CN1271185C - Lubricant compsns. for driving gear - Google Patents

Lubricant compsns. for driving gear Download PDF

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Publication number
CN1271185C
CN1271185C CNB011173513A CN01117351A CN1271185C CN 1271185 C CN1271185 C CN 1271185C CN B011173513 A CNB011173513 A CN B011173513A CN 01117351 A CN01117351 A CN 01117351A CN 1271185 C CN1271185 C CN 1271185C
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alkyl
carbon atom
acid
base
lubricant compositions
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CN1317554A (en
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小宫健一
矢口彰
黑泽修
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Eneos Corp
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Nippon Mitsubishi Oil Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049Phosphite
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/68Shear stability
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Abstract

Transmission lubricant compositions comprise a mineral oil as a base oil of which by CP and by CA defined in ASTM D 3238 are 70 or more and 3 or less, respectively, a viscosity index improver, and a friction modifier. The transmission lubricant compositions have excellent low temperature fluidity, shear stability, and durability of anti-shudder properties and thus can be used for extended periods of time.

Description

The lubricant compositions that is used for transmission mechanism
The present invention relates to the transmission mechanism lubricant compositions, more particularly, the present invention relates in addition after life-time service at the anti-undiminished lubricant compositions of aspect of performance that quivers.This lubricant compositions is specially adapted to the transmission of automatic transmission and continuous variable.
In recent years, in order to reduce the expense of changing oil and to reduce the amount of waste oil, for having secular work-ing life and even after life-time service, can keeping the demand of transmission mechanism lubricant compositions of their performance to increase.
Except automatic driver, most of constantly variable transmissions all are equipped with the hydraulic speed-changing machine.Recently, in the hydraulic speed-changing machine as efficient apparatus the self-insurance clutch coupling is housed, to improve mileage, like this, except passing through the power transmission of lubricant, engine torque directly is sent to transmission mechanism.But hydraulic speed-changing machine clutch coupling is only worked in high-speed range, when the hydraulic speed-changing machine is worked in low-speed range engine torque fluctuation less, the engine torque fluctuation causes the undesired vibration of car body, causes uncomfortable riving condition.Therefore, in low-speed range, for example between the starting period, because the difference between the input and output revolution, i.e. difference between engine output and the transmission input makes to produce the power transmission loss, causes gasoline mileage to reduce.
In order to reduce the loss of such power transmission, in some automobile, use slide control device, the hydraulic speed-changing machine is worked in low-speed range in these automobiles, and the relatively sliding by clutch coupling absorbs the engine torque fluctuation.But it is exactly the undesired vibration that car body takes place that a kind of possibility is arranged, and is called at hydraulic speed-changing machine clutch surface and trembles, and causes uncomfortable driving conditions under these circumstances.In order to prevent vibration, need this lubricant to have improved μ (frictional coefficient)-V (sliding velocity) performance, frictional coefficient just increases along with the increase of sliding velocity like this.In order to improve μ-V performance, effectively use friction improver, therefore, many friction improvers have been proposed.But do not obtain satisfied result for the long-term anti-performance of quivering that continues.
These transmission mechanisms with lubricator must keep suitable viscosity, with the oilgear bearing assembly, particularly lubricated those those gear-bearing devices that use in having the transmission that needs hydraulic control device to keep suitable viscosity, are revealed from control valve so that prevent it.In addition, need this transmission lubricant in addition after the use that prolongs the cycle reduction of its viscosity be seldom.In addition, also need these transmission lubricants to have excellent low-temperature fluidity,, make gasoline mileage reduce, therefore,, particularly importantly need low temperature viscosity in order to suppress this minimizing because the ability of its anti-stirring increases under the condition of cold.
In view of the foregoing, just be starved of the lubricant that exploitation is used for transmission, this lubricant will have excellent low-temperature fluidity and shear stability except having the long-term anti-performance of quivering that continues.
An object of the present invention is to provide the transmission lubricant compositions, these compositions have and keep the stable and anti-performance of quivering of excellent shear, do not degrade after the long-time use.
According to the present invention, a kind of transmission lubricant compositions is provided, said composition contains a kind of mineral oil as base oil and is used as main component, and this is called component (A) below mineral oil, press the ASTMD3238 definition, its %C PAnd %C ABe respectively 70 or bigger and 3 or littler; A kind of viscosity index improver below is called component (B); With a kind of friction improver, below be called component (C).
Introduce the present invention in more detail below.
In the present invention, has %C PBe 70 or bigger and %C ABe 3 or littler mineral oil as component (A), %C PAnd %C AAll define by ASTMD3238.
Because component (A) satisfies %C P〉=70 and %C A≤ 3 condition, so work in coordination with use with component (B) with (C), composition of the present invention presents excellent low-temperature fluidity and the long-term lasting anti-performance of quivering.
Kinematic viscosity for component (A) has no particular limits.But the kinematic viscosity of component (A) is 1-10mm 2/ s, preferred especially 1-4mm 2/ s.Use 100 ℃ of kinematic viscosity and be 1.0mm 2/ s or bigger mineral base oil can form oil film and oilness is provided for this lubricant compositions, in addition, can reduce the vaporization losses of this base oil under the temperature that improves.Use 100 ℃ of kinematic viscosity and be 10mm 2/ s or littler mineral base oil can reduce the resistance to flow of himself, make that the lubricating composition on friction means has lower rub resistance power.Use 100 ℃ of kinematic viscosity and be 4mm 2/ s or littler mineral base oil can also improve the low-temperature fluidity of resulting lubricant compositions.
Viscosity index for component (A) has no particular limits.But, the viscosity index preferred 50 of component (A) or bigger, preferred especially 80 or bigger.Use viscosity index 50 or bigger base oil help producing form can be more excellent aspect oil film and the anti-mobile reduction lubricant compositions.
Can produce the mineral oil that is used as component (A) with any appropriate method.For example, operable mineral oil comprises paraffin base mineral oil and naphthenic mineral oil, they are that the lubricant cut that the air distillation of crude oil and underpressure distillation obtain is carried out treating process, and for example solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid scrubbing and clay treatment are with the process of appropriate combination; With N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN base mineral oil.
