CN103249820A

CN103249820A - A motor having improved properties

Info

Publication number: CN103249820A
Application number: CN2011800496567A
Authority: CN
Inventors: J·A·朗斯顿; M·E·韦伯; P·摩尔; T·克莱斯曼; 王仁隆
Original assignee: Evonik Rohmax Additives GmbH
Current assignee: Evonik Oil Additives GmbH
Priority date: 2010-10-14
Filing date: 2011-08-23
Publication date: 2013-08-14
Also published as: EP2627742A1; KR20130108597A; US20130199482A1; BR112013008876A2; SG189247A1; JP2014501795A; CA2814558A1; RU2013121690A; WO2012048931A1

Abstract

The present invention describes a motor designed for Fuel compatibility comprising a lubricant composition comprises at least one ester group containing polymer having a high polarity.

Description

Has the engine that improves performance

Technical field

The application relates to a kind of engine that improves performance that has.In addition, the invention discloses polymkeric substance for improvement of the purposes of the stability of emulsion of lubricating oil.

Background technology

Now, fuel is obtained by fossil origin usually.Yet these resources are limited, thereby will seek substitute.Therefore, the concern to the renewable raw materials that can be used for producing fuel constantly promotes.

Garage research for many years already is used for alternative fuel such as methyl alcohol, the ethanol etc. of transportation.Though this class A fuel A provides some advantages of the engine emission that reduces, their use is accompanied by many defectives and restriction, if make them become feasible gasoline substitute, just must solve these defectives and restriction.

In view of the deterioration of eco-environmental quality and the minimizing of world's crude oil reserve, for example ethanol (E100) or methyl alcohol (M100) have become an important goal of a lot of countries to use pure biological alcohol.Yet, reported a lot of problems, the corrosion from different combustioncharacteristicss to sealing material has hindered biological alcohols as the use of the substitute of fossil class gasoline.Compare with conventional gasoline, another main obstacles be form in the combustion processes or based on a large amount of water that in the preparation process of alcohol, exists.

The water that forms in the combustion processes together with the side through piston ring or tend in oil product, accumulate by sewing the alcohol that gas carries away.

Use this alternative fuel may cause the accumulation of alcohol and water in lubricating oil, adopt this alternative fuel, the particularly corrosion of Chun engine and wear problem thereby increased.

The problems referred to above depend on the type of service of passenger vehicle.The use of automobile in the circulation of unusual short distance can cause very serious problem, and this causes the lubricating oil short period of time to change.And, more serious for having high-precision emission control systems and being used for for the engine of other technical scheme of fuel saving problem.Engine is more accurate, and its degradation to lubricating oil is more responsive, for example, and based on excessive water-content.

The degradation of lubricating oil, particularly high-moisture all have disadvantageous effect with the various performances that are separated to engine.These are especially severes for the engine with fuel flexible consistency.High-moisture may cause the problem of engine cold-start and cold operation characteristic aspect usually.In addition, the high-moisture of lubricating oil also has disadvantageous effect to work-ing life and the fuel consumption of engine.

Up to now, a lot of trials have been carried out to improve cold start-up and the cold operation characteristic of engine by engineering and new facility.Yet, these options with based on expensive and have only the shortcoming of the fact that up-to-date automobile could benefit from these improve be associated usually.Therefore, it will be useful improving the cold start-up of engine and the other chance of cold operation characteristic, work-ing life and fuel consumption.

The polymkeric substance that use contains ester group is known in the prior art, and for example US 4,290, and 925 disclose the polymethacrylate of the grafting that contains N-vinyl-2-Pyrrolidone, and it can be used for preparing stable olefin copolymer emulsion.

US 4,057, and 623 disclose the multipolymer of alkyl methacrylate and N-vinyl-2-Pyrrolidone, and it can be used for the water-in-oil emulsion that the production cosmetic applications is used.US 3,519, and 565 disclose the multipolymer of alkyl methacrylate and N-vinyl thiopyrrolidone, and it can be used for reducing engine mud and varnish.

In addition, GB2307916A discloses the stability of emulsion that multi-functional olefin copolymer vi modifiers with dispersing agent performance and other additive combination can improve lubricating oil.Yet, do not mention any about having the hint that contains the ester group polymkeric substance of high polarity.In addition, concrete engine type is not disclosed.

Summary of the invention

In view of prior art, therefore purpose of the present invention provides a kind of solution that is not limited to new engine designs and can be applicable to existing fuel flexible engine.Particularly the cold start-up of fuel flexible engine and cold operation characteristic are deserved to improve.In addition, another object of the present invention is to improve work-ing life and fuel consumption.

Should not have to realize these improvement under the situation of environmental gap.

Another object of the present invention provides for lubricated oil additives, and it provides improved cold start-up and cold operation characteristic for the fuel flexible engine.In addition, this additive should improve work-ing life and the fuel consumption of fuel flexible engine.

In addition, this additive should be simply and cheap way production, particularly should use the component that can buy acquisition.In this article, they should industrial-scale production, and does not need new factory or the factory of complex structure for this purpose.

Another object of the present invention provides a kind of additive, and it brings the performance of multiple hope in lubricating oil.This can make the number of different additive minimize.

In addition, this additive should not have any disadvantageous effect to fuel consumption or the Environmental compatibility of lubricating oil.

In addition, this additive should improve the stability of emulsion of the lubricating oil that contains the high water yield.

These purposes and clearly do not set forth but can direct derivation go out or other purpose of distinguishing is realized by the engine of all features with claim 1 by introducing context discussed herein.Suitable improvement to engine of the present invention is protected in quoting the claim of claim 1.As for purposes, claim 22 provide a kind of to based on the solution of problem.

Therefore, the invention provides a kind of engine that is designed for the fuel flexible consistency, it contains lubricating oil composition, it is characterized in that this lubricating oil composition contain at least a have high polarity contain the ester group polymkeric substance.

Therefore may provide a kind of engine that is designed for the fuel flexible consistency in a kind of unpredictalbe mode, it has improved cold start-up and cold operation characteristic.In addition, engine of the present invention shows the work-ing life of enhancing and the fuel consumption of reduction.

In addition, the function of starting of the present invention realizes the oil change interval that prolongs.Thus, based on the lower oil level on specific mileage basis, this engine provides significant improvement aspect economy.

In addition, the solution of the present invention's proposition is not limited to new engine design and can be applicable to existing fuel flexible engine.

In addition, engine of the present invention can have very high compression ratio and about the cold start-up of fuel flexible engine and cold operation characteristic and work-ing life and fuel consumption not being subjected to harmful effect.

In addition, for the employed additive of lubricating oil that obtains to address the above problem can be a kind of simple and cheap way prepare, particularly can use the component that can buy.Simultaneously, can industrial-scale production, and do not need new factory or the factory of complex structure for this purpose.

In addition, the polymkeric substance that uses according to the present invention demonstrates particularly advantageous performance profile.For example, configurable polymkeric substance is so that have unexpectedly shear stability, thereby makes lubricating oil have very long work-ing life.In addition, the additive that uses according to the present invention can bring the performance of multiple hope in lubricating oil.For example, can prepare and have comprising of outstanding low-temperature performance or viscosity performance of the lubricating oil that contains the ester group polymkeric substance of the present invention.This allows the number of different additive to minimize.In addition, the ester group polymkeric substance that contains of the present invention is compatible with many additives.This allows lubricating oil to regulate according to multiple different the requirement.

In addition, employed additive does not have any disadvantageous effect to fuel consumption or the Environmental compatibility of lubricating oil.

Unexpectedly, of the present inventionly contain the stability of emulsion that the ester group polymkeric substance improves the lubricating oil contain the high water yield.

The invention provides a kind of new engine that is designed for the fuel flexible consistency.These engines are the part of fuel flexible vehicle normally.

Fuel flexible vehicle (FFV) or dual-fuel vehicle (generically being called the fuel flexible vehicle) are a kind of alternative fuel vehicles, it has the employing of being designed for more than a kind of fuel, normally with the gasoline operating internal combustion engine of ethanol or methanol fuel blending, and two kinds of fuel all are stored in the same common fuel tank.Fuel flexible starts function to regulate spark automatically regularly with the gained blend burning of arbitrary proportion in the combustion chamber and according to the detected actual blend of electronic sensor when fuel sprays into.The fuel flexible vehicle is different from dual-fuel vehicle, in dual-fuel vehicle two kinds of fuel storage in the fuel tank that separates and engine is each adopts a kind of fuels run, for example, compressed natural gas (CNG), liquefied petroleum gas (LPG) (LPG), or hydrogen.

