CN1772855A - Lubricant for manual or automated manual transmissions - Google Patents

Lubricant for manual or automated manual transmissions Download PDF

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Publication number
CN1772855A
CN1772855A CNA2005101051054A CN200510105105A CN1772855A CN 1772855 A CN1772855 A CN 1772855A CN A2005101051054 A CNA2005101051054 A CN A2005101051054A CN 200510105105 A CN200510105105 A CN 200510105105A CN 1772855 A CN1772855 A CN 1772855A
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CN
China
Prior art keywords
oil
acid
component
weight
synchronizer
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CNA2005101051054A
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Chinese (zh)
Inventor
P·普尔默
C·A·斯蒂芬斯
R·F·沃茨
R·K·尼贝尔特
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Infineum International Ltd
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Infineum International Ltd
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Publication of CN1772855A publication Critical patent/CN1772855A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Mechanical Operated Clutches (AREA)
  • General Details Of Gearings (AREA)
  • Structure Of Transmissions (AREA)

Abstract

A method for lubricating a manual transmission or automated manual transmission apparatus having metallic synchronizers which comprises supplying to said transmission a lubricating composition comprising a major amount of an oil of lubricating viscosity containing effective amounts of two ZDDP's, a thiadiazole corrosion inhibitor, a fatty acid primary amide and at least one each of a supplemental anti-wear agent, a dispersant, an antioxidant and a metal detergent.

Description

The lubricant that is used for manual or automated manual transmissions
The present invention relates to satisfy manual shifted transmission lubricant to manual shifted transmission and automated manual transmissions requirement, wherein said variator comprises two clutches (double clutch) or dual clutch (dual cluth) variator, and it relies on synchronizer and finishes gear shift.More particularly; the present invention relates to have specific resistance to wearing and the manual shifted transmission lubricant of the strict combination of corrosion inhibiting additive, wherein said additive resistance to wears for manual shifted transmission or automated manual transmissions device provide, the protection of friction and oxidation.
Manual shifted transmission uses small-sized clutch coupling usually, is called synchronizer, to finish smooth shifting under broad range of conditions.The responsible multiple material of described synchronizer is to produce suitable rubbing characteristics.These friction materialss can be paper substrate, carbon back or metal.Have and depend on the manual shifted transmission of Special Metal (as brass, molybdenum, sintered bronze etc.), brought difficulty for lubricant formulation person, because they are unique with the synchronizer that produces the friction of necessary level.This class variator needs many performances owing to lubricant, to obtain acceptable synchronizer performance.Fabulous pressure that acceptable fluid must provide intervention (run-in) good under the lower temperature (60 ℃) and the low wearing and tearing under the higher temperatures (75 ℃), measure according to 4 ball methods of testing and wear resistance, according to the good resistance scraping and the spot corrosion performance of FZG experimental test, be applied to gearshift power low under the meshing condition of automated manual transmissions and good oxidation-resistance.
Specific frictional behaviour need be provided the manual shifted transmission fluid so that synchronizer can carry out steady speed change.For gear shift, variator must make drive shaft arrive identical speed with toothing.The constant speedization of gear speed of relative movement is finished by synchronizer.When the speed of relative movement of synchronization section (plate and plate, or ring and awl) was reduced to zero, the locking tooth bar is engagement just.If these parts do not obtain zero speed of relative movement, the phenomenon that synchronizer impacts (being sometimes referred to as bump) so just appears being called as.When the dynamic friction coefficient subcritical minimum value between the engagement synchronizer parts (plate and plate, or ring and awl), synchronizer just occurs and impact.Be lower than this critical minimum, the synchronizer parts can not obtain zero speed of relative movement in gearshift procedure.When speed of relative movement was not zero, blocking mechanism (for example rack inclined) contacted with rotatable parts (for example boring the inclined-plane), caused producing the ratchetting (ratcheting action) of (impact/bump) of very big noise.Can not finish gear shift between impact epoch.
Synchronizer failure in the manual shifted transmission promptly can not provide steadily ' do not have and impact ' gear shift, and its reason has two.Wherein first is wearing and tearing.Use flexible material such as brass to do the synchronizer often wearing and tearing in use of surface of friction.When abrasion loss has surpassed the permission stroke (travel) of synchronizer, just can not produce acceptable friction, and synchronizer can not make the speed of relative movement of meshing part reach zero, and the gear shift failure.Second failure mechanism is to produce sufficient dynamic friction, i.e. low-friction coefficient.For synchronizer with hard metal, for example use those of molybdenum or sintered bronze friction surface, this class fault is more common.In case synchronizer no longer can produce sufficiently high frictional coefficient, the speed of relative movement of meshing part can not reach zero distributing in the time of gear shift, and occurs impacting.
