole, 2,5 -Diphenyl-1,3,4-triazole, 1,2,5-triphenyl-1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2, 4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazo Benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzoisothiazole, benzopyrazole , Benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5- Triazine, tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimy , Purine, pteridine, or quinolidine, 4H-quinolidine, diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, indolizine, pyridopyridine, imidazopyrimidine , Pyrazinopyrimidine, carbazole, acylidine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridin, benzopteridine, phenanthroline, and phenanthrene, each optionally substituted.

  Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl group, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl, and eicosyl groups.

  Preferred cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, each optionally substituted with a branched or unbranched alkyl group.

  Preferred alkanoyl groups include formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl, and decanoyl groups.

  Preferred alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl, or dodecyloxycarbonyl group.

  Preferred alkoxy groups include those alkoxy groups whose hydrocarbon group is one of the aforementioned preferred alkyl groups.

  Preferred cycloalkoxy groups include cycloalkoxy groups in which the hydrocarbon group is one of the aforementioned preferred cycloalkyl groups.

Preferred heteroatoms present in the R ¹⁰ group include oxygen, nitrogen, sulfur, boron, silicon, and phosphorus, with oxygen and nitrogen being preferred.

The R ¹⁰ group contains at least 1, preferably at least 2 and preferentially at least 3 heteroatoms.

The R ¹⁰ group in the ester compound of formula (IV) preferably has at least two different heteroatoms. In this case, the R ¹⁰ group in at least one of the ester compounds of formula (IV) comprises at least one nitrogen atom and at least one oxygen atom.

  Examples of ethylenically unsaturated polar ester compounds of formula (IV) include aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides, hydroxyalkyl (meth) acrylates, (meth) acrylates of ether alcohols, heterocyclic ( And (meth) acrylate and / or carbonyl-containing (meth) acrylate.

As hydroxyalkyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate,
3,4-dihydroxybutyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate,
Examples include 2,5-dimethyl-1,6-hexanediol (meth) acrylate and 1,10-decanediol (meth) acrylate.

As a (meth) acrylate of ether alcohol,
Tetrahydrofurfuryl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1-butoxypropyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, propoxyethoxyethyl (meth) acrylate, benzyloxyethyl (meth) acrylate, furfuryl (Meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxy-2-ethoxyethyl (meth) acrylate, 2-methoxy-2-ethoxypropyl (meth) acrylate, ethoxylated (meth) acrylate, 1-ethoxy Butyl (meth) acrylate, methoxyethyl (meth) acrylate, 2-ethoxy-2-ethoxy-2-ethoxyethyl (meth) acrylate, esters of (meth) acrylic acid, and methoxy Polyethylene glycol.

Suitable carbonyl-containing (meth) acrylates include, for example,
2-carboxyethyl (meth) acrylate,
Carboxymethyl (meth) acrylate,
Oxazolidinylethyl (meth) acrylate,
N- (methacryloyloxy) formamide,
Acetonyl (meth) acrylate,
Mono-2- (meth) acryloyloxyethyl succinate,
N- (meth) acryloylmorpholine,
N- (meth) acryloyl-2-pyrrolidinone,
N- (2- (meth) acryloyloxyethyl) -2-pyrrolidinone,
N- (3- (meth) acryloyloxypropyl) -2-pyrrolidinone,
N- (2- (meth) acryloyloxypentadecyl) -2-pyrrolidinone,
N- (3- (meth) acryloyloxyheptadecyl) -2-pyrrolidinone, N- (2- (meth) acryloyloxyethyl) ethylene urea and the like can be mentioned.
2-acetoacetoxyethyl (meth) acrylate As the heterocyclic (meth) acrylate,
2- (1-imidazolyl) ethyl (meth) acrylate,
2- (4-morpholinyl) ethyl (meth) acrylate, and 1- (2- (meth) acryloyloxyethyl) -2-pyrrolidone.

In addition, aminoalkyl (meth) acrylates, and aminoalkyl (meth) acrylamides, such as
Dimethylaminopropyl (meth) acrylate,
Dimethylaminodiglycol (meth) acrylate,
Dimethylaminoethyl (meth) acrylate,
Dimethylaminopropyl (meth) acrylamide,
Of particular interest are 3-diethylaminopentyl (meth) acrylate and 3-dibutylaminohexadecyl (meth) acrylate.

Furthermore, as dispersible units, phosphorus-containing, boron-containing and / or silicon-containing (meth) acrylates, for example
2- (dimethylphosphato) propyl (meth) acrylate,
2- (ethylene phosphite) propyl (meth) acrylate,
Dimethylphosphinomethyl (meth) acrylate,
Dimethylphosphonoethyl (meth) acrylate,
Diethyl (meth) acryloylphosphonate,
Dipropyl (meth) acryloyl phosphate, 2- (dibutylphosphono) ethyl (meth) acrylate,
2,3-butylene (meth) acryloyl ethyl borate,
Methyldiethoxy (meth) acryloylethoxysilane,
Diethyl phosphatoethyl (meth) acrylate can be used.

  Preferred heterocyclic vinyl compounds include 2-vinyl pyridine, 3-vinyl pyridine, 2-methyl-5-vinyl pyridine, 3-ethyl-4-vinyl pyridine, 2,3 dimethyl-5-vinyl pyridine, vinyl pyrimidine, Vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinyl Pyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole and hydrogenated vinylthiazole, vinyloxazole and hydrogenated vinyloxazo Le can be mentioned, the use of N- vinylimidazole and N- vinylpyrrolidone for functionalization are particularly preferred.

  The monomers described in detail above can be used alone or as a mixture.

  In particular, having an ester group, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, mono-2-methacryloyloxyethyl succinate, N- (2-methacryloyloxyethyl) ethyleneurea, 2-acetoacetoxyethyl methacrylate, Of particular interest are polymers obtained using 2- (4-morpholinyl) ethyl methacrylate, dimethylaminodiglycol methacrylate, dimethylaminoethyl methacrylate, and / or dimethylaminopropyl methacrylamide.

  Certain improvements can be achieved by polymers with ester groups obtained using N-vinyl-2-pyrrolidine and / or N-vinyl-2-pyrrolidone.