Though exist technology to allow ethanol FFV with any mixture running of gasoline and ethanol, but up to 100% ethanol (E100), the fuel flexible vehicle in North America and Europe is through optimizing maximum blend (the being called E85 fuel) running with 15% gasoline and 85% dehydrated alcohol from pure gasoline.The setting of this restriction in ethanol content is for during reducing the ethanol discharging under the low temperature and avoiding cold snap, is lower than the cold start-up problem under the temperature of 11 ℃ (52 ℉).Drop to 0 ℃ of area below (32 ℉) in temperature during winter, pure content is lowered to the blend in winter that adopts E70 from November to March in the U.S., or Sweden adopts E75.Brazil's fuel flexible vehicle is through optimizing with E20-E25 gasoline with up to any mixture (E100) running of 100% aqueous alcohol fuel.The resilient vehicle of Brazil is built-in with small-sized gasoline storage tank and is used for being down to 15 ℃ (59 ℉) cold start engine when following in temperature.

Preferably, being designed for of engine of the present invention contains by volume at least 5%, and particularly at least 10%, especially 20%, more especially at least 50% and more preferably at least 80% alcohol, for example fuel of methyl alcohol and/or ethanol.In addition, the preferred design of engine of the present invention is used for containing by volume at least 5%, and particularly at least 10%, especially 20%, the fuel of at least 50% and more preferably at least 80% gasoline more especially.

Preferably, this engine has at least 10: 1, more preferably at least 12: 1 compression ratio.

According to special aspects of the present invention, engine can contain fuel-injection pump.

Can realize unpredictalbe advantage by the engine with many Valves Technology.

In addition, engine of the present invention can contain gas recirculation system and/or secondary ventilation system.

Preferably, engine contains the engine management device and is used for fuel injection and spark optimization regularly.

The preferred engine of the present invention satisfies the requirement in waste gas emission standard Europe 5, more preferably satisfies the requirement in the Europe 6 of stipulating among the Directive No.715/2007/EC.

Engine of the present invention contains lubricating oil composition, its contain at least a have high polarity contain the ester group polymkeric substance.

The polymkeric substance that contains ester group should be understood in the context of the present invention and refers to that this monomer composition contains the alefinically unsaturated compounds that has at least one ester group by the available polymkeric substance of polymeric monomer composite, and it is called the ester monomer hereinafter.Therefore, these polymkeric substance contain ester group as the part of side chain.These polymkeric substance gather fumaric acid alkyl ester and/or polymaleic acid alkyl ester particularly including poly-(methyl) alkyl acrylate (PAMA).

The ester monomer itself is known.They are particularly including (methyl) acrylate, maleic acid ester and fumarate, and it can have different pure residues.Methacrylic ester and acrylate are contained in the statement of " (methyl) acrylate ", and the mixture of the two.These monomers are known.

The polymkeric substance that contains ester group preferably contains at least 40 weight %, more preferably at least 60 weight %, preferred especially at least 80 weight % and the repeating unit derived from the ester monomer of at least 90 weight % most preferably.

According to the present invention can with polymkeric substance have high polarity.Therefore, polymkeric substance can be a kind of statistical copolymer, and it contains a large amount of dispersion repeating units derived from dispersed monomer.Preferably, this statistical copolymer contains by weight at least 7%, more preferably at least 9% the dispersion repeating unit derived from dispersed monomer.In addition, polymkeric substance can be a kind of graft copolymer, its have non-polar polymer as graft base and dispersed monomer as the grafting layer.Adopt following graft copolymer can realize beat all improvement, this graft copolymer preferably contains 0.5%-10% by weight, 0.8-7% by weight particularly, more preferably by weight 1%-5% derived from least a dispersed monomer, the dispersion repeating unit of preferred heterocycle vinyl compound.

Term " repeating unit " is well known in the art.Polymkeric substance of the present invention can be preferably radical polymerization by monomer obtain.This opens to form covalent linkage with two keys.Therefore, repeating unit comes from used monomer.

Dispersed monomer is interpreted as referring to especially have the monomer of functional group, can suppose this, polymkeric substance with these functional groups can keep particle, particularly soot particulates is in dissolved state (referring to R.M.Mortier, S.T.Orszulik (editor): " Chemistry and Technology of Lubricants ", Blackie Academic﹠amp; Professional, London, the 2nd edition, 1997).These are particularly including having boracic, phosphorous, siliceous, sulfur-bearing, containing the monomer of oxygen and nitrogen-containing group, the functionalized and functionalized monomer of nitrogen of preferred oxygen.

Nonpolar graft base can contain the dispersion repeating unit of low ratio, and it is preferably by weight less than 20%, more preferably by weight less than 10% with most preferably by weight less than 5%, based on the weight of nonpolar graft base.In a specially suitable design, nonpolar graft base is substantially free of the dispersion repeating unit.

The nonpolar graft base that contains the polymkeric substance of ester group can contain 5-100% by weight, 20-98% by weight particularly, preferred 30-95% by weight and most preferably 70-92% derived from the repeating unit that has the ester monomer of 7-15 carbon atom at pure residue.

One special aspect, the nonpolar graft base that contains the polymkeric substance of ester group can contain 0-80% by weight, preferred 0.5-60% by weight, more preferably by weight 2-50% and most preferably by weight 5-20% derived from the repeating unit that has the ester monomer of 16-40 carbon atom at pure residue.

In addition, the nonpolar graft base that contains the polymkeric substance of ester group can contain 0-40% by weight, preferred 0.1-30% by weight and more preferably by weight 0.5-20% derived from the repeating unit that has the ester monomer of 1-6 carbon atom at pure residue.

The nonpolar graft base that contains the polymkeric substance of ester group preferably contains by weight at least 40%, and more preferably by weight at least 60%, preferred especially by weight at least 80% and at least 90% the repeating unit derived from the ester monomer by weight most preferably.

The mixture that can be used for obtaining the available graft base that contains ester group polymkeric substance or statistics and convergence thing can contain 0-40% by weight, particularly 0.1-30% and more preferably connect the ethylenic unsaturated ester compound of one or more formulas (I) of weight meter 0.5-20% by weight

Wherein R is hydrogen or methyl, R ¹Be the straight or branched alkyl with 1-6 carbon atom, R ²And R ³Be respectively the group of hydrogen or formula-COOR ' independently, wherein R ' is hydrogen or the alkyl with 1-6 carbon atom.

The example of component (I) comprises (methyl) acrylate, fumarate and the maleic acid ester derived from saturated alcohol, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate and (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate;

(methyl) vinylformic acid cycloalkyl ester is (methyl) vinylformic acid cyclopentyl ester, (methyl) vinylformic acid cyclohexyl ester for example;

Derived from (methyl) acrylate of unsaturated alcohol, for example (methyl) vinylformic acid 2-propynyl ester, (methyl) vinylformic acid allyl ester and (methyl) vinylformic acid vinyl ester.

Be used for polymerization and preferably contain 5-100% by weight with the composition for preparing graft base or statistics and convergence thing, preferred 10-98% by weight and the preferred especially ethylenic unsaturated ester compound of one or more formulas (II) of 20-95% by weight

Wherein R is hydrogen or methyl, R ⁴Be the straight or branched alkyl with 7-15 carbon atom, R ⁵And R ⁶Be respectively hydrogen or formula-COOR independently " group, R wherein " be hydrogen or the alkyl with 7-15 carbon atom.