Manual shifted transmission fluid of the present invention provides high dynamic friction coefficient and low wearing and tearing between clutch ring and steel pricker.Under the quick synchronizer meshing condition that automated manual change gear case uses, these perfect conditions also exist.
According to the present invention, found a kind of lubricated method with manual shifted transmission or automated manual transmissions (it comprises two clutches or dual clutch speed changer) device of metal synchronizer, this method comprises the lubricating composition that the lubricant viscosity oil that comprises main amount is provided to described variator, and wherein said lubricant viscosity oil comprises significant quantity:
(a) by primary alconol deutero-ZDDP (zinc dialkyl dithiophosphate),
(b) by 50 weight % or more secondary alcohol deutero-ZDDP,
(c) be 2,5-dimercapto-1,3, the thiadiazoles corrosion inhibitor of 4-thiadiazoles or derivatives thereof and can choose wantonly but preferably,
(d) have active lipid acid primary amide friction modifiers at low temperature,
(e) at least a auxiliary antiwear agents,
(f) at least a lubricating oil dispersant,
(g) at least a antioxidant and
(h) at least a metal detergent.
Another embodiment of the present invention is manual shifted transmission or automated manual transmissions device, comprises two clutches or dual clutch speed-changing apparatus, and it has the metal synchronizer and contains aforesaid lubricating composition.
Be applicable to that lubricating oil of the present invention is that those are by natural lubricating oil, ucon oil and its mixture deutero-lubricant viscosity oil.Natural and ucon oil generally has about 1 respectively to about 100mm at 100 ℃ 2The kinetic viscosity of/s (cSt), but typical application requires to have about 2 to about 18mm under 100 ℃ 2The lubricating oil or the oil mixture of/s (cSt) viscosity.
Natural lubricating oil comprises animal oil, vegetables oil (for example Viscotrol C and lard), oil, mineral oil and be derived from coal or the oil of shale.Preferred natural lubricating oil is mineral oil.
Suitable mineral oil comprises the mineral oil oil base that all are common.This comprises that chemical structure is the oil of naphthenic hydrocarbon or paraffinic hydrocarbons.Described oil uses acid, alkali and clay or other reagent, and is refining by traditional method as aluminum chloride, or they can be by for example carrying out the extraction oil that solvent extraction produces with the solvent as phenol, sulfurous gas, furfural, Dichlorodiethyl ether etc.They can hydrotreatment or hydrofining, by rapid cooling or catalytic dewaxing process dewaxing, or hydrocracking.Described mineral oil can be by natural coarse raw materials production, or be made up of the residuum of isomerization wax material or other method of refining.
Described mineral oil generally has 2.0mm under 100 ℃ 2/ s (cSt)-18.0mm 2The kinetic viscosity of/s (cSt).The kinetic viscosity that preferred mineral oils has under 100 ℃ is 2-6mm 2/ s (cSt) more preferably has 3-5mm under 100 ℃ 2Those of/s (cSt) viscosity.
Ucon oil comprises hydrocarbon ils and halo hydrocarbon ils, for example oligomeric, polymeric and poly-mutually alkene [for example polybutene, polypropylene, propylene, isobutylene copolymers, chlorination polylactene, poly-(1-hexene), poly-(1-octene), poly-(1-decene) wait and their mixture]; Alkylbenzene [for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene etc.]; Many benzene [for example biphenyl, terphenyl, the many benzene of alkylation etc.]; With the alkylation diphenyl ether, alkylation diphenyl sulfide and their derivative, their analogue and homologue etc.The preferred oil that comes from such synthetic oil is the oligopolymer of alpha-olefin, particularly the oligopolymer of 1-decene.
Ucon oil also comprises oxirane ring polymkeric substance, interpretation, multipolymer and their derivative, and terminal hydroxy group wherein is by modifications such as esterification, etherificates.The example of this class synthetic oil is: by the polyoxyalkylene polymers of oxyethane or propylene oxide polymerization preparation; The alkyl of these polyoxyalkylene polymers and aryl ethers (for example, molecular weight is that 1000 methyl-poly-Isopropanediol ether, molecular weight are the polypropylene glycol diphenyl ether of 1000-1500); And their monocarboxylate and polycarboxylate (for example acetic ester, blended C 3-C 8The C of fatty acid ester and Tetraglycol 99 12The oxygen acid diester).