  Dispersible and non-dispersible monomers can be statistically distributed within the polymer having ester groups. The proportion of the dispersible repeating unit in the statistical polymer is preferably 0% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and most preferably 2.% by mass with respect to the mass of the polymer having the ester group. It is 5 mass%-10 mass%.

  More preferably, the dispersible repeating unit can be selected from dimethylaminopropyl methacrylamide (DMAPMA) and / or dimethylaminoethyl methacrylate (DMAEMA), and the amount of dispersible repeating unit relative to the mass of the polymer having the ester group Is preferably 0.5 mass% to 10 mass%, more preferably 1.2 mass% to 5 mass%.

  More preferably, the dispersible repeat unit can be selected from 2- (4-morpholinyl) ethyl methacrylate (MOEMA), 2-hydroxyethyl (meth) acrylate (HEMA), and / or hydroxypropyl methacrylate (HPMA). The amount of the dispersible repeating unit with respect to the mass of the polymer having an ester group is preferably 2% by mass to 20% by mass, more preferably 5% by mass to 10% by mass.

  According to another aspect of the present invention, the polymer having an ester group can have only a small amount of dispersible repeating units. According to such embodiments, the proportion of the dispersible repeat unit is preferably at most 5%, more preferably at most 2%, and most preferably at most 0.5%, based on the weight of the polymer having the ester group. is there.

  According to a particular embodiment of the present invention, the lubricant used in the motor may preferably comprise a mixture of polymers, and as mentioned above, at least one of the polymers has a significant amount of dispersible repeats. And at least one of the polymers has a small amount of dispersible repeating units.

  According to a preferred embodiment of the present invention, the polymer having an ester group is a graft copolymer having a non-dispersible alkyl (meth) acrylate polymer as a graft base and a dispersible monomer as a graft layer. Preferably, the non-dispersible alkyl (meth) acrylate polymer essentially has (meth) acrylate monomer units according to formulas (I), (II) and (III) as defined above and below. The proportion of the dispersible repeating unit in the graft copolymer or block copolymer is preferably 0% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and most preferably based on the mass of the polymer having the ester group. It is 2.5 mass%-10 mass%.

  The dispersible monomer is preferably a heterocyclic vinyl compound as mentioned above and below.

  According to a further aspect of the invention, the polymer having an ester group is an alkyl (meth) acrylate polymer having at least one polar block and at least one hydrophobic block.

  Preferably, the polar block comprises at least three units derived from a monomer of formula (IV) and / or a heterocyclic vinyl compound, which are directly bonded to each other.

  Preferred polymers have at least one hydrophobic block and at least one polar block, the polar block having at least 8 repeating units, and the mass proportion of dispersive repeating units in the polar block is , And at least 30% by mass with respect to the mass of the polar block.

  Preferred polymers of the present invention can have a polar block and a hydrophobic block. The term “block” in this context refers to a portion of a polymer. A block may have a constant composition consisting essentially of one or more monomer units. Furthermore, the block may have a gradient, in which case the concentration of different monomer units (repeat units) varies over the segment length. The polar block differs from the hydrophobic block by the proportion of dispersible monomer. The hydrophobic block may have at most a small amount of dispersible repeating units (monomer units), whereas the polar block contains a large amount of dispersible repeating units (monomer units).

  The polar block may preferably comprise at least 8, particularly preferably at least 12, most preferably at least 15 repeating units. At the same time, the polar block comprises at least 30% by weight, preferably at least 40% by weight of dispersible repeating units, based on the weight of the polar block. In addition to the dispersive repeat unit, the polar block may have repeat units that do not have any dispersive effect. The polar block may have a random structure in which different repeating units have a random distribution over the segment length. Further, the polar block may have a block structure or a gradient-form structure in which the non-dispersive repeating units and the dispersive repeating units within the polar block have a non-uniform distribution.

  The hydrophobic block may comprise a small amount of dispersible repeating units, which unit is preferably less than 20% by weight, more preferably less than 10% by weight, most preferably 5% by weight, based on the weight of the hydrophobic block. Is less than. In a particularly suitable configuration, the hydrophobic block is essentially free of dispersive repeat units.

  The hydrophobic block of the polymer having an ester group is 5 to 100% by mass, especially 20 to 98% by mass, preferably 30 to 95% by mass, most preferably 70 to 92% by mass, and 7 to 15 alcohol groups. It may have a repeating unit derived from an ester monomer having 5 carbon atoms.

  In certain embodiments, the hydrophobic block of the polymer having an ester group is 0-80% by weight, preferably 0.5-60% by weight, more preferably 2-50% by weight, most preferably 5-20% by weight. Of repeating units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol group.

  Furthermore, the hydrophobic block of the polymer having the ester group is 0 to 40% by mass, preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and 1 to 6 alcohol groups. It may have repeating units derived from ester monomers having carbon atoms.

  The hydrophobic block of the polymer having ester groups is preferably at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight, repeating from the ester monomer Includes units.

  The hydrophobic block length can vary within wide limits. The hydrophobic block preferably has a mass average degree of polymerization of at least 10, in particular at least 40. The mass average degree of polymerization of the hydrophobic block is preferably 20 to 5000, especially 50 to 2000.

  The proportion of the dispersible repeating unit is preferably 0.5% by mass to 20% by mass, more preferably 1.5% by mass to 15% by mass, and most preferably 2.5% by mass with respect to the mass of the polymer having an ester group. Mass% to 10 mass%. At the same time, these repeating units preferably have ester groups so that preferably at least 70% by weight, more preferably at least 80% by weight, are part of the polar block, based on the total weight of the dispersible repeating units. A segment-like structure is formed in the polymer.

  Preferably, the mass ratio of hydrophobic block to polar block is 100: 1 to 1: 1, more preferably 30: 1 to 2: 1, most preferably 10: 1 to 4: 1.

  The production of polymers having ester groups from the compositions described above is known per se. Thus, these polymers are obtained in particular by free radical polymerization and related processes such as ATRP (= atom transfer radical polymerization) or RAFT (= reversible addition-fragmentation chain transfer).