More particularly,, reclaim this lubricant cut then, can obtain mineral oil basis oil by refining stock oil or refining by the lubricant cut that method for refining commonly used therefrom reclaims.This stock oil distillate that can be (i) be obtained by the air distillation of paraffinic crude and/or polybase crude; The (ii) distillate that obtains by the underpressure distillation of the topped crude of paraffinic crude and/or polybase crude; The (iii) oil that obtains of oil (i) and/or mild hydrocracking (ii); (iv) two or three be selected from oil (i), (ii) and mixing oil (iii); (the v) deasphalted oil of oil (i)-(iv); (vi) oily (the oil that mild hydrocracking v) obtains; (vii) two or three be selected from oil (i)-(mixing oil vi).
To above-mentioned method for refining without limits, it can be used any method for refining in producing lubricating base oil.The object lesson of these method for refining is for example hydrocracking and hydrofinishings of (a) hydrofining; (b) for example furfural extraction of solvent treatment; (c) dewax for example solvent dewaxing and catalytic dewaxing; (d) with the clay treatment of acidic white earth or atlapulgite; (e) refining for example sulfuric acid scrubbing and caustic soda washing are learned in acid or alkalization.In the production of lubricant compositions of the present invention, can use separately or mix the above-mentioned method of using with any order.Not it should be noted that the refining condition of each method of these method for refining, the temperature and pressure in the promptly suitable selection unifining process, the feasible mineral oil that can obtain having desired properties.
Can obtain to be used as the mineral oil of component of the present invention (A) at an easy rate by following method, promptly based on the total mass of base oil, preferred 50% quality or more of using, more preferably 70% quality or more, the hydrocracking of passing through of preferred especially 80% quality is selected from oil (i)-(the vii) stock oil of component of producing itself or lubricant cut that therefrom reclaims; Resulting product of solvent dewaxing or catalytic dewaxing itself or the lubricant cut that therefrom reclaims; With resulting product of solvent treatment or resulting product after solvent dewaxing or this solvent treatment of catalytic dewaxing for example.
The mixture of component (A) refined mineral oil that can be two or more obtain by any above-mentioned process for purification or the single refined mineral oil that obtains by same method.But under any circumstance, the mineral oil that is used as component of the present invention (A) must satisfy %C P〉=70 and %C A≤ 3 condition.In other words, as long as they satisfy these conditions, the mineral oil of any kind of can be used as component (A).Therefore, the mineral oil that can be used as component (A) can contain a spot of synthetic oil for example poly-alpha olefins and ester group synthetic oil.
Suitable viscosity index improver, component promptly of the present invention (B) are non-decentralized and viscosity index improver decentralized.
The object lesson of non-dispersive type viscosity index improver is the polymkeric substance that obtains of the monomer by one or more following formulas of polymerization (1), (2) and (3) expression or the hydride of multipolymer and these polymkeric substance:
Figure C0111735100081
With
The object lesson of decentralized viscosity index improver be polymerization two or more be selected from multipolymer that the compound monomer by following formula (4) and (5) expression obtains and their hydride and one or more and be selected from compound monomer and multipolymer that is selected from the compound monomer of representing by following formula (4) and (5) and their hydride by top formula (1), (2) and (3) expression:
Figure C0111735100083
With
In formula (1), R 1Be hydrogen or methyl, R 2It is alkyl with 1-18 carbon atom.
For R 2; object lesson with alkyl of 1-18 carbon atom is an alkyl; this alkyl can be a straight or branched, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl heptadecyl and octadecyl.
In formula (2), R 3Be hydrogen or methyl, R 4It is alkyl with 1-12 carbon atom.
Object lesson with alkyl of 1-12 carbon atom is an alkyl, and this alkyl is a straight or branched, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl and dodecyl; Alkenyl, it can be a straight or branched, and the position of its pair key can change, for example butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl and dodecenyl succinic; Cycloalkyl with 5-7 carbon atom, for example cyclopentyl, cyclohexyl, suberyl; Alkyl-cycloalkyl with 6-11 carbon atom, alkyl wherein can be bonded on any position of cycloalkyl, for example methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl; Aryl, for example phenyl and naphthyl; Alkylaryl with 7-12 carbon atom, alkyl wherein can be on straight or branched and any position that can be bonded to aryl, for example tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl and own phenyl; With the phenylalkyl with 7-12 carbon atom, alkyl wherein can be a straight or branched, for example benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl.
In formula (3), D 1And D 2Be hydrogen independently of one another, by formula-OR 5The residue of the alkyl alcohol with 1-18 carbon atom of expression, wherein R 5Be alkyl, perhaps by formula-NHR with 1-18 carbon atom 6The monoalkylamine with 1-18 carbon atom of expression, wherein R 6It is alkyl with 1-18 carbon atom.
For R 5And R 6, the R in the object lesson of alkyl and the formula (1) 2Cited those are identical.
In the middle of the monomer of formula (1), (2) and (3), the preferably alkyl acrylate and the alkyl methacrylate of formula (1); The alkene of formula (2), wherein R 3Be hydrogen or methyl, R 4It is alkyl with 1-12 carbon atom; The vinylbenzene of formula (2), wherein R 3Be hydrogen, R 4It is phenyl; The alpha-methyl styrene of formula (2), wherein R 3Be methyl, R 4It is phenyl; The p-methylstyrene of formula (2), wherein R 3Be hydrogen, R 4It is tolyl; The maleic acid ester of formula (3), wherein D 1And D 2Be-OR 5, R wherein 5It is alkyl; And the maleinamide of formula (3), wherein D 1And D 2Be-NHR 6, R wherein 6It is alkyl.
In formula (4), R 7Be hydrogen or methyl, R 8Be alkylidene group with 1-18 carbon atom, E 1Be amine residue or the heterocycle residue with 1 or 2 nitrogen-atoms and 0-2 Sauerstoffatom, a is integer 0 or 1.
For R 8Object lesson with alkylidene group of 1-18 carbon atom is vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base and vaccenic acid base, and what they were all can be straight or branched.
E 1The object lesson of amine residue be dimethylamino, diethylin, dipropyl amino, dibutylamino, phenylamino, toluino, dimethylbenzene amino, kharophen and benzamido.The object lesson of heterocycle residue is morpholino, pyrryl, pyridyl, picolyl, pyrrolidyl, piperidyl, quinonyl, pyrroline ketone group, pyrrolidone-base, imidazolinyl and pyrazinyl.