The ucon oil of another suitable class comprises the ester of dicarboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc.) and various alcohol (for example, butanols, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol etc.).The specific examples of these esters comprises the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two-eicosyl ester, linoleic acid dimer and by making mixed ester that 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acid reactions form etc.The oil that comes from the preferred type of such synthetic oil is C 4-C 12The adipic acid ester of alcohol.
The ester that is suitable as ucon oil also comprises by C 5-C 12Monocarboxylic acid and polyvalent alcohol and polyol ethers, for example those of preparations such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol.
Silicon-based oil (for example many alkyl, polyaryl, many alkoxyl groups or many aryloxy silanes oil and silicic acid ester oil) constitutes the ucon oil of another available categories.These oil comprise tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four-(2-ethylhexyl) ester, silicic acid four-(4-methyl-2-ethylhexyl) ester, silicic acid four-(right-tert-butyl-phenyl) ester, six-(4-methyl-2-pentyloxy)-sily oxide, poly-(methyl)-siloxanes and poly-(aminomethyl phenyl) siloxanes etc.Other ucon oils comprise the liquid ester (for example, tri-o-cresyl phcsphate, trioctyl phosphate and decylphosphonic acid diethyl ester) of phosphoric acid, polymeric tetrahydrofuran (THF), poly-alpha olefins etc.
Described lubricating oil can be by refining oil, refining oil or their mixture are derived again.Unrefined oil is directly obtained by natural matter or synthesis material (for example, coal, shale or tar sands bitumen) without other purifications or processing.The example of refining oil does not comprise oil or the direct ester oil by the esterification process acquisition of directly being operated the shale oil of acquisition, directly being obtained by distillation by destructive distillation, and it uses without further handling directly separately.Refining oil is with refining oil is not similar, but refining oil has improved one or more performances with one or more purification step processing.Suitable purification techniques comprises distillation, hydrotreatment, dewaxing, solvent extraction, acid or alkali extraction, filtration and diafiltration, and all these is well known to a person skilled in the art.
In lubricating composition of the present invention, need two class oil soluble dialkyl zinc dithiophosphates (ZDDP), derived from the ZDDP of primary alconol with derived from the ZDDP of 50 weight %, preferred 80 weight % or more secondary alcohol.These components provide anti-oxidant and wear resistance for described lubricating composition.These compounds can prepare according to known technology, at first generally by making alcohol or phenol and P 2S 5Reaction generates phosphorodithioic acid, uses in the suitable zn cpds then and phosphorodithioic acid.Can use the mixture of alcohol, comprising the mixture of primary and secondary alkyl alcohol.These pure examples include but not limited to following: Virahol, isooctyl alcohol, 2-butanols, methyl isobutyl carbinol (4-methyl-1-pentene alkane-2-alcohol), 1-amylalcohol, 2-methyl butanol and 2-methyl isophthalic acid-propyl alcohol.Described alkyl can have 1-25 carbon atom, preferred 3-12 carbon atom.Has some advantage derived from uncle or the zinc dithiophosphate of secondary alcohol than the zinc dithiophosphate of other types.Primary alconol deutero-zinc dithiophosphate is more stable to heat than secondary alcohol deutero-zinc dithiophosphate, but the latter is more effective antiwear agents.
Based on active ingredient (a.i.), the present composition comprises about 1.00, the preferred about 0.25-0.75 weight %'s derived from the ZDDP of primary alconol and the ZDDP derived from 50 weight % or more secondary alcohol of 0.01-0.50, preferred 0.05-0.25 weight % of about 0.10-.
Except as otherwise noted, all per-cents described here and ratio promptly, are not considered solvent or carrier oil all based on a.i..
Be included in the lubricating composition of the present invention is that this inhibitor is 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) or derivatives thereof based on a.i., based on the thiadiazoles corrosion inhibitor of the significant quantity of lubricating composition weight.Appropriate vol is 0.01-1.00 weight %, preferred 0.20-0.50 weight %, most preferably 0.20-0.35 weight %.Using in these scopes is successfully lubricated the use manual shifted transmission with metal synchronizer of the present composition and the key of automated manual transmissions.
The derivative of DMTD comprises:
(a) 2-alkyl dithio-5-sulfydryl-1,3,4-thiadiazoles or 2,5-two (alkyl dithio)-1,3,4-thiadiazoles and composition thereof;
(b) carboxylicesters of DMTD;
(c) condensation product of alpha-halogen mono carboxylic acid of aliphatic series and DMTD;
(d) reaction product of unsaturated cyclic hydrocarbon and beta-unsaturated ketone and DMTD;
(e) reaction product of aldehyde and diarylamine and DMTD;
(f) amine salt of DMTD;
(g) dithiocar-bamate/ester derivative of DMTD;
(h) reaction product of aldehyde, alcohol or aromatic hydroxy compound and DMTD;
(i) reaction product of aldehyde, mercaptan and DMTD;
(j) 2-alkyl sulfo--5-sulfydryl-1,3, the 4-thiadiazoles; With
(k) by oil-soluble dispersant and DMTD bonded product; With their mixture.