The example of component (II) comprising:

(methyl) acrylate derived from saturated alcohol, fumarate and maleic acid ester, for example (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid 2-tertiary butyl heptyl ester, (methyl) vinylformic acid octyl group ester, (methyl) vinylformic acid 3-sec.-propyl heptyl ester, (methyl) vinylformic acid nonyl ester, (methyl) vinylformic acid decyl ester, (methyl) vinylformic acid undecyl ester, (methyl) vinylformic acid 5-methyl undecyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid 2-methyl dodecyl ester, (methyl) tridecyl acrylate, (methyl) vinylformic acid 5-methyl tridecyl ester, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester;

Derived from (methyl) acrylate of unsaturated alcohol, (methyl) vinylformic acid oleyl ester for example; (methyl) vinylformic acid cycloalkyl ester, for example (methyl) vinylformic acid 3-vinyl cyclohexyl ester, (methyl) vinylformic acid bornyl ester;

And corresponding fumarate and maleic acid ester.

In addition, preferred monomers composition for the preparation of graft base or statistics and convergence thing contains 0-80% by weight, preferred 0.5-60% by weight, more preferably 2-50% and most preferably the ethylenic unsaturated ester compound of one or more formulas (III) of 5-20% by weight by weight

Wherein R is hydrogen or methyl, R ⁷Be to have 16-40, the straight or branched alkyl of preferred 16-30 carbon atom, R ⁸And R ⁹Be respectively hydrogen or formula-COOR independently " ' group, R wherein " ' be hydrogen or have 16-40, the alkyl of preferred 16-30 carbon atom.

The example of component (III) comprises (methyl) acrylate derived from saturated alcohol, for example (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid 2-methyl cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid 5-sec.-propyl heptadecyl ester, (methyl) vinylformic acid 4-tertiary butyl stearyl, (methyl) vinylformic acid 5-ethyl stearyl, (methyl) vinylformic acid 3-sec.-propyl stearyl, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester, (methyl) vinylformic acid hexadecyl eicosyl ester, (methyl) stearyl acrylate base eicosyl ester, (methyl) vinylformic acid docosyl ester and/or (methyl) vinylformic acid eicosyl tetratriacontane base ester;

(methyl) vinylformic acid cycloalkyl ester, (methyl) vinylformic acid 2,4 for example, 5-tri-tert-3-vinyl cyclohexyl ester, (methyl) vinylformic acid 2,3,4,5-tetra-tert cyclohexyl ester;

And corresponding fumarate and maleic acid ester.

Ester cpds with long-chain alcohol residue, component (II) and (III) particularly, can for example obtain in the following way: with (methyl) acrylate, fumarate, maleic acid ester and/or corresponding acid and long chain aliphatic alcohol reaction, it is mixture of generation ester generally, for example has the mixture of (methyl) acrylate of different long-chain alcohol residue.These Fatty Alcohol(C12-C14 and C12-C18) comprise Oxo Alcohol

7911, Oxo Alcohol

7900, Oxo Alcohol

1100; Alfol

610, Alfol 810, Lial

125 and Nafol

Type (Sasol); Alphanol

79 (ICI); Epal

610 and Epal

810 (Afton); Linevol 79, Linevol

911 and Neodol 25E (Shell); Dehydad

Hydrenol

And Lorol

Type (Cognis); Acropol

35 and Exxal 10 (Exxon Chemicals); Kalcol 2465 (Kao Chemicals).

Among the ethylenic unsaturated ester compound, (methyl) acrylate is particularly preferred, is better than maleic acid ester and fumarate, i.e. particularly preferred embodiment Chinese style (I), (II) and R (III) ², R ³, R ⁵, R ⁶, R ⁸And R ⁹Be respectively hydrogen.

The weight ratio of the ester monomer of the ester monomer of formula (II) and formula (III) can be in a wide scope.The ratio that has an ester cpds of 16-40 carbon atom at pure residue that has the ester cpds of 7-15 carbon atom and a formula (III) at pure residue of formula (II) is preferably 50: 1-1: 30, more preferably 10: 1-1: 3, preferred especially 5: 1-1: 1.

In addition, can contain ethylenically unsaturated monomer for the preparation of the monomer mixture of graft base or statistics and convergence thing, its can with formula (I), (II) and/or ethylenic unsaturated ester compound copolymerization (III).

Preferred comonomer comprises halogen ethene, for example vinylchlorid, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Vinylbenzene, the vinylbenzene that has the replacement of alkyl substituent in the side chain, for example alpha-methyl styrene and α-ethyl styrene, the vinylbenzene that has the replacement of alkyl substituent on the ring, for example Vinyl toluene and p-methylstyrene, halogenated styrenes, for example monochlorostyrene, dichlorostyrene, tribromo-benzene ethene and tetrabromo-benzene ethene;

Vinyl and prenyl ether;

Toxilic acid and those the maleic acid derivatives that is different from (I), (II) and mentions (III), for example maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide;

Fumaric acid and those the fumaric acid derivatives that is different from (I), (II) and mentions (III).

In addition, the monomer mixture for the preparation of graft base can contain dispersed monomer.

The shared ratio of comonomer is preferably 0-50 weight %, and more preferably 0.1-40 weight % and most preferably 0.5-20 weight % are based on the weight for the preparation of the monomer composition of graft base or statistics and convergence thing.

Except graft base, according to the present invention can with preferred polymers comprise at least a grafting layer, this grafting layer contains the repeating unit derived from dispersed monomer.

Dispersed monomer be used for lubricating oil polymer-type additive functionalized for some time, and be well known by persons skilled in the art (referring to R.M.Mortier therefore, S.T.Orszulik (editor): " Chemistry and Technology of Lubricants ", Blackie Academic﹠amp; Professional, London, the 2nd edition, 1997).Suitably, may use the unsaturated polarity ester cpds of olefinic of heterocycle vinyl compound and/or formula (IV) as dispersed monomer especially,

Wherein, R is hydrogen or methyl, X be oxygen, sulphur or formula-NH-or-NR ^a-amino, R wherein ^aBe to have 1-40, the alkyl of preferred 1-4 carbon atom, R ¹⁰Be to contain 2-1000, particularly 2-100 and preferred 2-20 carbon atom and have at least one heteroatoms, preferred at least two heteroatomic groups, R ¹¹And R ¹²Be hydrogen or formula-COX ' R independently of one another ^{10 '}-group, wherein X ' be oxygen or formula-NH-or-NR ^{A '}-amino, R wherein ^{A '}Be to have 1-40, the alkyl of preferred 1-4 carbon atom, R ^{10 '}Be to contain 1-100, preferred 1-30 and the more preferably group of 1-15 carbon atom.

The residue with 2-1000 carbon atom of " group that contains 2-1000 carbon " expression organic compound.Similarly definition is applicable to corresponding term.It contains aromatics and heteroaromatic group, and contains alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy, thiazolinyl, alkyloyl, alkoxycarbonyl group, also has heterolipid family group.The above-mentioned group of mentioning can be branching or non-branching.In addition, these groups can have common substituting group.Substituting group is for example, to have straight chain and the branched alkyl group of 1-6 carbon atom, for example methyl, ethyl, propyl group, butyl, amyl group, 2-methyl butyl or hexyl; Group of naphthene base, for example cyclopentyl and cyclohexyl; Aromatic group is phenyl or naphthyl for example; Amino, hydroxyl, ether, ester group and halogen root.

According to the present invention, aromatic group represents preferably to have 6-20, particularly the residue of the monocycle of 6-12 carbon atom or polynuclear aromatic compound.Heteroaromatic group is represented the aryl that CH base that wherein at least one CH base is substituted by N and/or at least two adjacent is substituted by S, NH or O, and heteroaromatic group has 3-19 carbon atom.