In formula (5), R 9Be hydrogen or methyl, E 2Be the amine residue or have the heterocycle residue of 1 or 2 nitrogen and 0-2 oxygen.
E 2The object lesson of amine residue be dimethylamino, diethylamino, dipropyl amino, dibutylamino, anilino, toluino, dimethylbenzene amino, kharophen and benzamido.The object lesson of heterocycle residue is morpholino, pyrryl, pyridyl, picolyl, pyrrolidyl, piperidyl, quinonyl, pyrroline ketone group, pyrrolidone-base, imidazolinyl and pyrazinyl.
In the middle of the monomer of formula (4), (5) and (6), preferably the dimethylaminomethyl acrylate of formula (4), wherein R 7Be methyl, R 8Be methylene radical, E 1It is dimethylamino; The diethylamino methyl acrylate of formula (4), wherein R 7Be methyl, R 8Be methylene radical, E 1It is diethylamino; The dimethyl amino ethyl methacrylate of formula (4), wherein R 7Be methyl, R 8Be ethylidene, E 1It is dimethylamino; The diethylamino ethyl-methyl acrylate of formula (4), wherein R 7Be methyl, R 8Be ethylidene, E 1It is diethylamino; The morpholino methyl acrylate of formula (4), wherein R 7Be methyl, R 8Be methylene radical, E 1It is morpholino; The morpholino ethyl-methyl acrylate of formula (4), wherein R 7Be methyl, R 8Be ethylidene, E 1It is morpholino; 2-vinyl-5-picoline, the wherein R of formula (5) 9Be hydrogen, E 2It is the 5-picolyl; And the N-vinyl pyrrolidone of formula (5), wherein R 9Be hydrogen, E 2It is pyrrolidone-base.
When monomer copolymerization that the monomer of one or more formulas (1), (2) or (3) expression and one or more formulas (4) or (5) are represented, the former monomer and the monomeric mol ratio of the latter are optional, but its scope is 80: 20-95: 5.Polymerization starter for example benzoyl peroxide in the presence of, use the method for any routine, carry out polyreaction by monomeric radical solution polymerization.
Component (B), the object lesson that is viscosity index improver is polymethacrylate, ethene-alpha-olefin copolymer and their hydride, polyisobutene and their hydride, vinylbenzene-diene-hydrogenant multipolymer, styrene-maleic anhydride copolymer and polyoxyethylene alkylphenyl ethene.These viscosity index improvers can be decentralized or non-dispersive type.But decentralized viscosity index improver preferably is because they can keep the anti-performance of quivering.
Preferred ingredients (B) is a polymethacrylate, because they are being excellent aspect the raising low-temperature fluidity.The molecular weight of polymethacrylate is preferably selected according to shear stability.In general, consider life-time service, preferred polymethacrylate is that to have weight-average molecular weight be 10000-200000, those of preferred 10000-60000.
Content for component (B) has no particular limits.In general, based on the quality of total transmission lubricant composition, the preferred 0.1-25% of its content (quality), more preferably 0.5-20% (quality).When the content of component (B) is less than 0.1% (quality), be poor, and its content just can not present the effect of its respective amount when surpassing 26% (quality) improving aspect the low-temperature fluidity.
Component of the present invention (C) is a friction improver.Suitable friction improver is to have at least one to have 6-30 in its molecule, the alkyl or alkenyl of preferred 9-24 carbon atom and do not have those of alkyl of 31 or more carbon atoms.Alkyl or alkenyl can be a straight or branched.But, be less than 6 or be not preferred, because they may be harmful in frictional behaviour in wet clutch more than those of 30 carbon atoms.
The object lesson of alkyl and thiazolinyl is that it can be those alkyl of straight or branched, for example, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; Thiazolinyl, they can be straight or brancheds, and the position of its pair key can change, for example hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, the vaccenic acid base, 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base.
Preferred friction improver of the present invention is as follows: (C-1) have at least one alkyl or alkenyl with 6-30 carbon atom but do not have the amine compound of alkyl of 31 or more carbon atoms and their derivative in its molecule;
(C-2) in its molecule, have at least one alkyl or alkenyl but do not have the phosphorus compound of alkyl of 31 or more carbon atoms and their derivative with 6-30 carbon atom; With
(C-3) in its molecule, have at least one alkyl or alkenyl but do not have the acid amides or the metal-salt of lipid acid of the alkyl of 31 or more carbon atoms with 6-30 carbon atom.
(C-1) object lesson of amine compound is the aliphatic monoamine that is expressed from the next or their alkylene oxide adduct:
The aliphatic polyamines that is expressed from the next,
With the imidazolinium compounds that is expressed from the next,
Figure C0111735100123
In formula (6), R 10Be to have 6-30 carbon atom, the alkyl or alkenyl of preferred 9-24 carbon atom; R 11And R 12Be ethylidene or propylidene independently of one another; R 13And R 14Be hydrogen or alkyl independently of one another with 1-30 carbon atom; F and g are integer 0-10 independently of one another, preferred 0-6, and f+g=0-10, preferred 0-6.
In formula (7), R 15Be to have 6-30 carbon atom, the alkyl or alkenyl of preferred 9-24 carbon atom; R 16Be ethylidene or propylidene; R 17And R 18Be hydrogen or alkyl independently of one another with 1-30 carbon atom; H is integer 1-5, preferred 1-4.
In formula (8), R 19Be to have 6-30 carbon atom, the alkyl or alkenyl of preferred 9-24 carbon atom; R 20Be ethylidene or propylidene; R 21Be hydrogen or alkyl with 1-30 carbon atom; I is integer 0-10, preferred 0-6.
R 10, R 15And R 19Alkyl or alkenyl can be straight or branched, but have a 6-30 carbon atom, preferred 9-24 carbon atom.
R 10, R 15And R 19The object lesson of alkyl or alkenyl for can being the alkyl of straight or branched, for example hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; And thiazolinyl, they can be straight or brancheds, and the position of its pair key can change, for example hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, vaccenic acid base (oil base), 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base.In the middle of them, particularly preferably be alkyl or alkenyl with 12-18 carbon atom, for example lauryl, myristyl, palmityl, stearyl, iso stearyl (16-methyl heptadecyl) and oil base are because they can provide excellent frictional behaviour in wet clutch.
