JP2014501795A - Engine with improved characteristics - Google Patents

Abstract

  The present invention describes a motor designed for fuel compatibility comprising a lubricant composition comprising a highly polar polymer having at least one ester group.

Description

  The present application relates to a motor having improved characteristics. In addition, the present invention describes the use of polymers to improve the emulsion stability of lubricants.

  Today, fuel is generally obtained from fossil sources. However, because these resources are limited, alternatives are sought. Accordingly, there is a growing interest in renewable raw materials that can be used to produce fuel.

  Alternative fuels for transportation, such as methanol, ethanol, have been studied for many years in the automotive industry. While such fuels offer the advantage of reduced engine emissions, their use is accompanied by many drawbacks and limitations that must be addressed in order to be a viable alternative to gasoline.

  In view of reduced environmental quality and reduced global crude stock, the use of pure bioalcohols such as ethanol (E100) or methanol (M100) is an important goal in many countries. However, many problems ranging from various combustion properties to corrosion of sealing materials have been reported as obstacles to the use of bioalcohol as a fossil gasoline replacement. Another significant difficulty is the large amount of water formed by the combustion process or present based on the alcohol production process compared to conventional gasoline.

  The water formed during combustion tends to accumulate in the oil with the alcohol bypassing the piston ring or carried away by blow-by gas.

  Alcohol and water can accumulate in lubricating oils as a result of the use of such alternative fuels, increasing corrosion and wear problems in engines that use such alternative fuels, particularly alcohol.

  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 and results in changing the lubricant in a short period of time. Moreover, the problem is more acute in engines with high performance emission control systems and additional technical approaches for fuel saving. The higher the performance of the engine, the more susceptible it is to lubricant degradation based on excessive water content and the like.

  Lubricant degradation, particularly high water content and phase separation, has detrimental effects on various properties of the engine. These are particularly acute for flex-fuel compatible engines. High water content usually causes problems related to the cold start and cold running characteristics of the engine. In addition, motor life and fuel consumption are adversely affected by the high water content in 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.

  The use of polymers having ester groups is, for example, U.S. Pat. No. 4,290,925 which describes grafted polymethacrylate-containing N-vinyl-2-pyrrolidone useful for the preparation of stable emulsions of olefin copolymers. Known in the prior art.

  U.S. Pat. No. 4,057,623 describes a copolymer of alkyl methacrylate and N-vinyl-2-pyrrolidone useful for the preparation of water-in-oil emulsions for cosmetic applications. U.S. Pat. No. 3,519,565 describes a copolymer of alkyl methacrylate and N-vinylthiopyrrolidone useful for engine sludge and varnish reduction.

  In addition, in GB-A-2307916 (A), a viscosity index improver, which is a multifunctional olefinic copolymer having dispersion properties in combination with further additives, is the emulsion stability of the lubricant. It is disclosed that can be improved. However, there is no clue as to the highly polar polymer with ester groups. In addition, no specific mover type is disclosed.

  Therefore, in view of the prior art, an object of the present invention is to provide a solution that can be applied to existing flex fuel engines without being limited to new engine designs. Among other things, the cold start and cold travel characteristics of the flex fuel engine should be improved. Furthermore, a further object of the present invention is an improvement in lifetime and fuel consumption. These improvements should be achieved without burdening the environment.

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

  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 without using a new plant or a complex plant 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 number of different additives can be minimized.

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

  In addition, the additive should improve the emulsion stability of lubricating oils containing large amounts of water.

  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. In terms of use, claim 22 provides a solution to a potential problem.

  Accordingly, the present invention provides a motor designed for flex fuel compatibility comprising a lubricant composition, wherein the lubricant composition comprises a highly polar polymer having at least one ester group. I will provide a.

  It is thus possible to provide a motor designed for flex fuel compatibility with improved characteristics such as cold start and cold running in an unpredictable way. In addition, the engine of the present invention exhibits extended life and reduced fuel consumption.

  In addition, the engine of the present invention can increase the interval between oil changes. Thus, the motor provides a significant economic improvement based on a lower amount of motor oil for a particular mileage.