According to the preferred aromatics of the present invention or heteroaromatic group derived from benzene, naphthalene, biphenyl, phenyl ether, ditan, phenylbenzene dimethylmethane, benzophenone (bisphenone), sulfobenzide, thiophene, furans, pyrroles, thiazole,

Azoles, imidazoles, isothiazole, different

Azoles, pyrazoles, 1,3,4-

Diazole, 2,5-phenylbenzene-1,3,4-

Diazole, 1,3,4-thiadiazoles, 1,3,4-triazole, 2,5-phenylbenzene-1,3,4-triazole, 1,2,5-triphenyl-1,3,4-triazole, 1,2,4-

Diazole, 1,2,4-thiadiazoles, 1,2,4-triazole, 1,2,3-triazoles, pyrrotriazole, benzo [b] thiophene, benzo [b] furans, indoles, benzo [c] thiophene, benzo [c] furans, isoindole, benzo

Azoles, benzothiazole, benzoglyoxaline, benzisoxa

Azoles, benzisothiazole, benzopyrazoles, diazosulfide, benzotriazole, diphenylene-oxide, dibenzothiophene, carbazole, pyridine, dipyridyl, pyrazine, pyrazoles, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, tetrazine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, cinnolines, 1,8-naphthyridines, 1,5-naphthyridines, 1,6-naphthyridines, 1,7-naphthyridines, phthalazines, Pyridopyrimidine, purine, pteridine or quinolizine, 4H-quinolizine, phenyl ether, anthracene, benzopyrrole, benzo

Thiadiazoles, benzo

Diazole, benzo pyridine, benzopyrazines, benzopyrazines pyridine (benzopyrazidine), benzo pyrimidine, phentriazine, indolizine, pyridopyridine, imidazopyrimidine, pyrazine and pyrimidine, carbazole, acridine, azophenlyene, benzoquinoline, fen

Piperazine, thiodiphenylamine, azine (acridizine), benzo pteridine, phenanthroline and phenanthrene, wherein each also optionally is substituted.

Preferred alkyl comprises methyl, ethyl, propyl group, sec.-propyl, 1-butyl, 2-butyl, 2-methyl-propyl, tertiary butyl groups, amyl group, 2-methyl butyl, 1,1-dimethyl propyl, hexyl, heptyl, octyl group, 1,1,3,3-tetramethyl butyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and eicosyl.

Preferred cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group, and wherein each is optionally replaced by the alkyl of side chain or non-side chain.

Preferred alkyloyl comprises formyl radical, ethanoyl, propionyl, 2-methylpropionyl, butyryl radicals, pentanoyl, valeryl, caproyl, decanoyl and lauroyl.

Preferred carbalkoxy comprises methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, butoxy carbonyl, tertbutyloxycarbonyl, own oxygen carbonyl, the own oxygen carbonyl of 2-methyl, last of the ten Heavenly stems oxygen carbonyl or dodecane oxygen carbonyl.

Preferred alkoxyl group comprises that its alkyl is a kind of alkoxyl group in the above-mentioned preferred alkyl.

Preferred cycloalkyloxy comprises that its alkyl is a kind of cycloalkyloxy in the above-mentioned preferred cycloalkyl.

R ¹⁰The preferred heteroatoms that occurs in the base comprises oxygen, nitrogen, sulphur, boron, silicon and phosphorus, preferred oxygen and nitrogen.

R ¹⁰Base contains at least a, and preferably at least two kinds, more preferably at least three kinds of heteroatomss.

R in the ester cpds of formula (IV) ¹⁰Base preferably has at least two different heteroatomss.In this case, R in the ester cpds of at least a formula (IV) ¹⁰Base can contain at least one nitrogen-atoms and at least one Sauerstoffatom.

The example of the unsaturated polarity ester cpds of olefinic of formula (IV) comprises (methyl) aminoalkyl acrylate, aminoalkyl (methyl) acrylamide, (methyl) acrylic acid hydroxy alkyl ester, heterocycle (methyl) acrylate and/or contains (methyl) acrylate of carbonyl.

(methyl) acrylic acid hydroxy alkyl ester comprises (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3,4-dihydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, 2,5-dimethyl-1,6-hexylene glycol (methyl) acrylate and decamethylene-glycol (methyl) acrylate.

Suitable (methyl) acrylate that contains carbonyl comprises, for example, and (methyl) vinylformic acid 2-carboxyl ethyl ester, (methyl) vinylformic acid carboxymethyl ester, (methyl) vinylformic acid

The oxazolidinyl ethyl ester; N-(methacryloxy) methane amide; (methyl) vinylformic acid acetonyl ester; mono succinate-2-(methyl) acryloxy ethyl ester; N-(methyl) acryloyl morpholine; N-(methyl) acryl-2-Pyrrolidone; N-(2-(methyl) acryloxy ethyl)-2-Pyrrolidone; N-(3-(methyl) acryloxy propyl group)-2-Pyrrolidone; N-(2-(methyl) acryloxy pentadecyl)-2-Pyrrolidone; N-(3-(methyl) acryloxy heptadecyl)-2-Pyrrolidone and N-(2-(methyl) acryloxy ethyl) ethylidene-urea; (methyl) vinylformic acid 2-acetoacetoxy groups ethyl ester.

Heterocycle (methyl) acrylate comprises (methyl) vinylformic acid 2-(1-imidazolyl) ethyl ester, (methyl) vinylformic acid 2-(4-morpholinyl) ethyl ester and 1-(2-(methyl) acryloxy ethyl)-2-Pyrrolidone.

Cause (methyl) aminoalkyl acrylate and aminoalkyl (methyl) acrylamide, for example (methyl) vinylformic acid dimethyl aminopropyl ester, dimethylamino glycol ether (methyl) acrylate, (methyl) vinylformic acid dimethylaminoethyl ester, dimethyl aminopropyl (methyl) acrylamide, (methyl) vinylformic acid 3-diethyl amino amyl group ester and (methyl) vinylformic acid 3-dibutylamino cetyl ester in addition of concern especially.

In addition; can use phosphorous; boracic and/or siliceous (methyl) acrylate prepare polarity segment D; (methyl) vinylformic acid 2-(dimethyl phosphate) propyl diester for example; (methyl) vinylformic acid 2-(ethylidene phosphorous acid base) propyl diester; (methyl) vinylformic acid dimethyl phosphine ylmethyl ester; (methyl) vinylformic acid dimethyl phosphine acyl group ethyl ester; (methyl) acryl phosphonic acids diethyl ester; (methyl) acryl di(2-ethylhexyl)phosphate propyl diester; (methyl) vinylformic acid 2-(dibutyl phosphono) ethyl ester; boric acid 2,3-butylidene (methyl) acryl ethyl ester; methyl diethoxy (methyl) acryl Ethoxysilane; (methyl) vinylformic acid diethyl phosphate ethyl ester.

Use the heterocycle vinyl compound as dispersed monomer according to highly preferred embodiment.Astoundingly, the heterocycle vinyl compound is compared with other dispersed monomer and is shown improved performance.

Preferred heterocycle vinyl compound comprises the 2-vinyl pyridine, the 3-vinyl pyridine, 2-methyl-5-vinylpyrine, 3-ethyl-4-vinylpridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, the vinyl piperidines, the 9-vinylcarbazole, the 3-vinylcarbazole, the 4-vinylcarbazole, the 1-vinyl imidazole, the N-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, the N-vinyl pyrrolidone, the 2-vinyl pyrrolidone, the N-ethenyl pyrrolidone, the 3-ethenyl pyrrolidone, the N-caprolactam, the N-vinyl butyrate lactam, the vinyl tetrahydrofuran, the vinyl furans, the vinyl thiophene, the vinyl thiacyclopentane, vinylthiazole and hydrogenated vinyl thiazole, vinyl

Azoles and hydrogenated vinyl

Azoles, it is functionalized especially preferably to use N-vinyl imidazole and N-vinyl pyrrolidone to be used for.

More than the monomer of Xiang Shuing can be used alone or as a mixture in the form of use.

Special concern particularly contain ester group and the polymkeric substance by using following compound to obtain: methacrylic acid 2-hydroxypropyl ester, methacrylic acid 2-hydroxyethyl ester, mono succinate-2-methacryloxyethyl ester, N-(2-methacryloxyethyl) ethylidene-urea, methacrylic acid 2-acetoacetoxy groups ethyl ester, methacrylic acid 2-(4-morpholinyl) ethyl ester, dimethylamino glycol ether methacrylic ester, dimethylaminoethyl acrylate methyl base amino-ethyl ester and/or dimethylaminopropyl Methacrylamide.

Use is contained the ester group polymkeric substance and can be realized special improvement by what N-vinyl-2-tetramethyleneimine and/or N-vinyl-2-Pyrrolidone obtained.

Except dispersed monomer, also can contain the above non-dispersive monomer that has described in detail for the preparation of the composition of grafting layer.These are particularly including formula (I), (II) and/or ethylenic unsaturated ester compound (III).