Each R 13, R 14, R 17, R 18And R 21Object lesson is a hydrogen; Can be the alkyl of straight or branched, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; Thiazolinyl, they can be straight or brancheds, and the position of two keys wherein can change, for example butenyl, pentenyl, hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, the vaccenic acid base, 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base; Cycloalkyl with 5-7 carbon atom, for example cyclopentyl, cyclohexyl and suberyl; Alkyl-cycloalkyl with 6-11 carbon atom, alkyl wherein can be bonded on any position of cycloalkyl, for example methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl; Aryl is phenyl and naphthyl for example; Alkylaryl, alkyl wherein has 7-18 carbon atom, can be on straight or branched and any position that can be bonded to aryl, for example tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, undecyl phenyl and dodecylphenyl; With the arylalkyl with 7-12 carbon atom, alkyl wherein can be a straight or branched, for example benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl.
In the aliphatic monoamine of formula (6) and their alkylene oxide adduct, R in the formula (6) more preferably 13And R 14Be those of hydrogen or alkyl and f=g=0 independently of one another with 1-6 carbon atom, and R in the formula (6) 13And R 14All be hydrogen, f and g are the alkylene oxide adduct of the aliphatic monoamine of integer 0-6 and f+g=1-6 independently of one another, because they can provide excellent frictional behaviour in wet clutch.
In the aliphatic polyamines of formula (7), R in the formula (7) preferably 17And R 18Be those of hydrogen or alkyl independently of one another, because they can provide excellent frictional behaviour in wet clutch with 1-6 carbon atom.
In the imidazolinium compounds in formula (8), R wherein preferably 21Be those of hydrogen or formula (8), because they can provide excellent frictional behaviour in wet clutch with alkyl of 1-6 carbon atom.
The example of the first kind of derivative that is also referred to as the amine compound of (C-1) is the compound of sour modification, the compound of these sour modifications is to obtain by following method: the amine compound of following formula (6), (7) or (8) and the poly carboxylic acid that has the monocarboxylic acid (aliphatic acid) of 2-30 carbon atom or have a 2-30 carbon atom for example oxalic acid, phthalic acid, trimellitic acid and 1,2,4, the reaction of 5-pyromellitic acid, all or part of remaining amino and/or imino-so that neutralize, or transform all or part of remaining amino and/or imino-becomes acid amides.The example of second type is the compound of boron modification, and the compound of these boron modifications is to obtain by following method: the amine compound and the acid reaction of following formula (6), (7) or (8), so that neutralize all or part of remaining amino and/or imino-.The example of the 3rd type is the phosphoric acid salt that obtains by following method: the amine compound of following formula (6), (7) or (8) and phosphoric acid or phosphorous acid reaction, but each all has 1 or 2 alkyl that 1-30 carbon atom arranged does not have the alkyl of 31 or more carbon atom and have at least 1 hydroxyl in its molecule, so that neutralize all or part of remaining amino and/or imino-.The example of the 4th type is the alkylene oxide adduct of the amine compound that obtains by following method: the amine compound of wushu (7) or (8) and alkylene oxide be oxyethane and propylene oxide reaction for example.Except these compounds, can use by the amine compound of following formula (6), (7) or (8) being carried out the modified product that 2 kinds or multiple above-mentioned modification obtain.
Therefore, in view of the ability of the frictional behaviour that excellence is provided in wet clutch, the preferred amine compound and their derivative that are called component (C-1) are as follows:
(i) amine compound, for example lauryl amine, lauryl diethylamine, lauryl diethanolamine, dodecyl dipropanolamine, palmityl amine, stearic amine, stearyl four ethyleneamines, oil base amine, oil base propylene diamine, oil base diethanolamine and N-hydroxyethyl oil-based imidazoline;
The alkylene oxide adduct of (ii) above-mentioned amine compound (i);
(iii) above-mentioned amine compound (i) and phosphate ester acid be two-2-second hexyl phosphoric acid or the acid phosphorous acid ester salt of 2-second hexyl phosphorous acid for example for example;
(iv) above-mentioned amine compound (i), above-mentioned alkylene oxide adduct (ii) or boric acid modified product (iii) and
(v) any 2 kinds or multiple (i), mixture (ii), (iii) and (iv).
The carbon compound that is called component (C-2) is the phosphoric acid ester that following formula is represented:
Figure C0111735100161
With the phosphorous acid ester that is expressed from the next:
In formula (9), R 22Be to have 6-30 carbon atom, the alkyl or alkenyl of preferred 9-24 carbon atom; R 23And R 24Be hydrogen or alkyl independently of one another with 1-30 carbon atom, F 1, F 2, F 3And F 4Be oxygen or sulphur independently of one another, condition is F 1, F 2, F 3And F 4At least one be oxygen.
In formula (10), R 25Be to have 6-30 carbon atom, the alkyl or alkenyl of preferred 9-24 carbon atom; R 26And R 27Be hydrogen or alkyl independently of one another with 1-30 carbon atom, F 5, F 6And F 7Be oxygen or sulphur independently of one another, condition is F 5, F 6And F 7At least one be oxygen.
R 22And R 25Alkyl and thiazolinyl can be straight or branched, but have 6-30, preferred 9-24 carbon atom.Leave the carbonatoms of top specialized range, can be harmful to the frictional behaviour in the wet clutch.
R 22And R 25Alkyl and the object lesson of thiazolinyl for being the straight or branched alkyl, for example hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; And thiazolinyl, they can be straight or brancheds, and the position of its pair key can change, for example hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, vaccenic acid base (oil base), 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base.In the middle of them, particularly preferably be alkyl or alkenyl with 12-18 carbon atom, for example lauryl, myristyl, palmityl, stearyl and oil base are because they can provide excellent frictional behaviour in wet clutch.
R 23, R 24, R 26And R 27The object lesson of alkyl for can being the straight or branched alkyl, methyl for example, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; And thiazolinyl, they can be straight or brancheds, and the position of its pair key can change, for example butenyl, pentenyl, hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, vaccenic acid base (oil base), 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, the cerotene base, the cerotene base, two vaccenic acid bases, 29 carbene bases and triacontylene base; Cycloalkyl with 5-7 carbon atom, for example cyclopentyl, cyclohexyl and suberyl; Alkyl-cycloalkyl with 6-11 carbon atom, alkyl wherein can be bonded on any position of cycloalkyl, for example methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl; Aryl is phenyl and naphthyl for example; Alkylaryl, alkyl wherein has 7-18 carbon atom, can be on straight or branched and any position that can be bonded to aryl, for example tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, undecyl phenyl and dodecylphenyl; With the arylalkyl with 7-12 carbon atom, alkyl wherein can be a straight or branched, for example benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl.