  Furthermore, the solution presented by the present invention is not limited to new engine designs, but can also be applied to existing flex fuel engines.

  Moreover, the engine of the present invention can have very high compression without adversely affecting the properties of the flex fuel engine, such as cold start and cold running, as well as life and fuel consumption.

  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 a 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. This makes it possible to minimize the number of additives. Moreover, the present polymers having ester groups are compatible with many additives. This makes it possible to adapt the lubricant to a wide variety of requirements.

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

  Surprisingly, the present polymer having ester groups improves the emulsion stability of lubricating oils containing large amounts of water.

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

  Flexible fuel vehicles (FFV) or dual fuel vehicles (colloquially called flex fuel vehicles) are designed to run on two or more fuels, usually gasoline blended with either ethanol fuel or methanol fuel. An alternative fuel vehicle equipped with an internal combustion engine, where both fuels are stored in the same common tank. In a flex fuel engine, fuel injection and spark timing are automatically adjusted according to the actual blend sensed by the electronic sensor, so any proportion of the blend can be burned in the combustion chamber. A flex-fuel vehicle is distinguished from a bi-fuel vehicle, in which two types of fuel are stored in separate tanks, one type of fuel at a time, such as compressed natural gas (CNG), liquefied petroleum. It runs on gas (LPG) or hydrogen.

  Technically, the ethanol FFV can run on any mixture of gasoline and ethanol, from pure gasoline to 100% ethanol (E100), while North American and European flex-fuel vehicles are 15% Optimized to run on the largest blend of gasoline and 85% absolute ethanol (called E85 fuel). This limitation in ethanol content has been set to reduce ethanol emissions at low temperatures, as well as to avoid cold start problems during cold periods at temperatures below 11 ° C. (52 ° F.). The alcohol content is reduced in winter, when the temperature is below 0 ° C. (32 ° F.), until the E70 winter blend in the US, or E75 from November to March in Sweden. Brazilian flex-fuel vehicles are optimized to run on any mix of E20-E25 gasoline and up to 100% aqueous ethanol fuel (E100). Brazilian flex cars have a small petrol storage container built for a cold start when the temperature drops below 15 ° C (59 ° F).

  Preferably, the motor according to the invention has at least 5% by volume, in particular at least 10% by volume, in particular 20% by volume, even more particularly at least 50% by volume, more preferably at least 80% by volume of alcohol, such as methanol and / or ethanol, Designed for fuel containing. Moreover, the motor of the present invention is preferably based on 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 gasoline. Designed.

  Preferably, the mover has a compression of at least 10: 1, more preferably at least 12: 1.

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

  Unprecedented benefits can be achieved by a motor with multi-valve technology.

  Moreover, the engine of the present invention may comprise an exhaust gas recirculation and / or secondary air system.

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

  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 engine of the present invention includes a lubricant composition comprising a highly polar polymer having at least one ester group.

  A polymer having an ester group is obtained in the context of the present invention by polymerizing a monomer composition comprising an ethylenically unsaturated compound having at least one ester group (hereinafter referred to as ester monomer). It is understood to mean a polymer. Thus, these polymers have ester groups as part of the side chain. These polymers include, among others, polyalkyl (meth) acrylate (PAMA), polyalkyl fumarate, and / or polyalkyl maleate.

  Ester monomers are known per se. Among others, (meth) acrylates, maleates, and fumarate may be mentioned, which may have different alcohol groups. The expression “(meth) acrylate” includes methacrylates and acrylates, and mixtures of the two. These monomers are widely known.

  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.

  The polymers that can be used according to the invention have a high polarity. As a result, the polymer can be a random copolymer comprising a large amount of dispersible repeating units derived from dispersible monomers. Preferably, the random copolymer comprises at least 7% by weight, more preferably at least 9% by weight, of dispersible repeating units derived from dispersible monomers. In addition, the polymer can be a graft copolymer having a nonpolar polymer as the graft base and a dispersible monomer as the graft layer. A surprising improvement is preferably 0.5-10% by weight, in particular 0.8-7% by weight, more preferably 1-5% by weight, of at least one dispersible monomer, preferably a heterocyclic vinyl compound, Can be achieved by graft copolymers comprising dispersible repeat units derived from.