Disperse the ratio of repeating unit, based on the weight that contains the ester group polymkeric substance, be preferably 0.5 weight %-20 weight %, more preferably 1.5 weight %-15 weight % and most preferably 2.5 weight %-10 weight %.Simultaneously, these repeating units preferably form segment shape structure in containing the ester group polymkeric substance, feasible preferably at least 70 weight %, and more preferably at least 80 weight % based on the gross weight of disperseing repeating unit, are the parts of grafting layer.

The polymkeric substance that the present invention describes preferably has high oil soluble.Term " oil is molten " refers to prepare base oil can not form macroscopic view with containing the ester group mixture of polymers phase, and it contains at least 0.1 weight %, the polymkeric substance of preferred at least 0.5 weight %.Described polymkeric substance can disperse in this mixture and/or solubilized form exists.Oil soluble depends on ratio and the base oil of lipotropy side chain especially.This performance is well known by persons skilled in the art and can easily regulates via the ratio of lipophilic monomer for concrete base oil.

Cause especially containing of concern of weight-average molecular weight M ester group and that preferably have especially _WBe 7500-1 000000g/mol, more preferably 10 000-600 000g/mol and the most preferably polymkeric substance of 15 000-80 000g/mol.

Number-average molecular weight M _nCan be preferably 5000-800 000g/mol, more preferably 7500-500 000g/mol and most preferably 10 000-80 000g/mol.

According to specific embodiment of the present invention, contain the polymkeric substance of ester group, preferred poly-(methyl) alkyl acrylate, the weight-average molecular weight M that can have _WBe 2000-1 000 000g/mol, particularly 20 000-800000g/mol, more preferably 40 000-500 000g/mol and most preferably 60 000-250 000g/mol.

According to other aspect of the present invention, the described ester group polymkeric substance that contains, preferred poly-(methyl) alkyl acrylate, the number-average molecular weight Mn that can have is 2 000-100 000g/mol, particularly 4 000-60 000g/mol and most preferably 5 000-30 000g/mol.

Have high molecular weight polymers and can be used as viscosity index improver especially.Have low-molecular-weight polymkeric substance and can be used as pour point reducer and FLOW IMPROVERS especially.

Suitable is to contain ester group and its heterogeneity index M in addition _W/ M _nBe 1-5, more preferably the polymkeric substance of 1.05-4.Number average and weight-average molecular weight can be by currently known methodss, and example gel permeation chromatography (GPC) is measured.

According to the preferred embodiment of the invention, contain the ester group polymkeric substance have by FTIR spectrography (25 ℃) measure at 1689-1697cm ^-1In the scope, more preferably at 1689-1692cm ^-1In the scope-CO-NR ₂-peak.

The polymkeric substance that contains ester group can have multiple structure.Preferably, the form that this polymkeric substance especially can graft copolymer exists.

The polymkeric substance that contains ester group that uses according to the present invention can obtain in every way.Preferable methods is the free radical grafting copolymerization reaction, itself is known, wherein, for example, obtains nonpolar graft base in the first step, in second step dispersed monomer is grafted in the described substrate.

Therefore, according to embodiment preferred, the polymkeric substance that contains ester group is preferably graft copolymer, its have nonpolar (methyl) acrylic acid alkyl ester polymer as graft base and dispersed monomer as the grafting layer.

Common Raolical polymerizable, it is particularly suitable for preparing graft copolymer, is described in detail in K.Matyjaszewski, T.P.Davis, Handbook of Radical Polymerization, Wiley Interscience is among the Hoboken 2002.Usually, use polymerization starter and chain-transfer agent for this purpose.

Available initiator is included in azo initiator well known in the art; AIBN and 1 for example; 1-azo bicyclohexane nitrile; also has for example methylethyl ketone peroxide of peralcohol; diacetone peroxide; dilauroyl peroxide; peroxide-2 ethyl hexanoic acid tertiary butyl ester; ketone peroxide; the Peroxycaprylic acid tertiary butyl ester; the methyl-isobutyl ketone peroxide; cyclohexanone peroxide; dibenzoyl peroxide; peroxidized t-butyl perbenzoate; peroxidation sec.-propyl carbonic acid tertiary butyl ester; 2; two (the 2-ethyl hexanoyl base peroxides)-2 of 5-; the 5-dimethylhexane; peroxide-2 ethyl hexanoic acid tertiary butyl ester; peroxide-3; 5; 5-tri-methyl hexanoic acid tertiary butyl ester; dicumyl peroxide; 1; two (t-butyl peroxy) hexanaphthenes of 1-; 1; two (t-butyl peroxy)-3 of 1-; 3; the 5-trimethyl-cyclohexane; the hydroperoxidation cumyl; t-butyl hydroperoxide; two (4-tert-butylcyclohexyl) esters of peroxide two carbonic acid; in the above-claimed cpd two or more mixture each other, and above-claimed cpd and not mentioned but can form the mixture of the compound of free radical equally.Suitable chain-transfer agent is oil soluble mercaptan particularly, and for example n-dodecyl mercaptan or 2 mercapto ethanol perhaps are selected from other chain-transfer agent of terpenes, for example terpinolene.

Polymerization can be carried out under standard pressure, decompression or elevated pressure.Polymerization temperature also is not harsh.Yet, it typically is-20 ℃ to 200 ℃, preferred 50 ℃ to 150 ℃ and more preferably 80 ℃-130 ℃.

Polymerization can be carried out being with or without under the situation of solvent.Broad understanding answered here in term " solvent ".Solvent is selected according to the polarity of used monomer, preferably uses 100N oil, light relatively gas oil and/or aromatic hydrocarbons, for example toluene or dimethylbenzene.

Except the polymkeric substance that contains ester group, lubricating oil used in the engine of the present invention also contains base oil.Base of optimum selection oil is particularly including mineral oil, synthetic oil and natural oil.

Mineral oil is own known and can buys acquisition.They are usually available from mineral oil or crude oil, and by distillation and/or refining and optional further purification and finishing technique, term " mineral oil " is particularly including the higher cut of crude oil or mineral oil.Generally speaking, under 5000Pa, the boiling point of mineral oil is higher than 200 ℃, preferably is higher than 300 ℃.Carbonization at low temperature by shale oil, the coking of bituminous coal, brown coal under excluding air distillation and the production of the hydrogenation of bituminous coal or brown coal be possible equally.Therefore, mineral oil has the hydrocarbon of aromatic series, ring-type, branching and the straight chain of the different ratios that depends on its source.

Usually, divide into paraffin base, cycloalkane and aromatic fractions in crude oil or mineral oil, wherein term " paraffin base fraction " is represented than long-chain or highly branched isoalkane, cycloalkane fraction representative ring alkane.In addition, mineral oil according to its source and arrangement have different ratios normal alkane, have the isoalkane (being called the monomethyl branched paraffin) of reduced branching degree, with contain heteroatoms, the compound of O, N and/or S especially, the degree of nonpolar nature is owing to described heteroatoms.Yet, be difficult to specify, because group and naphthenic hydrocarbon group that each alkane molecule can existing long chain branching have the aromatics part again.With regard to the object of the invention, for example can specify according to DIN 51 378.Polar fraction also can be determined according to ASTM D 2007.

The normal alkane ratio is less than 3 weight % in preferred mineral oils, contains the mark of compound of O, N and/or S less than 6 weight %.The mark of aromatic substance and monomethyl branched paraffin is generally 0-40 weight % in each case.According to an interested aspect, mineral oil mainly contains cycloalkane and paraffin base alkane, and they have usually greater than 13, is preferably greater than 18, most preferably greater than 20 carbon atoms.The mark of these compounds usually 〉=60 weight %, preferred 〉=80 weight %, but do not wish that this will apply restriction.Preferred mineral oils contains 0.5-30 weight % aromatic fractions, 15-40 weight % cycloalkane fraction, 35-80 weight % paraffin base fraction, 3 weight % normal alkane and 0.05-5 weight % polar compound at the most are in each case based on the gross weight of mineral oil.