Because the frictional behaviour of their excellences in wet clutch, be phosphate ester acid as the preferred phosphorus compound of component (C-2) by formula (9) expression, R wherein 23And R 24At least one be hydrogen and by the acid phosphorous acid ester of formula (10) expression, wherein R 26And R 27At least one be hydrogen.
The object lesson of derivative that is also referred to as the phosphorus compound of component (C-2) is the salt that obtains by following method: R wherein 23And R 24At least one be the acid phosphorous acid ester or the R wherein of the formula (9) of hydrogen 26And R 27At least one be for example ammonia or hydrocarbon with 1-8 carbon atom is only arranged or the amine compound reaction of hydroxyl group in its molecule of the acid phosphorous acid ester of formula (10) of hydrogen and nitrogenous compound so that neutralize all or part of remaining acid-hydrolysis.
The object lesson of such nitrogenous compound is an ammonia; Alkylamine, alkyl wherein can be a straight or branched, for example single methylamine, mono aminoethane, single propylamine, dibutyl amine, monoamylamine, single hexylamine, single heptyl amice, single octylame, dimethylamine, thyl methyl amine, diethylamine, first propylamine, second propylamine, dipropyl amine, first butylamine, second butylamine, third butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; Alkanolamine, silane alcohol base wherein can be a straight or branched, for example single carbinolamine, monoethanolamine, single Propanolamine, only son's hydramine, single amylalcohol amine, single hexanol amine, single enanthol amine, single octanol amine, single nonyl alcohol amine, dimethanolamine, methanol amine, diethanolamine, methyl alcohol Propanolamine, ethanol propanol amine, dipropanolamine, methyl alcohol butanolamine, ethanol and butanol amine, propyl alcohol butanolamine, two butanolamines, diamyl hydramine, two hexanol amine, two enanthol amine and two octanol amine; With their mixture.
Because the frictional behaviour of their excellences in wet clutch, be single Tryfac 5573 as the particularly preferred phosphorus compound of component (C-2), the dilauryl phosphoric acid ester, single stearyl phosphoric acid ester, the distearyl phosphoric acid ester, single oil base phosphoric acid ester, two oil base phosphoric acid ester, single lauryl phosphorous acid ester, dilauryl phosphorite, single stearyl phosphorous acid ester, the distearyl phosphorous acid ester, single oil base phosphorous acid ester, two oil base phosphorous acid esters, single lauryl thiophosphatephosphorothioate, the dilauryl thiophosphatephosphorothioate, single stearyl thiophosphatephosphorothioate, the distearyl thiophosphatephosphorothioate, single oil base thiophosphatephosphorothioate, two oil base thiophosphatephosphorothioates, single lauryl thiophosphite, the dilauryl thiophosphite, single stearyl thiophosphite, the distearyl thiophosphite, single oil base thiophosphite, two oil base thiophosphites; The amine salt of these phosphoric acid ester, for example single 2-second hexyl amine salt, phosphite, thiophosphate and thiophosphorous acid salt; With their mixture.
Being called the fatty acid amide of component (C-3) or the lipid acid of fatty acid metal salt can be straight or branched and saturated or unsaturated fatty acids, but their alkyl or alkenyl has 6-30, preferred 9-24 carbon atom.Lipid acid with the alkyl or alkenyl that is less than 6 or 31 or more carbon atoms is not preferred, because they can cause frictional property loss of energy in wet clutch.
The object lesson of lipid acid is the straight or branched saturated fatty acid, for example enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, margaric acid, octadecanoic acid, nondecylic acid, arachic acid, heneicosanoic acid, docosoic acid, tricosanic acid, Lignoceric acid, pentacosoic acid, hexacosanoic acid, carboceric acid, octocosoic acid, montanic acid and triacontanoic acid; With the straight or branched unsaturated fatty acids, wherein the position of two keys can change, for example heptenoic acid, octylenic acid, nonenoic acid, decylenic acid, undecylenic acid, dodecenoic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, hexadecylenic acid, heptadecenoic acid, octadecenoic acid, jecoleic acid, eicosenoic acid, heneicosene acid, Decosahedaenoic acid, tricosenoic acid, tetracosenoic acid, Timnodonic Acid, hexacosenoic acid, cerotene acid, two octadecenoic acids, two jecoleic acids and lumequeic acid.Because the frictional behaviour of their excellences in wet clutch, particularly preferred lipid acid is straight chain fatty acid, they are that for example lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and oleic acid and the straight chain fatty acid that obtains by oxo synthesis and the mixture of branched chain fatty acid obtain by various types of fat and oil.
The fatty acid amide that is called component (C-3) can be the acid amides that obtains by following reaction: nitrogenous compound for example ammonia and each molecule only has the amine compound of the alkyl of alkyl with 1-8 carbon atom or hydroxyl to react.
The object lesson of such nitrogenous compound is an ammonia; Alkylamine, alkyl wherein can be a straight or branched, for example single methylamine, mono aminoethane, single propylamine, dibutyl amine, monoamylamine, single hexylamine, single heptyl amice, single octylame, dimethylamine, thyl methyl amine, diethylamine, first propylamine, second propylamine, dipropyl amine, first butylamine, second butylamine, third butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; And alkanolamine, silane alcohol base wherein can be a straight or branched, for example single carbinolamine, monoethanolamine, single Propanolamine, only son's hydramine, single amylalcohol amine, single hexanol amine, single enanthol amine, single octanol amine, single nonyl alcohol amine, dimethanolamine, methanol amine, diethanolamine, methyl alcohol Propanolamine, ethanol propanol amine, dipropanolamine, methyl alcohol butanolamine, ethanol and butanol amine, propyl alcohol butanolamine, two butanolamines, diamyl hydramine, two hexanol amine, two enanthol amine and two octanol amine.