  Customary free radical polymerization is described inter alia in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition. Generally, polymerization initiators and chain transfer agents are used for this purpose. Usable initiators include azo initiators widely known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl. Peroxide, tert-butylper-2-ethylhexanoate, ketone peroxide, tert-butylperoctoate, methylisobutylketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethyl Xanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of two or more of the foregoing compounds with another, and the foregoing A mixture with a compound that is not mentioned but can form a free radical is also mentioned. Suitable chain transfer agents are in particular oil-soluble mercaptans such as n-dodecyl mercaptan or 2-mercaptoethanol or terpene class chain transfer agents such as terpinolene.

  The ATRP process is known per se. It is assumed that it is a “living” free radical polymerization, and there is no intention that the description of the mechanism should impose limitations. In these processes, the transition metal compound reacts with a compound having a rearrangeable atomic group. This transfers the rearrangeable atomic group to the transition metal compound, thereby oxidizing the metal. This reaction forms an additional group on the ethylenic group. However, the transfer of the atomic group to the transition metal compound is reversible, so that the atomic group returns to the growing polymer chain, thereby forming a controlled polymerization system. The structure, molecular weight, and molecular weight distribution of the polymer can be controlled accordingly.

  This reaction is described, for example, by JS. Wang, et al. , J .; Am. Chem. Soc. , Vol. 117, p. 5614-5615 (1995), Matyjaszewski, Macromolecules, vol. 28, p. 7901-7910 (1995). Further, patent applications: WO 96/30421, 97/47661, 97/18247, 98/40415, and 99/10387 describe ATRP as described above. Variations are disclosed.

  Furthermore, the polymer of the present invention can be obtained, for example, by the RAFT method. This process is presented in detail, for example, in WO 98/01478 and 2004/083169, and is specifically mentioned for disclosure purposes.

  Furthermore, the polymers of the present invention are obtained by the NMP process (nitroxide mediated polymerization process), which is described inter alia in US Pat. No. 4,581,429.

  These methods are described in particular in further references, notably K.A. Matyjaszewski, T .; P. Davis, Handbook of Radical Polymerization, Wiley Interscience, Hoboken 2002, which is specifically mentioned for disclosure purposes.

  The polymerization can be carried out at standard pressure, reduced pressure, or increased pressure. The polymerization temperature is generally -20 ° C to 200 ° C, preferably 0 ° C to 160 ° C, more preferably 60 ° C to 140 ° C.

  The polymerization can be carried out with or without a solvent. The term solvent is to be understood here in a broad sense.

  The polymerization is preferably carried out in a nonpolar solvent. These solvents include hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which are It may exist in a branched form. These solvents can be used individually as well as as a mixture. Particularly preferred solvents are mineral oils, mineral-derived diesel fuels, natural vegetable and animal oils, biodiesel fuels, and synthetic oils (eg, ester oils such as dinonyl adipate), and mixtures thereof. Of these, very particularly preferred are mineral oil and mineral diesel fuel.

  According to a particular embodiment of the invention, polymers based on ethyl vinyl acetate can be used as polymers having ester groups. Preferred polymers based on ethyl vinyl acetate are described in EP 0739971 (B1), 0721492 (B2), and 0741181 (B1). Document European Patent No. 07399971 (B1) filed with the European Patent Office on June 29, 1993 in application number 96202136.6; filed with the European Patent Office on July 22, 1994 in application number 94924280.4 European Patent No. 0721492 (B2) and European Patent No. 0741181 (B1) filed with the European Patent Office on 29 June 1993 in application number 96202137.4 are hereby incorporated by reference.

  Preferably, mixtures of various ethylene vinyl acetate (EVA) based polymers can be used to improve the properties of lubricating oils containing biodiesel contaminants. The first EVA-based polymer can include ethylene, vinyl acetate, and alkyl esters of (meth) acrylates, fumarate, and / or maleate. The alkyl ester preferably contains 6 to 20, more preferably 7 to 12 carbon atoms in the alkyl residue. With respect to fumarate and / or maleate, diesters are preferred. The first EVA polymer preferably has an ethylene content of 50 to 90 mol% and a vinyl acetate content of 10 to 40 mol%. The amount of alkyl ester derived from (meth) acrylate, fumarate and / or maleate is preferably 1 to 20 mol%, more preferably 2 to 10 mol%. The mass average molecular weight Mw of the first EVA polymer can be preferably set in the range of 10,000 to 50,000 g / mol. The polydispersity Mw / Mn of the first EVA polymer is preferably 1.1 to 5, more preferably 1.5 to 3. The second EVA polymer preferably has an ethylene content of 60-95 mol% and a vinyl acetate content of 5-40 mol%. The mass average molecular weight Mw of the second EVA polymer can be preferably set in the range of 1000 to 10000 g / mol. The polydispersity Mw / Mn of the second EVA polymer is preferably 1.1 to 5, more preferably 2.0 to 4.

  Preferably, the lubricant comprises a mixture of polymers having at least two ester groups. More preferably, the lubricant comprises an alkyl (meth) acrylate polymer and an ethylene vinyl acetate polymer, as mentioned above and below.

  According to a particular embodiment of the present invention, the motor lubricant of the present invention preferably comprises a polymer having an ester group and preferably an olefinic polymer having a viscosity index improving effect and a thickening effect. Such polyolefins have long been known and are described in the literature mentioned in the prior art.

  These polyolefins include in particular polyolefin copolymers (OCP) and hydrogenated styrene / diene copolymers (HSD).

  The polyolefin copolymers (OCP) used according to the invention are known per se. Polymers synthesized primarily from ethylene-, propylene-, isoprene-, butylene-, and / or additional olefins having 5-20 carbon atoms, as already recommended as viscosity index improvers. Systems that are grafted with small amounts of oxygen-containing or nitrogen-containing monomers (e.g., 0.05-5 wt% maleic anhydride) can also be used. Copolymers containing diene components are generally hydrogenated to reduce the oxidation sensitivity and cross-linking tendency of viscosity index improvers.

  The molecular weight Mw is generally 10,000 to 300,000, preferably 50,000 to 150,000. Such olefin copolymers are described, for example, in German Patent Application Publication Nos. 1644941, 1769834, 1939037, 1963039, and 2059981, which are published German patent applications. Yes.