At United States Patent (USP) the 4th, 612, in No. 129 and the patent reference wherein quoted above-mentioned a)-k) DMTD derivative has been described.
Be used for some preferred thiadiazoles of the present invention and be above-mentioned a), h) and k) enumerate those.2,5-two-(alkyl dithio)-1,3,4-thiadiazoles (wherein alkyl is a nonyl) and its mono-substituted equivalent 2-alkyl sulfo--5-sulfydryl-1,3, the 4-thiadiazoles is these two kinds of compounds of buying from Ethyl company ratio blended mixtures " Hitec 4313 " with about 85% dialkyl and 15% 1 alkyl.
The lipid acid primary amide friction modifiers that is used for the present composition is long-chain carboxylic acid's a acid amides, and with structure RCONH 2Expression, wherein R has individual, the more preferably alkyl or alkenyl of 16-20 carbon atom of about 12-24.Preferred primary amide is an oleylamide.Described primary amide preferably exists with the amount based on about 0.01-1.00 weight % of full formulated oil weight percent, and most preferably the amount based on the 0.05-0.10 weight % of a.i exists.This friction modifiers is active at low temperatures.
Suitable auxiliary antiwear agents comprises, for example the amine salt of phosphoric acid salt, phosphoric acid ester, phosphoric acid ester/salt (it is preferred), phosphorous acid ester/salt, for example dialkyl group phosphorous acid hydrogen ester, tricresyl phosphate (o-toluene ester); Chlorating wax, sulfurized fat and alkene, for example thiodipropionate, dialkyl sulfide, dialkyl polysulfide, alkyl-mercaptan, dibenzothiophene and 2,2 '-dithio two (benzothiazole); Organo-lead compound, lipid acid, molybdenum match, for example molybdenumdisulphide, halo silicoorganic compound, silicoorganic compound, boric acid ester/salt and halogenated phosphorus compound.Preferably assisting antiwear agents is phosphamide, and its three esters that replace by hydroxyl (by phosphorodithioic acid and epoxide reaction preparation) react then with preparing with the acid that is obtained in the amine with Vanadium Pentoxide in FLAKES.The preparation of these materials is at US 3,197, description arranged in 405, and this patent is by with reference to incorporating this paper into.They can be separately exist with the amount of the about 3.00 weight % of 0.01-, preferred 0.1-1.00 weight %.
Be used for mixed ester/acid amides, the hydroxy ester of hydrocarbyl substituted succinic and the Manny phase condensation product of phenol, formaldehyde and polyamines that alkyl replaces that proper lubrication oil ashless dispersant of the present invention comprises hydrocarbyl succinic imide, hydrocarbon succinic amide, hydrocarbyl substituted succinic.The phenylic acid that polyamines and alkyl replace also is suitable for.Can also use the mixture of these dispersion agents.
The nitrogenous ashless sanitising agent of alkalescence is well-known lubricating oil additive, and its preparation method is extensively described in patent documentation.For example, the succinimide of alkyl replacement and succinic diamide and preparation method thereof are described in following United States Patent (USP): 3,018,247,3,018,250,3,018,291,3,361,673 and 4,234,435.The mixing ester-acid amide of hydrocarbyl substituted succinic is for example at United States Patent (USP) 3,576, describes in 743,4,234,435 and 4,873,009.The Mannich dispersant of phenol, formaldehyde and polyamines condensation product that alkyl replaces is for example at United States Patent (USP) 3,368, and 972,3,413,347,3,539,633,3,697,574,3,725,277,3,725,480,3,726,882,3,798,247,3,803,039,3,985,802,4, describe in 231,759 and 4,142,980.The amine dispersion agent and by the method for polymer aliphatic series or cyclic aliphatic halogenide and amine preparation for example at United States Patent (USP) 3,275, describe in 554,3,438,757 and 3,565,804.