Because their excellent frictional behaviours in wet clutch, be lauric amide as the object lesson of the fatty acid amide of component (C-3), lauric acid diethyl amide, the single propyl alcohol acid amides of lauric acid, the tetradecanoic acid acid amides, the tetradecanoic acid diglycollic amide, tetradecanoic acid list propyl alcohol acid amides, palmitic amide, the palmitinic acid glycollic amide, palmitinic acid list propyl alcohol acid amides, stearic amide, Stearic acid diethanolamine salt, stearic acid list propyl alcohol acid amides, amine hydroxybenzene, oleic acid diethyl amide, oleic acid list propyl alcohol acid amides, the Oleum Cocois fatty amide, cocoanut fatty acid diethanolamide, coconut grease list propyl alcohol acid amides, synthetic mixed fatty acid acid amides with 12-13 carbon atom, synthetic mixed fatty acid diglycollic amide with 12-13 carbon atom, synthetic mixed fatty acid list propyl alcohol acid amides with 12-13 carbon atom, with their mixture.
The object lesson that is also referred to as the aliphatic metal acid-salt of component (C-3) is an alkaline earth salt, for example the magnesium salts of above-named any lipid acid, calcium salt and zinc salt.Because their excellent frictional behaviours in wet clutch, particularly preferred fatty acid metal salt be calcium laurate, calcium myristate, calcium palmitate, calcium stearate, calcium oleate, coco-nut oil fatty acid calcium, the synthetic mixed fatty acid calcium with 12 or 3 carbon atoms, zinc laurate, Zinc tetradecanoate, zinc palmitate, Zinic stearas, zinc oleate, coco-nut oil fatty acid zinc, have the synthetic mixed fatty acid zinc and their mixture of 12-13 carbon atom.
Can be optional any or multiple compound from said components (C-1)-(C-3), join in the transmission lubricant composition of the present invention with any appropriate vol, for example oxidative stability is just passable as long as they are not harmful to other performance of resultant composition.In order to obtain the frictional behaviour for a long time of said composition, need avoid being harmful to frictional behaviour owing to the infringement of friction improver.A large amount of adding components (C) are effective for the frictional behaviour that obtains for a long time.But too a large amount of component (C) can reduce static friction coefficient, needs this static friction coefficient very high, so that keep the coupling or the engagement of wet clutch.Therefore, the amount of component (C) is restricted to certain degree.
Therefore, based on the total mass of transmission lubricant composition of the present invention, the preferred content scope of component (C) is 0.005-3.0% (quality), more preferably 0.01-2.0% (quality).
Blended together the viscosity index improver of specific mineral base oil and appropriate amount and friction improver, can obtain transmission lubricant composition of the present invention.Though the weather resistance of the anti-performance of quivering of composition of the present invention and low-temperature fluidity are good, but in order further to improve these performances, can mix various additives, for example wear preventive additive, extreme-pressure additive, ashless dispersant, metal detergent, oxidation retarder, sanitas.Suds suppressor and dyestuff.These additives can use or mix use separately.
Wear preventive additive can be the wear preventive additive that is used for lubricant of any routine.Suitable wear inhibitor is one or more phosphorus compounds, for example the ester of monophosphate, diphosphate, triphosphate, single phosphite, diphosphorous acid salts, three phosphites or they and amine or alkanolamine.Based on the total mass of transmission lubricant composition, the content of these wear inhibitors is selected from 0.005-2% (quality).
Extreme-pressure additive can be any conventional extreme-pressure additive that is used for lubricant.Suitable extreme-pressure additive is a sulphur compound, for example disulphide, olefine sulfide and sulfurized fat and oil.Based on the total mass of transmission lubricant composition, the preferred add-on of one or more these compounds is 0.1-5.0% (quality).
Ashless dispersant can be any conventional ashless dispersant that is used for lubricant, for example has amino or the imino-compound and their the improvement product of at least one alkyl or alkenyl that 40-400 carbon atom arranged in their molecule.
Alkyl or alkenyl can be a straight or branched.Preferably by the oligopolymer of for example alkene of propylene, 1-butylene and iso-butylene or the co-oligomer deutero-branched-chain alkyl or the thiazolinyl of ethene and propylene.These alkyl and thiazolinyl preferably have 60-350 carbon atom.Have the alkyl and the thiazolinyl that are less than 40 carbon atoms and can produce the compound poor, have alkyl that surpasses 400 carbon atoms and the low-temperature fluidity that thiazolinyl can damage the transmission lubricant composition lubricating base oil solubleness.
The example of the derivative of amino and/or imino-compound is the compound of (i) sour modification, the compound of these sour modifications is to obtain by following method: above-mentioned amino or imino-compound and monocarboxylic acid with 2-30 carbon atom for example oxalic acid, phthalic acid, trimellitic acid and 1 of aliphatic acid or poly carboxylic acid with 2-30 carbon atom for example, 2,4, the reaction of 5-pyromellitic acid, all or part of remaining amino and/or imino-so that neutralize, or transform all or part of remaining amino and/or imino-becomes acid amides; The (ii) compound of boron modification, the compound of these boron modifications is to obtain by following method: above-mentioned amino or imino-compound and acid reaction, all or part of remaining amino and/or imino-so that neutralize, or transform all or part of remaining amino and/or imino-becomes acid amides; The (iii) compound of sulphur modification, they are by above-mentioned amino or imino-compound and sulphur compound reaction are obtained.
Can be blended together as ashless dispersant above-mentioned amino or imino-compound and one or more its improved product.Based on the total mass of transmission lubricant composition, their content is selected from 0.1-10% (quality).
Metal detergent can be any common metal purification agent that is used for lubricant.Suitable metal detergent is sulfonate, phenates and the salicylate of basic metal or alkaline-earth metal.These compounds can use or mix use separately.Alkali-metal example is sodium and potassium, and the example of alkaline-earth metal is calcium and magnesium.The object lesson of metal detergent is sulfonate, phenates and the salicylate of calcium or magnesium.
According to the needed performance of transmission lubricant composition, can arbitrarily choose the content of metal detergent.General, based on the total mass of transmission lubricant composition, the amount of the metal detergent that mixes is 0.1-5.0% (quality).