  Ethylene / propylene copolymers are particularly useful and terpolymers with known ternary components, such as ethylidene-norbornene (see Macromolecular Reviews, Vol. 10 (1975)) are also possible, but their tendency to crosslink Must also be considered in the degradation process. The distribution can be substantially random, but continuous polymers containing ethylene blocks can also be used advantageously. The ratio of ethylene monomer / propylene monomer is variable within certain limits, which can be set as upper limits up to about 75% for ethylene and up to about 80% for propylene. Polypropylene is not as suitable as an ethylene / propylene copolymer because of its reduced tendency to dissolve in oil. In addition to polymers that predominantly incorporate atactic propylene, polymers that more significantly incorporate isotactic or syndiotactic propylene may also be used.

  Such products are, for example, trade names: Dural (R) CO 034, Dural (R) CO 038, Dural (R) CO 043, Dural (R) CO 058, Buna (R) EPG 2050. , Or Buna® EPG 5050.

  Similarly, hydrogenated styrene / diene copolymers (HSD) are known and these polymers are described, for example, in DE 2156122. They are generally hydrogenated isoprene / styrene copolymers or hydrogenated butadiene / styrene copolymers. The ratio of diene to styrene is preferably 2: 1 to 1: 2, particularly preferably about 55:45. The molecular weight Mw is generally from 10,000 to 300,000, preferably from 50 to 150,000. According to a particular embodiment of the invention, the proportion of double bonds after hydrogenation is 15% or less, particularly preferably 5% or less, relative to the number of double bonds before hydrogenation.

  Hydrogenated styrene / diene copolymers are commercially available under the trade name SHELLVIS® 50, 150, 200, 250, or 260.

  According to a highly preferred embodiment of the invention, the polymer having ester groups is a block copolymer comprising a block of ester group-containing units and an olefinic block. Preferably, the olefinic block is derived from an HSD polymer and / or OCP polymer.

  A block copolymer having a block of ester group-containing units and an olefinic block is disclosed in German Patent Application Publication No. 3339103, filed on October 28, 1983, at the German Patent Office (Deutsches Patentatent) with application number P3339103.3. (A1) and publications such as German Patent Application Publication No. 2905954 (A1) filed with the German Patent Office on February 16, 1979 and having application number P2905954.9. Which is incorporated herein by reference.

  The lubricant used in the motor of the present invention contains a base oil in addition to the polymer having an ester group. Preferred base oils include, among others, mineral oils, synthetic oils, and natural oils.

  Mineral oils are known per se and are commercially available. They are generally obtained from mineral oil or crude oil by distillation and / or rectification and optionally further refining and finishing steps, and the term mineral oil includes in particular high-boiling fractions of crude oil or mineral oil. In general, the boiling point of mineral oil is above 200 ° C., preferably above 300 ° C. at 5000 Pa. Low temperature carbonization of shale oil, coking of bituminous coal, distillation of lignite with exclusion of air, and hydrogenation of bituminous and lignite are possible as well. Thus, mineral oils have different proportions of aromatic hydrocarbons, cyclic hydrocarbons, branched and straight chain hydrocarbons depending on their origin.

  In general, a distinction is made between paraffin-based fractions, naphthene fractions, and aromatic fractions in crude oil or mineral oil, and the term paraffin-based fraction refers to longer chains or highly branched isoalkanes, Minute represents cycloalkane. In addition, mineral oils are responsible for various fractions of n-alkanes, low-branching isoalkanes known as mono-methyl-branched paraffins, and some degree of polar properties, depending on their origin and finishing process. Having compounds with heteroatoms, in particular O, N, and / or S. However, clear delineation is difficult because individual alkane molecules may have both long-chain branching groups and cycloalkane groups, as well as aromatic moieties. For the purposes of the present invention, for example, the line can be drawn according to DIN 51 378. Polar fractions can also be identified according to ASTM D 2007.

  The proportion of n-alkane in the preferred mineral oil is less than 3% by weight, and the fraction of O-containing, N-containing and / or S-containing compounds is less than 6% by weight. The fraction of aromatic and mono-methyl-branched paraffins is generally 0-40% by weight in each case. In one interesting aspect, the mineral oil mainly comprises naphthenic alkanes and paraffin-based alkanes having generally more than 13, preferably more than 18, most preferably more than 20 carbon atoms. The fractions of these compounds are generally ≧ 60% by weight, preferably ≧ 80% by weight, but this is not intended to impose certain limitations. Preferred mineral oils are in each case 0.5-30% by weight aromatic fraction, 15-40% by weight naphthene fraction, 35-80% by weight paraffin-based fraction, based on the total weight of the mineral oil. Containing up to 3% by weight of n-alkane and 0.05 to 5% by weight of polar compounds.

Analysis in certain preferred mineral oils performed by conventional methods, such as urea separation and liquid chromatography on silica gel, for example, shows the following components, where the percentage is for the particular mineral oil used: For the total mass:
N-Alkanes having about 18 to 31 carbon atoms:
0.7-1.0%,
Slightly branched alkanes having 18 to 31 carbon atoms:
1.0-8.0%,
Aromatics having 14 to 32 carbon atoms:
0.4-10.7%,
Isoalkanes and cycloalkanes having 20 to 32 carbon atoms:
60.7-82.4%,
Polar compounds:
0.1-0.8%,
loss:
6.9 to 19.4%.

  Improved classes in mineral oil (reduced sulfur content, reduced nitrogen content, higher viscosity index, lower pour point), hydrotreating the mineral oil (hydroisomerization, hydrocracking, hydrotreating, hydrotreating) As a result of finishing). This essentially reduces the aromatic component and increases the naphthene component in the presence of hydrogen.

Various information regarding the analysis of mineral oils as well as a list of mineral oils with various components can be found, for example, in T.W. Mang, W.M. Dresel (eds.): “Lubricants and Lubrication”, Wiley-VCH, Weinheim 2001; M.M. Mortier, S.M. T. T. et al. Orszulik (eds.): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2 nd ed. 1997; Bartz: “Additive fuer Schmierstoff”, Expert-Verlag, Renningen-Malmsheim 1994. Preferably, the mineral oil can be selected from Group I, Group II, and / or Group III oils, with Group II and Group III oils being preferred.

  Synthetic oils include organic esters such as diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, among which poly alpha-olefins (PAO), silicone oils, and perfluoroalkyl ethers. Is preferred. In addition, synthetic base oils derived from gas liquefaction (GTL) processes, coal liquefaction (CTL) processes, or biomass liquefaction (BTL) processes can be used. They are usually somewhat more expensive than mineral oil, but have advantages with regard to their performance.