By ordinary method, as the liquid chromatography on urea separation and the silica gel, the analysis that especially preferred mineral oil is carried out shows that following composition is for example arranged, and wherein percentage relates to the gross weight of employed concrete mineral oil:

The normal alkane that contains about 18-31 carbon atom:

0.7-1.0％，

The alkane that contains the slight branching of 18-31 carbon atom:

1.0-8.0％，

The aromatic substance that contains 14-32 carbon atom:

0.4-10.7％，

The isoalkane and the naphthenic hydrocarbon that contain 20-32 carbon atom:

60.7-82.4％，

Polar compound:

0.1-0.8％，

Loss:

6.9-19.4％。

The mineral oil (sulphur content of reduction, the nitrogen content of reduction, higher viscosity index, lower pour point) of improvement classification is handled (hydroisomerization, hydrocracking, hydrotreatment, hydrogenation arrangement) by the hydrogen of mineral oil and is obtained.In the presence of hydrogen, this reduces aromatic component and accumulation ring alkanes component significantly.

The valuable information relevant with the analysis of mineral oil and the mineral oil with different compositions enumerate can referring to, for example, T.Mang, W.Dresel (editor): " Lubricants and Lubrication ", Wiley-VCH, Weinheim 2001; R.M.Mortier, S.T.Orszulik (editor): " Chemistry and Technology of Lubricants ", Blackie Academic﹠amp; Professional, London, second edition, 1997; Or J.Bartz: " Additive f ü r Schmierstoffe ", Expert-Verlag, Renningen-Malmsheim 1994.

Synthetic oil comprises organic ester, for example diester and polyester, polyalkylene glycol, polyethers, synthetic hydrocarbon, particularly polyolefine, preferred poly-alpha olefins (PAO) wherein, silicone oil and perfluoroalkyl ethers.In addition, can use be derived from gas to liquid (GTL), coal to liquid (CTL) or biomass to the synthetic base oil of liquid (BTL) technology.They are more expensive slightly than mineral oil usually, still have the processing performance advantages associated with them.

Natural oil is animal or plant oil, for example neatsfoot stock or Jojoba oil.

The base oil that is used for lubricant formula is divided into several groups according to API (API).Mineral oil be divided into I group (non-hydrogen processing) and, depend on saturation ratio, sulphur content and viscosity index, be divided into II and III group (all through hydrotreatment).PAO organizes corresponding to IV.All other base oils are included in the V group.

These lubricating oil can also and be commercially available as the mixture use under many circumstances.

The concentration of polymkeric substance in lubricating oil composition that contains ester group is 0.01-30 weight % preferably, more preferably 0.1-20 weight %, and 0.5-10 weight % most preferably is based on the gross weight of described composition.

Except the described polymkeric substance that contains ester group used according to the invention, the lubricating oil composition of Xiang Shuing can also comprise other additive here.These additives comprise VI improving agent, pour point improver and DI additive (dispersion agent, purification agent, defoamer, corrosion inhibitor, antioxidant, wear-resistant and extreme-pressure additive, friction improver).

Extra available VI improving agent is particularly including poly-(methyl) alkyl acrylate (PAMA that has 1-30 carbon atom in alcohol groups; Part N/O official can have a favourable extra performance as dispersion agent, wear preventive additive and/or friction improver), it is different from the multipolymer that describes in detail in the claim 1 and vinylbenzene-diene copolymers (HSD) and the olefin copolymer (OCP) that gathers (different) butylene (PIB), fumarate-olefin copolymer, styrene-maleic acid ester copolymer, hydrogenation.

Pour point improver is particularly including poly-(methyl) alkyl acrylate (PAMA) that has 1-30 carbon atom in alcohol groups.

Be used for the VI improving agent of lubricating oil and the compilation of pour point improver and also be specified in T.Mang, W.Dresel (editor): " Lubricants and Lubrication ", Wiley-VCH, Weinheim 2001:R.M.Mortier, S.T.Orszulik (editor): " Chemistry and Technology of Lubricants ", Blackie Academic﹠amp; Professional, London, second edition, 1997; Or J.Bartz: " Additive f ü r Schmierstoffe ", Expert-Verlag is among the Renningen-Malmsheim 1994.

Suitable dispersion agent comprises poly-(iso-butylene) derivative, for example poly-(iso-butylene) succinimide (PIBSI); The ethylene-propylene oligopolymer that contains N/O functional group.

Preferred purification agent comprises metallic compound, for example phenoxide; Salicylate; Thio-phosphonates, particularly sulfo-pyrophosphonate, thio-phosphonates and phosphonate; Sulfonate and carbonate.As metal, these compounds can comprise calcium, magnesium and barium especially.These compounds can be preferably with neutral or alkalization form use excessively.

Interested especially defoamer in addition, they are divided under many circumstances and contain silicone and no silicone defoamer.Contain the silicone defoamer and comprise linear poly-(dimethyl siloxane) and ring-type poly-(dimethyl siloxane).Operable no silicone defoamer is polyethers under many circumstances, for example poly-(ethylene glycol) or tributyl phosphate.

In a specific embodiment, lubricating oil composition of the present invention can comprise corrosion inhibitor.They are divided into rust-inhibiting additive and metal passivator/deactivator under many circumstances.Employed rust-inhibiting additive especially can be sulfonate, for example sulfonated petro-leum or (alkalizing excessively under many circumstances) synthesis of alkyl benzene sulfonate, for example dinonylnaphthalene sulfonic acid salt; Carboxylic acid derivative, for example wool wax (lanolin), oxidative chain alkane, zinc naphthenate, alkylated succinic acid, 4-nonylphenoxyacetic acid, acid amides and imide (N-acyl group sarkosine, imidazolidine derivatives); List and the dialkyl group phosphoric acid salt of amine neutralization; Morpholine, dicyclohexyl amine or diethanolamine.Metal passivator/deactivator comprises benzotriazole, tolyl-triazole, 2-mercaptobenzothiazole, dialkyl group-2,5-dimercapto-1,3,4-thiadiazoles; N, N '-two salicylidene ethylene diamine, N, N '-two salicylidene trimethylene diamine; The dialkyl dithiophosphate of zinc and dialkyl dithiocarbamate.

Other preferred additives class is antioxidant.Antioxidant comprises for example phenol, for example 2,6-two-tert.-butyl phenol (2,6-DTB), Yoshinox BHT (BHT), 2,6 di tert butyl 4 methyl phenol, 4,4 '-methylene radical-two (2,6-, two-tert.-butyl phenols); Aromatic amine, particularly alkylated diphenylamine, N-phenyl-1-naphthylamine (PNA), polymer-type 2,2,4-trimethylammonium quinol (TMQ); The compound that comprises sulphur and phosphorus, for example metal dithionite is for phosphoric acid salt, zinc dithiophosphate (ZnDTP) for example, " OOS-three esters "=phosphorodithioic acid and reaction product (not having ash content during burning) from the two keys of activation of alkene, cyclopentadiene, norbornadiene, α-Pai Xi, polybutene, acrylate, maleic acid ester; Organosulfur compound is dialkyl sulfide for example, diaryl sulfide, polysulfide, modification mercaptan, thiophene derivant, xanthate, sulfo-glycol, thioaldehydes, contains thionothiolic acid; Sulphur/the nitrogen compound of heterocycle, particularly dialkyl group dimercaptothiodiazole, 2-mercaptobenzimidazole; Two (dialkyldithiocarbamacompositions) zinc and methylene-bis (dialkyl dithio amino formate); Organo phosphorous compounds, for example triarylphosphite and trialkyl phosphite; Organocopper compound and cross alkalization based on calcium with based on phenates and the salicylate of magnesium.

Preferably wear-resistant (AW) and extreme pressure (EP) additive comprise P contained compound, for example the monoalkyl of the monoalkyl of trialkylphosphate, triaryl phosphate such as Tritolyl Phosphate, amine neutralization and dialkyl phosphate, ethoxylation and dialkyl phosphate, phosphorous acid ester, phosphonic acid ester, phosphine; The compound that comprises sulphur and phosphorus, for example metal dithionite is for phosphoric acid salt such as C _3-12Zinc dialkyl dithiophosphate (ZnDTP), dialkyl dithiophosphoric acid ammonium, dialkyl dithiophosphoric acid antimony, molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid lead, " OOS three esters "=phosphorodithioic acid and reaction product from the two keys of activation of alkene, cyclopentadiene, norbornadiene, α-Pai Xi, polybutene, acrylate, maleic acid ester, tri o cresyl thiophosphate phenylester (TPPT); Comprise sulphur and nitrogen compound, for example two (diamyl disulfide is for carboxylamine) zinc or methylene-bis (second, n-butyl dithiocarbamate ester); The sulphur compound of containing element sulphur and H ₂The hydrocarbon (diisobutylene, terpenes) of S-sulfuration; Glyceryl ester and the fatty acid ester of sulfuration; Cross alkalization sulfonate; Chlorine-containing compound or solid are as graphite or molybdenumdisulphide.