Oxidation retarder can be any conventional oxidation retarder that is used for lubricant.Suitable oxidation retarder is phenolic group compound or amino-complex.These compounds can use or mix use separately.The object lesson of oxidation retarder is an alkylphenol, for example 2-6-di-t-butyl-4-sylvan; Bis-phenol is methylene radical-4 for example, 4-bis-phenol (2,6-di-t-butyl-4-cresols); Naphthylamines is phenyl-a-naphthylamine for example, the dialkyl group diphenylamine; Zinc dialkyl dithiophosphate, two-2-ethylhexyl zinc dithiophosphate for example, 3,5-di-tert-butyl-hydroxy phenyl lipid acid (propionic acid) and list or polyvalent alcohol be methyl alcohol, octadecanol, 1 for example, the ester of 6-hexylene glycol, neopentyl glycol, thio-diethylene glycol, triethylene glycol or tetramethylolmethane.
Based on the total mass of transmission lubricant composition, the incorporation of oxidation retarder is 0.01-5.0% (quality).
Sanitas can be any conventional preservatives that is used for lubricant, suitable sanitas be based on benzotriazole-, tolyl-triazole-, thiadiazoles-and imidazoles-compound.They can use or mix use separately.Based on the total mass of transmission lubricant composition, the common incorporation of sanitas is 0.01-3.0% (quality).
Suds suppressor can be any conventional suds suppressor that is used for lubricant, and suitable suds suppressor is for example dimethyl-silicon and a fluoro silicon of silicone.They can use or mix use separately.Based on the total mass of transmission lubricant composition, the common incorporation of suds suppressor is 0.001-0.05% (quality).
When mixing dyestuff in lubricant compositions of the present invention, they can be conventional dyestuffs.Based on the total mass of transmission lubricant composition, the common incorporation of dyestuff is 0.001-1.0% (quality).
To further specify the present invention with embodiment and comparative example below, these examples only are illustrative.
Embodiment
According to the prescription shown in the table 1, prepare of the present invention and transmission lubricant composition comparative example, make that each composition is 7.3mm 100 ℃ kinematic viscosity 2/ s.
Every kind of composition is resisted the endurance test of quivering, measure low temperature viscosity and shear stability test.Listed the result of anti-quiver weather resistance, low-temperature fluidity and shear stability test in the table 1.
Table 1
Inventive embodiments Comparing embodiment 1
1 2 3 4
Base oil Mineral oil A 1)Quality % 79 55.3 12.3 79 -
Mineral oil A 2)Quality % - 11.9 75.7 - -
Mineral oil A 3)Quality % - 11.8 - - 44.9
Mineral oil A 4)Quality % - - - - 35.3
The kinematic viscosity of base oil (100 ℃) mm 2/s 2.8 2.8 3.8 2.8 2.8
The %Cp of base oil 76 75 81 76 62
The %C of base oil A 2 2 0.6 2 5.6
Viscosity index improver A 5)Quality % - - - 15 -
Viscosity index improver B 6)Quality % 15 15 - - 13.8
Viscosity index improver C 7)Quality % - - 6.4 - -
Ashless dispersant A 8)Quality % 3 3 3 3 3
Ashless dispersant B 9)Quality % 1 1 0.5 1 1
Wear preventive additive 10)Quality % 0.2 0.2 0.2 0.2 0.2
Ca base purification agent 11)Quality % 0.4 0.4 0.5 0.4 0.4
Oxidation retarder A 12)Quality % 0.5 0.5 0.5 0.5 0.5
Oxidation retarder B 13)Quality % 0.5 0.5 0.5 0.5 0.5
Friction improver A 14)Quality % 0.1 0.1 0.1 0.1 0.1
Friction improver B 15)Quality % 0.2 0.2 0.2 0.2 0.2
Sanitas 16)Quality % 0.1 0.1 0.1 0.1 0.1
Low temperature viscosity (40 ℃) mPa.s 8300 8300 16200 8100 20400
Be less than the time h of 0 usefulness up to d μ/dV 144 144 168 120 48
Shear back viscosity and reduce % 4.8 4.8 14.2 4.8 4.3
1) hydrorefined mineral oil (viscosity index: 110, %Cp:76, %CA:2.0)
2) hydrorefined mineral oil (viscosity index: 125, %Cp:81, %CA:0.5)
3) solvent-refined mineral oil (viscosity index: 95, %Cp:60, %CA:5.2)
4) solvent-refined mineral oil (viscosity index: 100, %Cp:67, %CA:6.5)
5) non-dispersive type polymethacrylate (weight-average molecular weight: 40000)
6) decentralized polymethacrylate (weight-average molecular weight: 40000)
7) decentralized polymethacrylate (weight-average molecular weight: 120000)
8) polybutylene succinimide (dimorphism)
9) the improved polybutylene succinimide of boric acid (monotype)
10) aromatic yl phosphite
11) petroleum base calcium sulphonate (total basicnumber: 300mg KOH/g)
12) the dialkyl group diphenylamine is the basis
13) bis-phenol is the basis
14) oil base amine
15) the oil base amine of ethoxylation
16) tolyl-triazole
[the anti-endurance test of quivering]
Use the μ-V evaluating characteristics test-results of wet clutch to be used as the tolerance of the anti-performance of quivering of transmission lubricant composition.Estimate μ-V characteristic according to " automatic driver resists the test method of the performance of quivering with fluidic " in JASO M349-98, introduced.By the d μ/dV (50) of following formula definition or d μ/dV (150) less than 0 situation under, think the not anti-performance of quivering of transmission lubricant composition.
dμ/dV(50)=(μ 501)/(V 50-V 1)
dμ/dV(150)=(μ 15050)/(V 150-V 50)
Wherein: μ 1It is frictional coefficient at 1rpm
μ 50It is frictional coefficient at 50rpm
μ 150It is frictional coefficient at 150rpm
V 1Be sliding velocity 0.006m/s at 1rpm
V 50Be sliding velocity 0.03m/s at 50rpm
V 150Be sliding velocity 0.9m/s at 150rpm
Every kind of above-mentioned lubricant compositions, test temperature at 150 ℃, change the test period, " test method of internal combustion engine lubricant oxidative stability " according to " test method of lubricant oxidation stability " described in the JIS K2514-1993 tested, and obtains the various oil that suffer damage thus.Estimate the μ-V characteristic of each oil that suffers damage.By measuring the anti-weather resistance of quivering up to d μ/dV (50) or d μ/dV (150) 0 used time that was less than.