  Natural oils are animal oils or vegetable oils, such as cow leg oil or jojoba oil.

  Base oils for lubricating oil formulations are divided into several groups by the API (American Petroleum Institute). Mineral oils are divided into Group I (non-hydrogenated) and Group II and Group III (both hydrotreated) depending on saturation, sulfur content, and viscosity index. PAO is group IV. All other base oils are included in Group V.

  These lubricating oils can also be used as a mixture and are often commercially available.

  The concentration of the polymer having an ester group in the lubricating oil composition is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and most preferably the total mass of the composition. 0.5 to 10% by mass.

  The polymer having the ester group can be mixed with a lubricating oil. Moreover, the polymer can be produced in a lubricating oil as mentioned above. In addition, the polymer having the ester group can be used as a concentrate or as a component of an additive package. The polymer having an ester group may be added to virgin oil and / or aging oil. Furthermore, polymers having ester groups can be added to the engine oil either directly or indirectly by a dilution effect using a diesel mixture containing these polymers.

  The lubricating oil composition described in detail herein may also contain further additives in addition to the polymer having ester groups for use according to the present invention. These additives include viscosity index improvers, pour point improvers, and DI additives (dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, antiwear and extreme pressure additives, friction Adjusting agent).

  Further usable viscosity index improvers include poly (iso) butene (PIB), fumarate-olefin copolymers, styrene-maleate copolymers, hydrogenated styrene-diene copolymers (HSD), and olefin copolymers (OCP). .

A compilation of viscosity index improvers and pour point improvers for lubricating oils is described in T.W. Mang, W.M. Dresel (eds.): “Lubricants and Lubrication”, Wiley-VCH, Weinheim 2001: R. M.M. Mortier, S.M. T. T. et al. Orszulik (eds.): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2 nd ed. 1997; Bartz: “Additive fuer Schmierstoff”, Expert-Verlag, Renningen-Malmsheim 1994.

  Suitable dispersants include poly (isobutylene) derivatives such as poly (isobutylene) succinimide (PIBSI); ethylene-propylene oligomers having N / O functional groups.

  Preferred detergents include metal containing compounds such as phenoxides; salicylates; thiophosphonates, especially thiopyrophosphonates, thiophosphonates, and phosphonates; sulfonates, and carbonates. These compounds can include, among others, calcium, magnesium, and barium as metals. These compounds can preferably be used in neutral or overbased form.

  In addition, antifoaming agents that are often divided into silicone-containing antifoaming agents and silicone-free antifoaming agents are of particular interest. Silicone-containing antifoaming agents include linear poly (dimethylsiloxane) and cyclic poly (dimethylsiloxane). Silicone-free defoamers that can be used are often polyethers, such as poly (ethylene glycol) or tributyl phosphate.

  In certain embodiments, the lubricating oil composition of the present invention may include a corrosion inhibitor. These are often divided into anti-rust additives and metal passivators / deactivators. Anti-rust additives used are, inter alia, sulfonates such as petroleum sulfonates, or synthetic alkylbenzene sulfonates (often overbased) such as dinonyl naphthene sulfonates; carboxylic acid derivatives such as lanolin (wool oils) ), Oxidized paraffin, zinc naphthenate, alkylated succinic acid, 4-nonylphenoxy-acetic acid, amide, and imide (N-acyl sarcosine, imidazoline derivatives); amine neutralized monoalkyl and dialkyl phosphates; morpholine, dicyclohexyl It can be an amine or diethanolamine. Metal passivators / deactivators include benzotriazole, tolyltriazole, 2-mercaptobenzothiazole, dialkyl-2,5-dimercapto-1,3,4-thiadiazole; N, N′-disalicylidene And ethylenediamine, N, N′-disalicylidenepropylenediamine; zinc dialkyldithiophosphate, and dialkyldithiocarbamate.

  A further preferred group of additives is the group of antioxidants. Examples of the antioxidant include phenols such as 2,6-di-tert-butylphenol (2,6-DTB), butylated hydroxytoluene (BHT), 2,6-di-tert-butyl-4-methyl. Phenol, 4,4'-methylenebis (2,6-di-tert-butylphenol); aromatic amines, especially alkylated diphenylamine, N-phenyl-1-naphthylamine (PNA), polymeric 2,2,4-trimethyl Dihydroquinone (TMQ); compounds containing sulfur and phosphorus, such as metal dithiophosphate, zinc dithiophosphate (ZnDTP), “OOS triester” = reaction of dithiophosphoric acid with activated double bonds from olefins , Cyclopentadiene, norbornadiene, α-pinene, polybutene, a Rylates, maleates (ashless in combustion); organic sulfur compounds such as dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates, thioglycols, thioaldehydes, sulfur-containing carboxylic acids; heterocyclic Sulfur / nitrogen compounds, especially dialkyl dimercaptothiadiazoles, 2-mercaptobenzimidazoles; zinc and methylene bis (dialkyldithiocarbamates); organophosphorus compounds such as triaryl phosphites and trialkyl phosphites; organocopper compounds, and overbases Calcium-based and magnesium-based phenolates and salicylates.

Preferred antiwear additives (AW) and extreme pressure (EP) additives include phosphorus compounds such as trialkyl phosphates, triaryl phosphates such as tricresyl phosphate, amine-neutralized monoalkyl phosphates and dialkyl phosphates. , Ethoxylated monoalkyl and dialkyl phosphates, phosphites, phosphonates, phosphines; sulfur and phosphorus containing compounds such as metal dithiophosphates such as zinc C _3-12 dialkyl dithiophosphate (ZnDTP), ammonium dialkyl dithiophosphate, antimony dialkyl Dithiophosphate, molybdenum dialkyldithiophosphate, lead dialkyldithiophosphate, "OOS triester" = from dithiophosphoric acid and olefin Products of activated double bonds of cyclopentadiene, norbornadiene, α-pinene, polybutene, acrylate ester, maleate ester, triphenyl phosphorothioate (TPPT); sulfur and nitrogen containing compounds such as , zinc bis (amyl dithiocarbamate) or methylene bis (di -n- butyl dithiocarbamate); elemental sulfur-containing sulfur compounds and H ₂ S- sulfurized hydrocarbons (diisobutylene, terpene); sulfurized glycerides and fatty acid esters; overbased sulfonates A chlorine compound, or a solid such as graphite or molybdenum disulfide.