Other preferred additives class is the friction improver class.Used friction modifiers can comprise mechanical activation compound for example molybdenumdisulphide, graphite (comprising the graphite of fluoridizing), poly-(trifluoro-ethylene), polymeric amide, polyimide; Form the compound of adsorption layer, for example long-chain carboxylic acid, fatty acid ester, ether, alcohol, amine, acid amides, imide; By the cambial compound of friction chemical reaction, for example saturated fatty acid, phosphoric acid and thiophosphatephosphorothioate, xanthate, sulfide aliphatic acid; The compound of formation polymer class layer is dicarboxylic acid partial ester, bialkyl ortho phthalate, methacrylic ester, unsaturated fatty acids, olefine sulfide or the organometallic compound of ethoxylation for example, the for example combination of molybdenum compound (molybdenum dithiophosphate and molybdenum dithiocarbamate MoDTC) and they and ZnDTP, the cupric organic compound.

Some additives that describe in detail above can be fulfiled multi-functional.For example, ZnDTP mainly is wear preventive additive and extreme-pressure additive, still also has antioxidant and corrosion inhibitor (: feature metal passivator/deactivator) here.

The additive that describes in detail above is especially at T.Mang, W.Dresel (editor): " Lubricants and Lubrication ", Wiley-VCH, Weinheim 2001; J.Bartz: " Additive f ü r Schmierstoffe ", Expert-Verlag, Renningen-Malmsheim 1994; R.M.Mortier, S.T.Orszulik (editor): " Chemistry and Technology of Lubricants ", Blackie Academic﹠amp; Professional, London, second edition has carried out in 1997 describing in more detail.

Preferred lubricating oil composition has 10-120mm ²/ s, more preferably 20-100mm ²The viscosity according to ASTM D 445 measurement under 40 ℃ of/s.At 100 ℃ of kinematic viscosity KV that measure down ₁₀₀5.0mm at least preferably ²/ s, particularly 5.2mm at least ²/ s, most preferably 5.4mm at least ²/ s.

Of the present invention one special aspect in, preferred lubricating oil composition has 100-400, more preferably 125-325, the most preferably viscosity index of measuring according to ASTM D 2270 of 150-250.

In addition, the lubricating oil composition that is used for engine of the present invention preferably can comprise 2.4mPas at least, more preferably at least 2.6mPas according to ASTM D4683 150 ℃ of high temperature high-shear (HTHS) viscosity of measuring down.According to a further aspect of the present invention, lubricating oil preferably can comprise maximum 10mPas, particularly 7mPas, more preferably the high temperature high-shears according to ASTM D4683 measurement under 100 ℃ of 5mPas at most at most.Difference HTHS between high temperature high-shear (HTHS) viscosity of measuring under 100 ℃ and 150 ℃ ₁₀₀-HTHS ₁₅₀Be preferably maximum 4mPas, particularly maximum 3.3mPas, more preferably maximum 2.5mPas.At 100 ℃ of high temperature high-shear (HTHS) viscosity (HTHS that measure down ₁₀₀) and at 150 ℃ of high temperature high-shear (HTHS) viscosity (HTHS that measure down ₁₅₀) ratio HTHS ₁₀₀/ HTHS ₁₅₀Be preferably maximum 2.0mPas, particularly maximum 1.9mPas.Can measure high temperature high-shear (HTHS) viscosity according to D4683.

In addition, the lubricating oil that can be used as the component of engine of the present invention can also comprise high shear stability index (SSI).According to a useful embodiment of the present invention, the shear stability index of measuring according to ASTM D2603Ref.B (12.5 minutes sonic treatment) (SSI) preferably can equal 35 or lower, more preferably equals 20 or lower.Preferably, can use have according to DIN51381 (the Bosch-pumps of 30 circulations) measure maximum 5, particularly maximum 2, the more preferably lubricating oil of maximum 1 shear stability index (SSI).

Can be used for the requirement that lubricating oil of the present invention preferably can design to satisfy the SAE classification of stipulating among the SAE J300.For example, can regulate viscosity grade 0W, 5W, the requirement of 10W, 15W, 20W, 25W, 20,30,40,50 and 60 (single-stages) and 0W-40,10W-30,10W-60,15W-40,20W-20 and 20W-50 (multistage).

Preferably, lubricating oil composition satisfies the GF-5 of petrol engine oil quality specification ILSAC, particularly emulsion keeps engine bench test, and the mixture of its regulation formulated oil (80%), E85 fuel (10%) and water (10%) must form stable emulsion and keep at least 24 hours after mixing under 0 and 25 ℃.

Therefore, lubricating oil of the present invention can contain by volume at least about 1%, and particularly at least 5%, at least 10% water especially.Amazing is that so the high water yield did not have the highland to weaken characteristic such as work-ing life, cold operation performance and the fuel consumption of engine.

Astoundingly, the invention provides the lubricating oil that a kind of and water form high stability emulsion.Therefore, a particular aspects of the present invention is to have the polymkeric substance of high polarity as the purposes of the emulsion stabilizer in the lubricating oil.

The present invention will be hereinafter reference example and Comparative Examples carry out illustrated in greater detail, but do not wish that this can apply restriction.Except as otherwise noted, per-cent is weight percentage.

Embodiment

Preparation embodiment

Acronym lists:

The MMA=methyl methacrylate

The methacrylic ester of N1214MA=NAFOL1214

The methacrylic ester of L125MA=LIAL125

The methacrylic ester of A1618MA=ALFOL 1620

DMAEMA=dimethylaminoethyl acrylate methyl base amino-ethyl ester

NVP=N-vinyl-2-Pyrrolidone

The nDDM=n-dodecyl mercaptan

TBPO=Peroxycaprylic acid tertiary butyl ester

The tBPB=t-butyl-oxybenzoate

Comparative Examples 1

The mineral oil adding of 107.5 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 100 ℃.Through two hours processes 500 gram L125MA, 8.5 gram nDDM and 2 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 100 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 100 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Comparative Examples 2

The mineral oil adding of 107.5 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 100 ℃.Through two hours processes 375 gram N1214MA, 125 gram MMA, 7.5 gram nDDM and 2 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 100 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 100 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Comparative Examples 3

The mineral oil adding of 111 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 100 ℃.Through two hours processes 385 gram N1214MA, 100 gram MMA, 15 gram DMAEMA, 4.0 gram nDDM and 2 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 100 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 100 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Comparative Examples 4

The mineral oil adding of 112.5 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 100 ℃.Through two hours processes 225 gram N1214MA, 275 gram A1618MA, 5.0 gram nDDM and 2 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 100 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 100 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Comparative Examples 5

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through two hours processes 415 gram N1214MA, 70 gram MMA, 15 gram NVP and 5.0 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 1

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 100 ℃.Through three hours processes 485 gram N1214MA and 3.75 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 100 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 100 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 15 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 2

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through three hours processes 415 gram N1214MA, 70 gram MMA and 5.0 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 15 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 3

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through three hours processes 210 gram N1214MA, 275 gram A1618MA and 7.5 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 15 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 4

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through three hours processes 320 gram N1214MA, 160 gram L125MA, 5 gram MMA and 7.5 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 25 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 5

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through three hours processes 475 gram N1214MA and 7.5 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 25 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 6

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through three hours processes 450 gram N1214MA and 7.5 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Temperature is risen to 130 ℃, in reaction mixture, add 50 gram NVP and 2 gram tBPB.Reaction mixture kept extra 1 hour at 130 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Embodiment 7

The mineral oil adding of 325 grams is equipped with four neck round bottom glass flask of glassed agitator, condenser and thermopair, and under nitrogen atmosphere, is heated to 110 ℃.Through two hours processes 425 gram N1214MA, 25 gram MMA, 50 gram NVP and 5.0 mixtures that restrain tBPO are added round-bottomed flask via feed hopper.The temperature of reaction mixture remains at 110 ℃ in the whole interpolation process.After the interpolation mixture was finished, reaction mixture kept extra 2 hours at 110 ℃.Add extra mineral oil to reach the desired concn of polymkeric substance in oil.