[low temperature viscosity evaluation]
According at " the gear oil low temperature viscosity measuring method " described in the JPI-5S-26-85, in cryogenic liquid is bathed, measure every kind of transmission mechanism lubricant compositions-40 ℃ low temperature viscosity.
[shear stability test]
According in " the shear stability test method of power transmitting fluids automatically " described in the JASO M347-95, every kind of above-mentioned transmission mechanism lubricant compositions is used ultrasonic wave radiation 1 hour.With following equation, before the radiation and after kinematic viscosity calculate the viscosity drop lower velocity of every kind of composition:
ΔV=(V 0-V r)/V 0×100
Wherein: Δ V is viscosity drop lower velocity (%)
V 0Be the kinematic viscosity (mm before the radiation 2/ s)
V rBe the kinematic viscosity (mm after the radiation 2/ s)
From the result shown in the table 1 significantly as can be seen, it is longer that the transmission mechanism lubricant compositions of embodiment 1-4 reached for 0 used time up to d μ/dV, therefore has good performance, i.e. good low temperature viscosity.
And the transmission mechanism lubricant compositions of comparative example 1 contains %Cp different with the range of definition of the present invention and/or the base oil of %CA, and it is shorter that it reached for 0 used time up to d μ/dV value, and the weather resistance of the anti-performance of quivering is relatively poor, and low temperature viscosity is very high.

Claims (11)

1. transmission mechanism lubricant compositions comprises:
(A) as the mineral oil of base oil, the percentage ratio of the total number of carbon atoms in the described mineral oil in the paraffin chain, %C p, be 70% or bigger, and the percentage ratio of the total number of carbon atoms of aromatic ring structure, %C A, be 3% or littler;
(B) viscosity index improver of 0.1-25% quality, being selected from weight-average molecular weight is 10,000-200,000 various polymethacrylate; And
(C) friction improver of 0.005-3.0% quality, more than the mass percent of each component be total restatement with described composition.
2. according to the transmission mechanism lubricant compositions of claim 1, wherein said mineral oil is 1-10mm 100 ℃ kinematic viscosity 2/ s.
3. according to the transmission mechanism lubricant compositions of claim 1, wherein said viscosity index improver is selected from non-dispersive type and decentralized viscosity index improver.
4. according to the transmission mechanism lubricant compositions of claim 1, wherein said %C pBe 75 or bigger.
5. according to the transmission mechanism lubricant compositions of claim 1, wherein said %C ABe 2 or littler.
6. according to the transmission mechanism lubricant compositions of claim 1, wherein said viscosity index improver is the viscosity index improver of non-decentralized and is polymkeric substance or its hydride that is obtained by the monomer that one or more formulas of polymerization (1) are represented:
Figure C011173510002C1
R wherein 1Be methyl, R 2It is alkyl with 1-18 carbon atom.
7. according to the transmission mechanism lubricant compositions of claim 1, wherein said viscosity index improver is the viscosity index improver of decentralized and is multipolymer or its hydride that the monomer of the compound represented of monomer and one or more formulas (4) of one or more compounds that are selected from formula (1) expression by polymerization obtains:
Figure C011173510003C1
R wherein 1Be methyl, R 2Be alkyl with 1-18 carbon atom,
R wherein 7Be methyl, R 8Be alkylidene group with 1-18 carbon atom, E 1Be amine residue or heterocycle residue, and a is integer 0 or 1 with 1 or 2 nitrogen and 0-2 oxygen.
8. according to the transmission mechanism lubricant compositions of claim 1, wherein said friction improver is to be selected from (C-1) to have at least one alkyl with 6-30 carbon atom or alkenyl but the amine compound or derivatives thereof that do not have the alkyl of 31 or more carbon atoms in its molecule, (C-2) in its molecule, have at least one alkyl or alkenyl with 6-30 carbon atom but do not have 31 or more carbon atoms alkyl the phosphorus compound or derivatives thereof and (C-3) in its molecule, have at least one alkyl or alkenyl but do not have the acid amides or the metal-salt of lipid acid of the alkyl of 31 or more carbon atoms with 6-30 carbon atom.
9. transmission mechanism lubricant compositions according to Claim 8, wherein (C-1) described amine compound be select the aliphatic monoamine of free style (6) expression and alkylene oxide adduct thereof, by the aliphatic polyamines of formula (7) expression with by at least a compound in the imidazolinium compounds of formula (8) expression:
Figure C011173510003C3
R wherein 10, R 15And R 19Be alkyl or alkenyl independently of one another with 6-30 carbon atom, R 11, R 12, R 16And R 20Be ethylidene or propylidene independently of one another, R 13, R 14, R 17, R 18And R 21Be hydrogen or the alkyl with 1-30 carbon atom independently of one another, and f and g be integer and the f+g=0-10 of 0-10 independently of one another, h is that integer and the i of 1-5 is the integer of 0-10.
10. transmission mechanism lubricant compositions according to Claim 8, wherein (C-2) described phosphorus compound is the compound of the phosphorous acid ester of at least a phosphoric acid ester that is selected from formula (9) expression and formula (10) expression:
Figure C011173510004C1
R wherein 22And R 25Be alkyl or alkenyl independently of one another with 6-30 carbon atom; R 23, R 24, R 26And R 27Be hydrogen or alkyl independently of one another with 1-30 carbon atom; F 1, F 2, F 3And F 4Be oxygen or sulphur independently of one another, condition is F 1, F 2, F 3And F 4In at least one be oxygen; F 5, F 6And F 7Be oxygen or sulphur independently of one another, condition is F 5, F 6And F 7In at least one is an oxygen.
11. transmission mechanism lubricant compositions according to Claim 8, wherein (C-3) described acid amides is the amine compound deutero-acid amides that the alkyl of hydrocarbon with 1-8 carbon atom or hydroxyl is only arranged by the lipid acid of the alkyl or alkenyl with 6-30 carbon atom and ammonia or per molecule, and the metal-salt of described lipid acid is lipid acid and metal deutero-metal-salt by the alkyl or alkenyl with 6-30 carbon atom.
CNB011173513A 2000-03-21 2001-03-21 Lubricant compsns. for driving gear Expired - Fee Related CN1271185C (en)

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