More preferably, the antiwear additive and / or extreme pressure additive is a phosphorus compound, a compound containing sulfur and phosphorus, a compound containing sulfur and nitrogen, a sulfur compound containing elemental sulfur and H ₂ S-sulfurized hydrocarbon, sulfurized Selected from glycerides and sulfurized fatty acid esters, overbased sulfonates, chlorine compounds, graphite, or molybdenum disulfide.

  A further preferred group of additives is the group of friction modifiers. The friction modifier used is a mechanically active compound such as molybdenum disulfide, graphite (including fluorinated graphite), poly (trifluoroethylene), polyamide, polyimide; a compound that forms an adsorbing layer, such as , Long chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds that form layers by tribochemical reactions, such as saturated fatty acids, phosphate esters and thiophosphate esters, xanthogenates, sulfurized fatty acids; polymers Compounds that form such layers, such as ethoxylated dicarboxylic acid partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulfurized olefins, or organometallic compounds such as molybdenum compounds (molybdenum dithiophosphate and molybdenum dithiocarbonate) Bameto MoDTC) and combinations thereof with ZnDTP, copper-containing organic compound may include.

  Some of the additives described in detail above may achieve multiple functions. For example, ZnDTP is primarily an antiwear and extreme pressure additive, but also has the properties of an antioxidant and a corrosion inhibitor (here, a metal passivator / deactivator).

The additives described in detail above are notably T.W. Mang, W.M. Dresel (eds.): “Lubricants and Lubrication”, Wiley-VCH, Weinheim 2001; Bartz: “Additive fuer Schmierstoff”, Expert-Verlag, Renningen-Malmsheim 1994; M.M. Mortier, S.M. T. T. et al. Orszulik (eds.): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2 nd ed. 1997, described in more detail.

Preferred lubricating oil compositions have a viscosity of 10 to 120 mm ² / s, more preferably 20 to 100 mm ² / s as measured at 40 ° C. according to ASTM D 445. The kinematic viscosity KV ₁₀₀ measured at 100 ° C., preferably at least 3.5 mm ² / s, especially at least 4.0 mm ² / s, more preferably at least 5.0 mm ² / s, most preferably at least 5.4 mm ² / s.

  In certain aspects of the invention, preferred lubricating oil compositions have a viscosity index measured according to ASTM D 2270 of 100 to 400, more preferably 125 to 325, most preferably 150 to 250.

Moreover, the lubricant composition for use in the motor of the present invention preferably has a high temperature high shear of at least 2.4 mPas, more preferably at least 2.6 mPas, as measured at 150 ° C. according to ASTM D4683. (HTHS) may have a viscosity. According to a further aspect of the invention, the lubricant may preferably have a high temperature high shear of up to 10 mPas, especially up to 7 mPas, more preferably up to 5 mPas, as measured at 100 ° C. according to ASTM D4683. HTHS ₁₀₀ -HTHS _150, which is the difference in high temperature high shear (HTHS) viscosity as measured at 100 ° C. and 150 ° C., is preferably up to 4 mPas, especially up to 3.3 mPas, more preferably up to 2.5 mPas. . The ratio of the measured high-temperature high-shear at 0.99 ° C. (HTHS) viscosity high-temperature high-shear measured at 100 ° C. for (HTHS ₁₅₀₎ (HTHS) viscosity (HTHS ₁₀₀₎ is preferably up to 2.0 mPas, particularly up to 1. It has 9 mPas. High temperature high shear (HTHS) viscosity can be specified according to D4683.

  In addition, a lubricant useful as a component of the present motor can have a high shear stability index (SSI). In accordance with a useful embodiment of the present invention, the shear stability index (SSI) as measured according to ASTM D2603 Reference B (12.5 min sonication) is preferably 35 or less, more preferably 20 or less. . Preferably, a lubricant having a shear stability index (SSI) of up to 5, especially up to 2, more preferably up to 1, as measured according to DIN 51381 (30 cycles with a Bosch pump) can be used. I will.

  Lubricants useful for the present invention can preferably be designed to meet the requirements of SAE classification as specified in SAE J300. For example, viscosity grades 0W, 5W, 10W, 15W, 20W, 25W, 20, 30, 40, 50, and 60 (single grade) and 0W-40, 10W-30, 10W-60, 15W-40, 20W-20 And could be adapted to the requirements of 20W-50 (multigrade).

  As a result, the lubricant of the present invention may contain at least about 1% by volume, especially at least 5% by volume, especially at least 10% by volume, more particularly at least 20% by volume of biodiesel. Surprisingly, such a large amount of water does not cause an excessively large reduction in motor characteristics such as life, cold running performance, and fuel consumption.

  Surprisingly, the fuel dilution of motor oil has only an acceptable effect on properties such as viscosity and viscosity index and low temperature performance. In addition, the additive is highly compatible with biodiesel fuel contaminants in motor oils, so the efficiency of these additives is not unduly reduced. Moreover, the fine particles and sludge formed by biodiesel fuel can be dispersed in the lubricant by a surprising method, especially when polymers with dispersible groups are used. Regarding the influence of biodiesel components, canola oil methyl ester (RME) usually has a large amount of unsaturated groups. Therefore, a lubricant having a dispersible unit is preferred. On the other hand, palm oil methyl ester (PME) usually has a detrimental effect on low temperature performance. Such effects can be surprisingly counteracted by the engine and the ester group-containing polymer, respectively.

  The oil pumpability at low temperatures, as measured by a mini rotary viscometer (MRV), is related to the viscosity under low shear conditions at engine start. Since the MRV test is an indicator of pumpability, the engine oil must be sufficiently fluid so that it can be pumped to all engine parts after engine startup to provide adequate lubricity. ASTM D-4684-08 deals with viscosity measurements in the temperature range of −10 to −40 ° C. and describes the TP-1 MRV test. SAE J300 Engine Oil Viscosity Classification (December 1999) uses the ASTM D-4684-08 test procedure to 60 Pascal * seconds (pa * sec) or 600 poise at -35 ° C for SAE 5W-30 oil. The maximum value of is possible. Another aspect of low temperature performance measured by the TP-1 MRV test is yield stress (recorded in Pascals), where the yield stress target is “zero” Pascal, but 35 Pascals (device sensitivity limit) Any value less than) is recorded as a “zero” yield stress. A yield stress value of over 35 Pascals means an increase in the degree of undesired performance.