  The term “repeat unit” is widely known in the art. The polymer is preferably obtained by free radical polymerization of monomers. This opens a double bond and forms a covalent bond. The repeat unit is thus derived from the monomers used.

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). Mention may be made in particular of monomers having a group containing boron, a group containing phosphorus, a group containing silicon, a group containing sulfur, a group containing oxygen, and a group containing nitrogen, with oxygen being preferred. Functionalized monomers and nitrogen functionalized monomers.

  The nonpolar graft base may comprise a small amount of dispersible repeating units, which unit is preferably less than 20 wt%, more preferably less than 10 wt%, most preferably 5 wt%, based on the weight of the nonpolar graft base. %. In a particularly suitable configuration, the nonpolar graft base comprises essentially non-dispersible repeat units.

  The non-polar graft base of the polymer with ester groups is 5 to 100% by weight, in particular 20 to 98% by weight, preferably 30 to 95% by weight, most preferably 70 to 92% by weight, 7 to 15% of alcohol groups. It may have repeating units derived from ester monomers having 1 carbon atom.

  In certain embodiments, the non-polar graft base 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 40 carbon atoms in the alcohol group.

  Furthermore, the nonpolar graft base of the polymer having an 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 a repeating unit derived from an ester monomer having 5 carbon atoms.

  The nonpolar graft base of the polymer with ester groups is preferably derived from 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 of ester monomers. Includes repeat units.

［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。 Useful polymers with ester groups or random polymer graft bases are obtained from 0 to 40% by weight, in particular from 0.1 to 30% by weight, more preferably from 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;
Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;
(Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate, and vinyl (meth) acrylate,
Is mentioned.

［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（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）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する。 The composition polymerized to produce the graft base or random polymer is preferably 5 to 100% by weight, preferably 10 to 98% by weight, particularly preferably 20 to 95% 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 One or more ethylenically unsaturated ester compounds of formula I, hydrogen or a group of formula —COOR ″, wherein R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms Containing.

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, 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、１６〜４０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（ここで、Ｒ’’’は、水素または、１６〜４０個、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）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。 Furthermore, the preferred monomer composition for producing the graft base or random polymer is 0-80% by weight, preferably 0.5-60% by weight, more preferably 2-50% by weight, most preferably 5-20% by weight. % Of formula (III):

Wherein R is hydrogen or methyl, R ⁷ is a linear or branched alkyl group having 16 to 40 carbon atoms, and R ⁸ and R ⁹ are each independently One of hydrogen or a group of formula —COOR ″ ′, where R ′ ″ is hydrogen or an alkyl group having 16 to 40, preferably 16 to 30 carbon atoms. The above ethylenically unsaturated ester compounds are included.

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.

  Ester compounds having long chain alcohol groups, in particular components (II) and (III), can be obtained by reacting, for example, (meth) acrylates, fumarate, maleate and / or the corresponding acids with long chain fatty alcohols. This generally results in a mixture of esters, for example (meth) acrylates with various long chain alcohol groups. 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); Alphalol (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); A Ropol (R) 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.
The mass ratio of the ester monomer of formula (II) and the ester monomer of formula (III) can be within a wide range. The ratio of the ester compound of formula (II) having 7 to 15 carbon atoms in the alcohol group to the ester compound of formula (III) having 16 to 40 carbon atoms in the alcohol group is preferably 50: 1 to 1. : 30, more preferably 10: 1 to 1: 3, particularly preferably 5: 1 to 1: 1.

  Furthermore, the monomer mixture for producing the graft base or random polymer comprises an ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated ester compound of formula (I), (II), and / or (III). obtain.

Preferred comonomers include
Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
Styrene, substituted styrenes having an alkyl substituent on the side chain, such as α-methyl styrene and α-ethyl styrene, substituted styrenes having an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrene, For example, monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene;
Vinyl and isoprenyl ethers;
Maleic acid and maleic acid derivatives different from those mentioned in (I), (II) and (III), such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide;
Mention may be made of fumaric acid and fumaric acid derivatives different from those mentioned in (I), (II) and (III).