Purposes embodiment

Stability of emulsion

1.0 gram experimental supplement are mixed with 99.0 gram API I group oil, and the kinematic viscosity of mixture under 100 ℃ is 5.4cSt.This additive of 80mL and the mixture of oil are transferred in the 100mL graduated cylinder, to wherein adding 10mL ethanol/heptane (85/15v/v) solution and 10mL water.Stir this mixture 5 minutes rapidly and it was at room temperature left standstill 24 hours.Regulation by test is not have water layer to form during 24 hours after the end.

The FTIR spectrography

Additive is placed between the chlorination silver plate and sandwich in Teflon cuvette clamper.Use Thermo Nicolet Avatar 370FT-IR, with the resolution scan additive of 4cm-1 32 times.After sample scanning, carry out background scans.Observe two and replace amine-CO-NR ₂-peak position be set to the acromion at strong carbonyl C=O stretching peak.

Table 1: compositions of additives

Table 2: compositions of additives

Table 2: compositions of additives (continuing)

The result of table 1 and table 2 shows that the lubricating oil composition that contains the multipolymer of the present invention's description can improve the emulsion reservation of lubricating oil preparaton.

In addition, the polymer properties of the present invention that adopted improved stability of emulsion experimental test.

When changing, the concentration of embodiment additive obtains the result of table 3.

Table 3: the additional result * of improved stability of emulsion test

Embodiment	Amount of additives	Stability of emulsion
			6	0.15	By
9	0.15	By

When mixing with SAE 5W-30 engine oil, the embodiment additive obtains the result of table 4.

Table 4: the additional result of improved stability of emulsion test ^*

Embodiment	Amount of additives	Stability of emulsion
			8	0.15	By
9	0.15	By

Claims

1. engine that is designed for the fuel flexible consistency, it contains lubricating oil composition, it is characterized in that this lubricating oil composition contain at least a have high polarity contain the ester group polymkeric substance.

2. engine according to claim 1 is characterized in that this engine has at least 10: 1 compression ratio.

3. according to the engine of claim 1 or 2, it is characterized in that this engine comprises fuel-injection pump.

4. according at least one engine of aforementioned claim, it is characterized in that this engine has many Valves Technology.

5. according at least one engine of aforementioned claim, it is characterized in that this engine satisfies the requirement of Europe 5 waste gas emission standards.

6. according at least one engine of aforementioned claim, it is characterized in that this engine comprises gas recirculation system.

7. according at least one engine of aforementioned claim, it is characterized in that this engine comprises secondary ventilation system.

8. according at least one engine of aforementioned claim, it is characterized in that the described ester group polymkeric substance that contains with high polarity is a kind of statistical copolymer, it contains at least 7% the dispersion repeating unit derived from dispersed monomer by weight.

9. according at least one engine of aforementioned claim, it is characterized in that the described ester group polymkeric substance that contains with high polarity is a kind of statistical copolymer, it contains at least 7% the dispersion repeating unit derived from least a heterocycle vinyl compound by weight.

10. according at least one engine of aforementioned claim, it is characterized in that the described ester group polymkeric substance that contains is graft copolymer, its have non-polar polymer as graft base and dispersed monomer as the grafting layer.

11. according to the engine of claim 10, it is characterized in that the described ester group polymkeric substance that contains contains at least a heterocycle vinyl compound as the grafting layer.

12. according to the engine of claim 10 or 11, it is characterized in that the described ester group polymkeric substance that contains is a kind of graft copolymer, it contains the dispersion repeating unit derived from least a heterocycle vinyl compound of 0.5-10% by weight.

13. according at least one the engine of claim 10-12, it is characterized in that the described ester group polymkeric substance that contains is a kind of graft copolymer, it contains the dispersion repeating unit derived from least a heterocycle vinyl compound of 1-5% by weight.

14. according at least one engine of aforementioned claim, it is characterized in that described contain the ester group polymkeric substance have by the FTIR spectroscopy measurements at 1689-1692cm ^-1In the scope-CO-NR ₂-peak.

15. according at least one engine of aforementioned claim, it is characterized in that the described ester group polymkeric substance that contains is selected from poly-(methyl) alkyl acrylate (PAMA), poly-fumaric acid alkyl ester and/or polymaleic acid alkyl ester.

16. according at least one engine of aforementioned claim, it is characterized in that the described weight-average molecular weight that contains the ester group polymkeric substance is 10 000-600 000g/mol.

17. according at least one engine of aforementioned claim, it is characterized in that the described ester group polymkeric substance that contains is graft copolymer, it contains the graft base that can obtain by the monomer composition polymerization, this monomer composition comprises

A) based on the weight for the preparation of the monomer composition of nonpolar segment, one or more of 0-40% have the ethylenic unsaturated ester compound of formula (I) by weight

Wherein R is hydrogen or methyl, R ¹Be the straight or branched alkyl with 1-6 carbon atom, R ²And R ³Be respectively the group of hydrogen or formula-COOR ' independently, wherein R ' is hydrogen or the alkyl with 1-6 carbon atom,

B) based on the weight for the preparation of the monomer composition of nonpolar segment, one or more of 5-100% have the ethylenic unsaturated ester compound of formula (II) by weight

Wherein R is hydrogen or methyl, R ⁴Be the straight or branched alkyl with 7-15 carbon atom, R ⁵And R ⁶Be respectively hydrogen or formula-COOR independently " group, R wherein " be hydrogen or the alkyl with 7-15 carbon atom,

C) based on the weight for the preparation of the monomer composition of nonpolar segment, one or more of 0-80% have the ethylenic unsaturated ester compound of formula (III) by weight

Wherein R is hydrogen or methyl, R ⁷Be the straight or branched alkyl with 16-30 carbon atom, R ⁸And R ⁹Be respectively hydrogen or formula-COOR independently " ' group, R wherein " ' be hydrogen or the alkyl with 16-30 carbon atom,

D) based on the weight for the preparation of the monomer composition of hydrophobic segment, the comonomer of 0-50% by weight.

18. at least one engine according to aforementioned claim, it is characterized in that described heterocycle vinyl compound is selected from the 2-vinyl pyridine, the 3-vinyl pyridine, 2-methyl-5-vinylpyrine, 3-ethyl-4-vinylpridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, the vinyl piperidines, the 9-vinylcarbazole, the 3-vinylcarbazole, the 4-vinylcarbazole, the 1-vinyl imidazole, the N-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, the N-vinyl pyrrolidone, the 2-vinyl pyrrolidone, the N-ethenyl pyrrolidone, the 3-ethenyl pyrrolidone, the N-caprolactam, the N-vinyl butyrate lactam, the vinyl tetrahydrofuran, the vinyl furans, the vinyl thiophene, the vinyl thiacyclopentane, vinylthiazole and hydrogenated vinyl thiazole, vinyl

Azoles and hydrogenated vinyl

Azoles.

19. according at least one engine of aforementioned claim, it is characterized in that described lubricating oil composition contains at least a extra additive, its be not have high polarity contain the ester group polymkeric substance.

20. according to the engine of claim 19, it is characterized in that described additive is viscosity index improver, pour point improver, dispersion agent, sanitising agent, defoamer, corrosion inhibitor, antioxidant, wear preventive additive, extreme-pressure additive and/or friction improver.

21. according to the engine of claim 20, it is characterized in that wear preventive additive and/or extreme-pressure additive are selected from P contained compound, the compound of sulfur-bearing and phosphorus, sulfur-bearing and nitrogen compound contain element sulphur and H ₂The sulphur compound of S-sulfuration hydrocarbon, sulfuration glyceryl ester and fatty acid ester are crossed alkalization sulfonate, chlorine compound, graphite or molybdenumdisulphide.

22. what have high polarity contains the ester group polymkeric substance as the purposes of the emulsion stabilizer in the lubricating oil.