  The improvement achievable with the present engine could be evaluated by using engine oil aging samples. Aged samples may be CEC (Coordinating European Council) or GFC (Group Francais de Coordination) method A or B, or ROBO (Romaszewski Oil Bench Oxidation) test, or any of the following test method procedures as reported by the ROMA (Romaszewski Oil Bench Oxidation) test. It could be produced by standard oxidation tests for oil.

  The present invention will be illustrated in more detail below by examples and comparative examples, but it is not intended that the present invention be limited to these examples. All quantities are expressed in weight percent unless otherwise specified.

Example 1 and Comparative Example 1
Unused motor oil was used for a long time in a diesel engine. It was specified that the biodiesel content in this aging motor oil was at least 5.5% by mass (Comparative Example 1).

  The motor oil originally met the specification SAE 5W-30, but the aging oil did not meet the specification, especially with respect to low temperature performance. The aging motor oil is 0.1% by weight 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. The pour point depressant was added (Example 1).

  LMA (lauryl-myristyl methacrylate) is a methacrylate mixture having 12 and 14 carbon atoms in a linear alkyl residue.

  DPMA (dodecyl-pentadecyl methacrylate) is a methacrylate mixture having 12 to 15 carbon atoms in an alkyl residue containing about 20% by weight branched alkyl residue and about 80% by weight linear alkyl residue. SMA (cetyl-stearyl methacrylate) is a methacrylate mixture having mainly 16 and 18 carbon atoms in a linear alkyl residue.

  Such polyalkyl (meth) acrylate compositions are commercially available from Evonik Industries AG under the trademark VISCOPLEX®.

MRV-TP1 measurement was performed according to ASTM D-4684-08. Furthermore, kinematic viscosity was measured at 40 ° C. (KV ₄₀ ) and 100 ° C. (KV ₁₀₀ ) according to ASTM D 445. The results achieved are shown in Table 1.

Table 1

  Example 1 clearly shows that polymers having ester groups, especially polyalkyl (meth) acrylates, improve the cold start performance of aging oils to the characteristics of virgin oils. Regarding viscosity data, consider that the aging oil is within the specifications of SAE J300 5W-30 oil.

Comparative Examples 2 and 3
A commercially available 15W-40 motor oil was oxidized at 170 ° C. for 72 hours at a larger volume according to the modified GFC specification. In addition, a mixture of 10 wt% biodiesel (B100, rapeseed oil methyl ester) and 90 wt% of the same SAE 15W-40 motor oil was produced and oxidized in the same manner. Low temperature performance was evaluated using MRV-TP1 measurements at −25 ° C. according to ASTM D-4684-08.

Table 2

Examples 2 and 3
An oil mixture comprising about 90% by weight of commercially available 15W-40 motor oil and about 10% by weight of biodiesel (B100) as mentioned in Comparative Example 3 was added to about 66.2% by weight of LMA and 33 Treated with a small amount of pour point depressant based on a polyalkyl (meth) acrylate composition containing 8 wt% SMA. Such pour point depressants based on polyalkyl (meth) acrylate compositions are commercially available from Evonik Industries AG.

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification.

  The amount of pour point depressant (PPD) is given in mass% and the results achieved are shown in Table 3.

Example 4
An oil mixture comprising about 90% by weight of commercially available 15W-40 motor oil and about 10% by weight of biodiesel (B100) as mentioned in Comparative Example 3 was prepared by adding about 57.5% by weight of LMA and 42 Treated with 0.3 wt% pour point depressant based on polyalkyl (meth) acrylate composition containing 5 wt% SMA. Such pour point depressants based on polyalkyl (meth) acrylate compositions are commercially available from Evonik Industries AG.

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification. The results achieved are shown in Table 3.

Table 3

  The results of Examples 2-4 clearly show that the addition of a small amount of ester group-containing polymer, especially a polyalkyl (meth) acrylate resin, maintains the cold start performance of the oil.

Examples 5-9
A SAE 15W-40 motor oil mixture comprising about 85.5 wt% base oil mixture, 8.7 wt% DI-package, and 5.5 wt% polyalkyl (meth) acrylate composition has a viscosity index and Improve the 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. including.

  IDMA (isodecyl methacrylate) is a methacrylate mixture having about 10 carbon atoms in the branched alkyl residue.

  MMA is methyl methacrylate and NVP is N-vinyl-2-pyrrolidone.

  The polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG.

  As mentioned above, an oil mixture comprising 5.5% by weight of a polyalkyl (meth) acrylate composition that improves the viscosity index and pour point is fed with various amounts of biodiesel (according to FAME EN 14214, B100). Processed.

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification. The amount of biodiesel is given in mass% and the results achieved are shown in Table 4.

Table 4

Examples 10-13
An oil mixture comprising 5.5% by weight of a polyalkyl (meth) acrylate composition that improves viscosity index and pour point, as mentioned above, is converted to a mineral diesel comprising various amounts of about 15% by volume biodiesel. Treated according to (FAME EN 14214, B15).

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification. The amount of biodiesel is given in mass% and the results achieved are shown in Table 5.

Table 5

Examples 14-22
A SAE 5W-30 motor oil mixture comprising about 83.4 wt% base oil mixture, 13.3 wt% DI-package, and 3.3 wt% polyalkyl (meth) acrylate composition has a viscosity index and Improve the 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. including.

  The polyalkyl (meth) acrylate composition that improves viscosity index and pour point comprises about 3.7% by weight pour point depressant and 96.3% by weight viscosity index improver. The polyalkyl (meth) acrylate composition is commercially available from Evonik Industries AG.

  An oil mixture comprising 3.3% by weight of a polyalkyl (meth) acrylate composition that improves the viscosity index and pour point, as mentioned above, is mixed with various amounts of biodiesel (according to FAME EN 14214, B100). Processed.

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification. The amount of biodiesel is given in mass% and the results achieved are shown in Table 6.