  Furthermore, the monomer mixture for making the graft base may comprise a dispersible monomer.

  The proportion of comonomer is preferably 0-50% by weight, more preferably 0.1-40% by weight, most preferably 0.5-0.5% by weight of the monomer composition for producing the graft base or random polymer. 20% by mass.

  Preferred polymers that can be used according to the invention also have, in addition to the graft base, at least one graft layer comprising repeating units derived from dispersible monomers.

［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’Ｒ¹⁰’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、この場合、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、Ｒ¹⁰’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。 Dispersible monomers have been used for some time to functionalize polymeric additives in lubricating oils and are therefore known to those skilled in the art (RM Mortier, ST Orszulik (eds .): "Chemistry and Technology of Lubricants", Blackie Academic & Professional, see London, 2 ^nd ed.1997). 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 2 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 ′ —, where 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 carbons An ethylenically unsaturated polar ester compound which is a group having an atom).

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 means a monocyclic or polycyclic aromatic compound having preferably 6 to 20, in particular 6 to 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-thiadiazole, 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, acridinidine, benzopteridine, phenanthroline, and phenanthrene, each of which may be 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 dodecanoyl 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) acrylate, aminoalkyl (meth) acrylamide, hydroxyalkyl (meth) acrylate, heterocyclic (meth) acrylate, and / or carbonyl Contains (meth) acrylates.

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

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, and N- (2- (meth) acryloyloxyethyl) ethylene urea 2-acetoacetoxyethyl (meth) acrylate may be mentioned.

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, phosphorus-containing, boron-containing, and / or silicon-containing (meth) acrylates such as
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,
Diethylphosphatoethyl (meth) acrylate can be used to produce polar segment D.

  According to a highly preferred embodiment, heterocyclic vinyl compounds are used as dispersible monomers. Surprisingly, when considering other dispersible monomers, the heterocyclic vinyl compounds exhibit improved properties.

  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. Particularly preferred is the use of N- vinylimidazole and N- vinylpyrrolidone for functionalization.

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

  Of particular interest are inter alia ester groups, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, mono-2-methacryloyloxyethyl succinate, N- (2-methacryloyloxyethyl) ethylene urea. , 2-acetoacetoxyethyl methacrylate, 2- (4-morpholinyl) ethyl methacrylate, dimethylaminodiglycol methacrylate, dimethylaminoethyl methacrylate, and / or dimethylaminopropylmethacrylamide.

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

  In addition to the dispersible monomer, the composition for producing the graft layer may also include the non-dispersible monomer described in detail above. These include, inter alia, ethylenically unsaturated ester compounds of formula (I), (II), and / or (III).

  The ratio of the dispersible repeating unit is preferably in the range of 0.5% by mass to 20% by mass, more preferably in the range of 1.5% by mass to 15% by mass, most preferably, based on the mass of the polymer having an ester group. Is in the range of 2.5 mass% to 10 mass%. At the same time, these repeating units preferably have ester groups such that at least 70% by weight, more preferably at least 80% by weight, are part of the graft layer, based on the total weight of the dispersible repeating units. A segment-like structure is formed in the polymer.

  The present invention describes polymers that preferably have high oil solubility. The term “oil-soluble” means that a mixture of base oil and polymer having ester groups can be produced without forming a macrophase, which is at least 0.1% by weight, preferably at least 0.1% by weight. It has 0.5% polymer by weight. The polymer may be present in the mixture in a dispersed and / or dissolved state. 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.

Of particular interest are those having an ester group, preferably 7500-1,000,000 g / mol, more preferably 10,000-600,000 g / mol, most preferably 15,000-80. , A polymer having a weight average molecular weight M _w in the range of

The number average molecular weight M _n is preferably in the range of 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 M _w in the range 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 in the range of ~ 30,000 g / mol.

  High molecular weight polymers are particularly useful as viscosity index improvers. Polymers having a low molecular weight are particularly useful as pour point depressants and flow improvers.

Further suitable are polymers having an ester group and a polydispersity index M _w / M _n in the range of 1 to 5, more preferably in the range of 1.05 to 4. Number average molecular weight and mass average molecular weight can be determined by known processes such as gel permeation chromatography (GPC).

According to a preferred embodiment of the present invention, the polymer having an ester group is -CO-NR _{2 in} the range of 1689 to 1697 cm ⁻¹ , more preferably in the range of 1689 to 1692 cm ⁻¹ as measured by FTIR spectroscopy (25 ° C.). -Peak.

  Polymers having ester groups can have various structures. Preferably, the polymer may be present inter alia as a graft copolymer.

  Polymers having ester groups for use according to the invention can be obtained in various ways. A preferred process consists of free radical graft copolymerization known per se, in which case, for example, a nonpolar graft base is obtained in the first step and the dispersible monomer is grafted in the second step.

  Thus, according to a preferred embodiment, the polymer having an ester group is preferably a graft copolymer having a nonpolar alkyl (meth) acrylate polymer as the graft base and a dispersible monomer as the graft layer.

  For customary free radical polymerizations that are particularly suitable for preparing graft copolymers, see K. et al. Matyjaszewski, T .; P. It is described in detail in Davis, Handbook of Radical Polymerization, Wiley Interscience, Hoboken, 2002. In general, a polymerization initiator and a chain transfer agent 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-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhe Sanoate, 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, a mixture of two or more of the foregoing compounds with another compound, and the foregoing Mention may be made of mixtures with compounds which are not mentioned as compounds but which can likewise form free radicals. 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 polymerization can be carried out at standard pressure, reduced pressure, or increased pressure. The polymerization temperature is not critical. However, the temperature is generally in the range of −20 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C., more preferably 80 ° C. to 130 ° 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 solvent is selected according to the polarity of the monomers used and preferably 100N oil, a relatively light gas oil, and / or an aromatic hydrocarbon such as toluene or xylene is used.

  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 or mineral oils, the term paraffin-based fractions representing longer chains or highly branched isoalkanes, where naphthene fractions are 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 line drawing 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. Aromatic and mono-methyl-branched paraffin fractions generally range from 0 to 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 fraction of these compounds is generally ≧ 60% by weight, preferably ≧ 80% by weight, but there is no intent to impose any restrictions on this. Preferred mineral oils are in each case 0.5-30% by weight aromatic fraction, 15-40% by weight naphthoene 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 of 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 the total mass of the particular mineral oil used: Is for:
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 oils (reduced sulfur content, reduced nitrogen content, higher viscosity index, lower pour point) allow hydroprocessing (hydroisomerization, hydrocracking, hydrotreating, hydrofinishing) of the mineral oil ) As a result. 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.

  Synthetic oils include organic esters such as diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, among which polyalpha-olefins (PAO), silicone oils, and perfluoroalkyls are preferred. Ether. In addition, synthetic base oils derived from natural 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 in their performance.

  Natural oils are animal 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 corresponds to 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 in the range of 0.01 to 30% by mass, more preferably in the range of 0.1 to 20% by mass, with respect to the total mass of the composition. Most preferably, it is the range of 0.5-10 mass%.

  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 VI improvers, pour point improvers, and DI additives (dispersants, surfactants, antifoaming agents, corrosion inhibitors, antioxidants, antiwear additives and extreme pressure additives, A friction modifier).

  Further usable VI improvers are especially advantageous as polyalkyl (meth) acrylates (PAMA; dispersants, antiwear additives, and / or friction modifiers) having 1 to 30 carbon atoms in the alcohol group. (Partial N / O-functionality with additional properties) (which differs from the copolymer described in detail in claim 1), as well as poly (iso) butene (PIB), fumarate-olefin copolymers, styrene-male Acrylate copolymers, hydrogenated styrene-diene copolymers (HSD), and olefin copolymers (OCP).

  Pour point improvers include, among others, polyalkyl (meth) acrylates (PAMA) having 1 to 30 carbon atoms in the alcohol group.

A compilation of VI 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 for Schmierstoff”, Expert-Verlag, Renningen-Malmsheim 1994 is also described in detail.

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

  Preferred surfactants include metal-containing compounds such as phenol salts; 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.