Table 6

  An oil mixture comprising 3.3% by weight of a polyalkyl (meth) acrylate composition that improves the viscosity index and pour point, as mentioned above, is mixed with various amounts of minerals comprising about 15% by volume of biodiesel. Treated with diesel (B15 according to FAME EN 14214).

  The oil mixture was oxidized at 170 ° C. for 72 hours according to the modified GFC specification. The amount of biodiesel is given in mass% and the results achieved are shown in Table 7.

Table 7

  Examples 5-22 show that polymers with ester groups, especially polyalkyl (meth) acrylate compositions, which improve the viscosity index and pour point, maintain the cold start performance of the oil.

Claims (22)

  A motor designed for biodiesel compatibility, comprising a particulate filter, a motor control unit capable of injecting fuel into an engine to increase exhaust temperature, and a lubricant composition, An engine comprising an agent composition containing a polymer having at least one ester group.   The engine according to claim 1, characterized in that it meets the requirements of Euro 5 which is an exhaust emission standard.   The engine according to claim 1, further comprising a common rail system.   The engine according to any one of claims 1 to 3, characterized by comprising exhaust gas recirculation.   The engine according to any one of claims 1 to 4, wherein the particulate filter is a wall flow type filter.   The engine according to any one of claims 1 to 5, wherein the polymer having an ester group is an alkyl (meth) acrylate polymer.   The engine according to any one of claims 1 to 6, characterized in that the lubricant comprises a mixture of polymers having at least two ester groups.   The engine according to any one of claims 1 to 7, wherein the lubricant comprises an alkyl (meth) acrylate polymer and an ethylene vinyl acetate polymer.   The motor according to any one of claims 1 to 8, wherein the lubricant includes a polymer having an ester group and an olefinic polymer.   The engine according to any one of claims 1 to 9, wherein the polymer having an ester group is an alkyl (meth) acrylate polymer having a dispersible group.   11. The polymer according to claim 1, wherein the polymer having an ester group is an alkyl (meth) acrylate polymer having a unit derived from a (meth) acrylate having 23 to 4000 carbon atoms. The engine according to one item.   12. The polymer according to claim 1, wherein the polymer having an ester group is a graft copolymer having a nonpolar alkyl (meth) acrylate polymer as a graft base and a dispersible monomer as a graft layer. The listed mover.   The engine according to any one of claims 1 to 12, wherein the polymer having an ester group has a mass average molecular weight in the range of 10,000 to 600,000 g / mol. The polymer having an ester group is obtained by polymerizing a monomer composition, and the monomer composition is
a) 0 to 40% by weight of the formula (I) with respect to the weight of the monomer composition for producing the polymer:

Wherein R is hydrogen or methyl, R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently , Hydrogen or a group of formula —COOR ′, wherein R ′ is hydrogen or an alkyl group having 1 to 6 carbon atoms]], one or more ethylenically unsaturated ester compounds
b) 5 to 100% by weight of the formula (II) with respect to the weight of the monomer composition for producing the polymer:

Wherein R is hydrogen or methyl, R ⁴ is a linear or branched alkyl group having 7 to 15 carbon atoms, and R ⁵ and R ⁶ are each independently , Hydrogen or a group of formula —COOR ″ where R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms]] ,
c) 0 to 80% by weight, based on the weight of the monomer composition for producing the polymer, of formula (III):

Wherein R is hydrogen or methyl, R ⁷ is a linear or branched alkyl group having 16 to 4000 carbon atoms, and R ⁸ and R ⁹ are each independently One or more ethylenically unsaturated esters of hydrogen or a group of formula —COOR ″ ′, where R ′ ″ is hydrogen or an alkyl group having 16 to 4000 carbon atoms Compound,
The engine according to any one of claims 1 to 13, characterized in that it contains 0-50% by weight of comonomer, d) based on the weight of the monomer composition for producing the polymer.   The polymer having an ester group includes a unit derived from an ester monomer having 7 to 15 carbon atoms in the alcohol portion and a unit derived from an ester monomer having 16 to 4000 carbons in the alcohol portion, and an alcohol The mass ratio of units derived from ester monomers having 7 to 15 carbon atoms in the portion and units derived from ester monomers having 16 to 4000 carbon atoms in the alcohol portion is 3: 1 to 1.1: 1 The engine according to any one of claims 1 to 14, wherein the engine is a range. The dispersible repeating unit of the polar block of the polymer is one or more heterocyclic vinyl compounds and / or formula (IV):

[Wherein R is hydrogen or methyl, X is oxygen, sulfur, or an amino group of the formula —NH— or —NR ^a —, where R ^a is 1 to 40 carbon atoms R ¹⁰ is a group having 2 to 1000 carbon atoms and having at least one heteroatom, and R ¹¹ and R ¹² are each independently hydrogen or A group of formula —COX′R ^{10 ′} (where X ′ is oxygen or an amino group of formula —NH— or —NR ^{a ′} —, wherein R ^{a ′} is 1 to 40 R ^{10 ′} is a group having 1 to 100 carbon atoms)]] and / or a heterocyclic vinyl compound The engine according to claim 15, characterized in that:   The motor according to claim 15 or 16, wherein a mass ratio of the hydrophobic block and the polar block is in a range of 100: 1 to 1: 1.   The engine according to any one of claims 1 to 17, wherein the polymer having an ester group is a block copolymer including a block of an ester group-containing unit and an olefinic block.   The engine according to any one of claims 1 to 18, wherein the lubricant composition comprises at least one additive.   The additive is a viscosity index improver, pour point improver, dispersant, detergent, antifoam agent, corrosion inhibitor, antioxidant, antiwear additive, extreme pressure additive, and / or friction modifier. The motor according to claim 19, wherein The antiwear additive and / or extreme pressure additive is a phosphorus compound, a compound having sulfur and phosphorus, a compound containing sulfur and nitrogen, a sulfur compound containing elemental sulfur and H ₂ S-sulfurized hydrocarbon, sulfurized glyceride and sulfurized The engine according to claim 20, characterized in that it is selected from fatty acid esters, overbased sulfonates, chlorine compounds, graphite or molybdenum disulfide.   Use of a polymer having an ester group in a motor according to any one of claims 1 to 21 for improving the low temperature performance of biodiesel containing a lubricant.