  Of particular interest are further antifoaming agents, which are often divided into silicone-containing antifoaming agents and silicone-free antifoaming agents. 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 derived from olefins , Cyclopentadiene, norbornadiene, α-pinene, polybutene, a Rylate, maleate (ashless in combustion), etc .; 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 methylenebis (dialkyldithiocarbamates); organophosphorus compounds such as triaryl phosphites and trialkyl phosphites; organocopper compounds, And overbased calcium 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 phosphates and dialkyl phosphates, phosphites, phosphonates, phosphines; sulfur and phosphorus containing compounds such as metal dithiophosphates such as zinc _C3-12 dialkyldithiophosphate (ZnDTP), ammonium dialkyldithiophosphate, antimony dialkyl Dithiophosphate, molybdenum dialkyldithiophosphate, lead dialkyldithiophosphate, "OOS triester" = derived 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.

  A further preferred group of additives is the group of friction modifiers. The friction modifiers used are mechanically active compounds such as molybdenum disulfide, graphite (including fluorinated graphite), poly (trifluoroethylene), polyamide, polyimide; compounds that form the adsorbing layer, such as long Chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds that form layers by tribochemical reactions, eg saturated fatty acids, phosphate esters and thiophosphate esters, xanthogenates, sulfurized fatty acids; polymer-like Compounds that form 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 dithiol) Combination of carbamate MoDTC) and their ZnDTP, it may include copper-containing organic compounds.

  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 in the range of 10 to 120 mm ² / s, more preferably in the range of 20 to 100 mm ² / s, as measured at 40 ° C. according to ASTM D 445. Kinematic viscosity KV ₁₀₀ measured at 100 ° C. is preferably at least 5.0 mm ² / s, more preferably at least 5.2 mm ² / s, most preferably at least 5.4 mm ² / s.

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

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. . The difference in high temperature high shear (HTHS) viscosity measured at 100 ° C. and 150 ° C., HTHS ₁₀₀ -HTHS ₁₅₀ is preferably at most 4 mPas, especially at most 3.3 mPas, more preferably at most 2.5 mPas. is there. The ratio of the high temperature high shear (HTHS) viscosity measured at 100 ° C. to the high temperature high shear (HTHS) viscosity measured at ₁₅₀ ° C. (HTHS ₁₀₀ ) is preferably at most 2.0 mPas, especially at most 1.9 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) measured according to DIN 51381 (30 cycles with a Bosch pump) of at most 5, especially at most 2, more preferably at most 1 can be used. Will.

  Lubricants useful for the present invention can preferably be designed to meet the requirements of the SAE classification method 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).

  Preferably, the lubricant composition comprises a gasoline engine oil quality standard ILSAC GF-5, in particular a blend of blended oil (80%), E85 fuel (10%), and water (10%). Meet an emulsion holding bench test stating that a stable emulsion must be formed for at least 24 hours after mixing at 25 ° C.

  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 of water. Surprisingly, such large amounts of water do not cause excessively large reductions in engine characteristics such as life, cold running performance, and fuel consumption.

  Surprisingly, the present invention provides a lubricant that forms a highly stable emulsion with water. Thus, a particular aspect of the present invention is the use of highly polar polymers as emulsion stabilizers in lubricants.

  The present invention is not intended to be limiting and is described in detail herein below with reference to examples and comparative examples. Unless otherwise noted, percentages are percent by weight.

Preparation Examples List of abbreviations:
MMA = methyl methacrylate N1214MA = methacrylic ester of NAFOL 1214 L125MA = methacrylic ester of LIAL125 A1618MA = methacrylic ester of ALFOL1620 DMAEMA = dimethylaminoethyl methacrylate NVP = N-vinyl-2-pyrrolidone nDDM = n-dodecyl mercapton tBPO = t -Butyl peroctoate tBPB = t-butyl perbenzoate

Comparative Example 1
107.5 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 500 grams of L125MA, 8.5 grams of nDDM, and 2 grams of tBPO was added to the round bottom flask via an addition funnel over 2 hours. The temperature of the reaction mixture was maintained at 100 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 100 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Comparative Example 2
107.5 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 375 grams N1214MA, 125 grams MMA, 7.5 grams nDDM, and 2 grams tBPO was added to the round bottom flask via an addition funnel over 2 hours. The temperature of the reaction mixture was maintained at 100 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 100 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Comparative Example 3
111 grams of mineral oil was charged into a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 385 grams N1214MA, 100 grams MMA, 15 grams DMAEMA, 4.0 grams nDDM, and 2 grams tBPO was added to the round bottom flask via an addition funnel over 2 hours. The temperature of the reaction mixture was maintained at 100 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 100 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Comparative Example 4
112.5 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 225 grams N1214MA, 275 grams A1618MA, 5.0 grams nDDM, and 2 grams tBPO was added to the round bottom flask over 2 hours via an addition funnel. The temperature of the reaction mixture was maintained at 100 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 100 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Comparative Example 5
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 415 grams of N1214MA, 70 grams of MMA, 15 grams of NVP, and 5.0 grams of tBPO was added to the round bottom flask via an addition funnel over 2 hours. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 1
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 100 ° C. under a nitrogen atmosphere. A mixture of 485 grams of N1214MA and 3.75 grams of tBPO was added to the round bottom flask via an addition funnel over 3 hours. The temperature of the reaction mixture was maintained at 100 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 100 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 15 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 2
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 415 grams of N1214MA, 70 grams of MMA, and 5.0 grams of tBPO was added to the round bottom flask over 3 hours via an addition funnel. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 15 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 3
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 210 grams N1214MA, 275 grams A1618MA, and 7.5 grams tBPO was added to the round bottom flask via an addition funnel over 3 hours. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 15 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 4
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 320 grams N1214MA, 160 grams L125MA, 5 grams MMA, and 7.5 grams tBPO was added to the round bottom flask via an addition funnel over 3 hours. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 25 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 5
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 475 grams of N1214MA and 7.5 grams of tBPO was added to the round bottom flask over 3 hours via an addition funnel. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 25 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 6
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 450 grams N1214MA and 7.5 grams tBPO was added to the round bottom flask via an addition funnel over 3 hours. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. The temperature was raised to 130 ° C. and 50 grams of NVP was added to the reaction mixture along with 2 grams of tBPB. The reaction mixture was maintained at 130 ° C. for an additional hour. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example 7
325 grams of mineral oil was charged to a glass four-necked round bottom flask equipped with a glass stirrer, cooler, and thermocouple and heated to 110 ° C. under a nitrogen atmosphere. A mixture of 425 grams of N1214MA, 25 grams of MMA, 50 grams of NVP, and 5.0 grams of tBPO was added to the round bottom flask via an addition funnel over 2 hours. The temperature of the reaction mixture was maintained at 110 ° C. during the addition. After the addition of the mixture was complete, the reaction mixture was maintained at 110 ° C. for an additional 2 hours. Additional mineral oil was added to achieve the desired concentration of polymer in the oil.

Example of use
Emulsion stability 1.0 gram of experimental additive was mixed with 99.0 grams of API Group I oil mixture having a kinematic viscosity of 5.4 cSt at 100 ° C. 80 mL of this blend of additive and oil was transferred to a 100 mL graduated cylinder and 10 mL of ethanol / heptane (85/15 v / v) solution and 10 mL of water were added. The mixture was stirred vigorously for 5 minutes and allowed to stand at room temperature for 24 hours. Passing the test was defined as no water layer after 24 hours.

The FTIR spectroscopic additive was positioned between the silver chloride plates and sandwiched between Teflon cell holders. The additive was scanned 32 times at 4 cm ⁻¹ resolution using a Thermo Nicolet Avatar 370 FT-IR. After the background scan, the sample was scanned. The peak position of the disubstituted amine —CO—NR ₂ — was observed as a shoulder peak with respect to the strong stretching peak of carbonyl C═O.

Table 1: Additive composition

Table 2: Additive composition

Table 2: Additive composition (continued)

  The results in Tables 1 and 2 show that lubricant compositions containing the copolymers described by the present invention can improve emulsion retention of lubricating oil formulations.

  In addition, the properties of the polymer were tested using a modified emulsion stability test.

  The results in Table 3 were obtained by changing the concentration of the example additive.

Table 3: Additional results of the modified emulsion stability test ^*

  The results in Table 4 were obtained by mixing the example additives with SAE 5W-30 engine oil.

Table 4: Additional results of the modified emulsion stability test ^*

Claims (22)

  An engine designed for flex fuel compatibility comprising a lubricant composition, wherein the lubricant composition comprises a highly polar polymer having at least one ester group. Machine.   The engine according to claim 1, characterized in that it has a compression ratio of at least 10: 1.   The engine according to claim 1, further comprising a fuel injection pump.   The engine according to any one of claims 1 to 3, characterized by comprising multi-valve technology.   Engine according to any one of claims 1 to 4, characterized in that it meets the requirements of the Euro 5 emission standard.   The engine according to any one of claims 1 to 5, characterized by comprising exhaust gas recirculation.   The engine according to any one of claims 1 to 6, characterized by comprising a secondary air system.   The polymer according to claim 1, wherein the polymer having a high polarity having an ester group is a random copolymer containing at least 7% by mass of a dispersible repeating unit derived from a dispersible monomer. The engine described in the item.   The high-polarity polymer having an ester group is a random copolymer containing at least 7% by mass of a dispersible repeating unit derived from at least one heterocyclic vinyl compound. 9. The engine according to any one of up to 8.   10. The polymer according to claim 1, wherein the polymer having an ester group is a graft copolymer having a nonpolar polymer as a graft base and a dispersible monomer as a graft layer. Mover.   The motor according to claim 10, wherein the polymer having an ester group contains at least one heterocyclic vinyl compound as a graft layer.   The polymer having an ester group is a graft copolymer containing 0.5 to 10% by mass of a dispersible repeating unit derived from at least one heterocyclic vinyl compound. The engine described in 1.   13. The polymer according to claim 10, wherein the polymer having an ester group is a graft copolymer containing 1 to 5% by mass of a dispersible repeating unit derived from at least one heterocyclic vinyl compound. The engine according to any one of the above items. 14. The polymer according to claim ¹ , wherein the polymer having an ester group has a peak of —CO—NR ₂ — in the range of 1689 to 1692 cm ⁻¹ as measured by FTIR spectroscopy. The listed mover.   15. The polymer according to claim 1, wherein the polymer having an ester group is selected from polyalkyl (meth) acrylate (PAMA), polyalkyl fumarate, and / or polyalkyl maleate. The engine described in the item.   The engine according to any one of claims 1 to 15, 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 a graft polymer including a graft base obtained by polymerizing a monomer composition, and the monomer composition includes:
a) 0 to 40% by weight of the formula (I) with respect to the weight of the monomer composition for producing the nonpolar segment:

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 nonpolar segment:

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 One or more ethylenically unsaturated ester compounds of formula I, hydrogen or a group of formula —COOR ″, wherein R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms ,
c) 0 to 80% by weight of the formula (III) with respect to the weight of the monomer composition for producing the nonpolar segment:

Wherein R is hydrogen or methyl, R ⁷ is a linear or branched alkyl group having 16 to 30 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 30 carbon atoms. Compound,
17. Activation according to any one of claims 1 to 16, characterized in that it comprises 0-50% by weight of comonomer with respect to the weight of the monomer composition for producing the hydrophobic segment. Machine.   The heterocyclic vinyl compound is 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, Vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinyl From pyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole and hydrogenated vinylthiazole, vinyloxazole and hydrogenated vinyloxazole That is characterized from being selected group, movers according to any one of claims 1 to 17.   Engine according to any one of the preceding claims, characterized in that the lubricant composition comprises at least one further additive that is not a highly polar polymer with ester groups.   The additive is a viscosity index improver, pour point improver, dispersant, surfactant, defoamer, corrosion inhibitor, antioxidant, antiwear additive, extreme pressure additive, and / or friction modifier. The engine according to claim 19, wherein: 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 glyceride and fatty acid The engine according to claim 20, characterized in that it is selected from esters, overbased sulfonates, chlorinated compounds, graphite or molybdenum disulfides.   Use of highly polar polymers with ester groups as emulsion stabilizers in lubricants.