Preferred dispersing agent is alkenyl succinimide and succinic diamide.Described succinimide and succinic diamide dispersion agent can be by comprising basic nitrogen and another one or a plurality of hydroxyl forms.Usually, described amine is polyamines, for example the polyamines and the polyalkylene oxide polyamines of polyalkylenepolyamines, hydroxyl replacement.The example of polyalkylenepolyamines comprises diethylenetriamine, Triethylenetetramine (TETA), tetren, penten.The low cost of on average about 5-7 the nitrogen-atoms of per molecule gather (ethyleneamines) (PAM ' s) can trade(brand)name " Polyamine H ", " Polyamine 400 ", Dow Polyamine E-100 " etc. buy.The amine that hydroxyl replaces comprises N-hydroxyalkyl alkylene polyamine, for example N-(2-hydroxyethyl) quadrol, N-(2-hydroxyethyl) piperazine and at United States Patent (USP) 4,873, the Alkylenediamine of the N-hydroxyalkylation of describing in 009.The polyalkylene oxide polyamines generally comprises polyethylene oxide and Polypropylene oxide diamine and the triamine that molecular-weight average is 200-2500.The type product can obtain by trade mark " Jeffamine ".
The alkenyl succinimide of handling with boronating agent also is applicable to the present composition, because they are with more compatible by the resilient seal of for example fluoroelastomer and silicon-containing elastomer preparation.Described dispersion agent can with well known to a person skilled in the art many reagent aftertreatments (referring to, for example United States Patent (USP) 3,254,025,3,502,677 and 4,857,214).
Preferred ashless dispersant is the polyisobutenyl succinimide that the alkylene polyamine by polyisobutenyl succinic anhydride and for example Triethylenetetramine (TETA) or tetren forms, and polyisobutenyl substituting group wherein is that the polyisobutene of 300-2500 (preferably 400-2200) is derived by number-average molecular weight.Have been found that and in the alkenyl succinimide of wide region, select specific dispersant to produce the fluid of rubbing characteristics with improvement.The most preferred dispersion agent of the present invention be wherein the polyisobutene substituting group to have the molecular weight of about 950 atomic mass units, alkaline nitrogenous residue be those of polyamines (PAM).
Ashless dispersant of the present invention can any significant quantity use.But in finished lubricants, they are generally using based on the amount of the about 0.1-10.0 quality of a.i %, preferably about 0.5-7.0 quality %, and about 5.0 quality % of 2.0-most preferably from about.
The antioxidant that is adapted at being used in combination in the present composition comprises amine and phenol antioxidant.The example of amine antioxidants (being preferred in the present invention) comprises that the phenylbenzene amine of phenyl-a-naphthylamine, Phenyl beta naphthylamine and dialkyl groupization is (for example right, right '-two (alkyl phenyl)-amine, wherein alkyl respectively comprises 8-12, particularly 9 carbon atoms).Phenol antioxidant comprises sterically hindered phenol (for example 2,6-two-tert.-butyl phenol, 4-methyl-2,6-two-tert.-butyl phenol) and bisphenols (for example 4,4 " methylene radical-two (2, the 6-tert.-butyl phenol)).The derivative that another kind of suitable phenol antioxidant is styracin and laurate (for example 3,5-dimethyl-4-hydroxycinnamic acid monooctyl ester).In the present invention, the usage quantity of antioxidant is the about 3.0 weight % of 0.1-, preferably about 0.15-1.0 weight %.
The metal detergent that can be used for the present composition can be the salt of the oil soluble neutrality of following one or more acidic substance (or its mixture) or high-alkaline base metal, alkaline-earth metal (comprising magnesium): (1) sulfonic acid, (2) carboxylic acid, (3) Whitfield's ointment, (4) alkylphenol and (5) sulfurized alkylphenol.
The neutral metal-containing detergent of oil soluble is those sanitising agents that amount and the amount of acidic moiety of metal in the sanitising agent equates on stoichiometry.Thereby, to compare with their high alkalinity analogue, mild detergent generally has low alkalinity.The acid material that is used to form described sanitising agent comprises carboxylic acid, Whitfield's ointment, alkylphenol, sulfonic acid, sulfenyl phenolate etc.
About the term " high alkalinity " of metal detergent, be meant the metal-salt that metal wherein exists greater than the amount of organic group with stoichiometry.The method that is generally used for preparing high alkalinity salt comprises: under about 50 ℃, mineral oil solution and the excessive metal neutralizing agent of stoichiometry with acid, for example metal oxide, oxyhydroxide, carbonate, supercarbonate or sulfide heat together, and filter the product that is obtained.Use " promotor " to help a large amount of excess metals of combination at neutralization procedure, this is known equally.The examples for compounds that is suitable as described promotor comprises aldehydes matter, for example phenol, naphthols, alkylphenol, thiophenol, sulfurized alkylphenol, and the condensation product of formaldehyde and aldehydes matter; Alcohol, for example methyl alcohol, 2-propyl alcohol, octanol, Mierocrystalline cellulose alcohol, Trivalin SF, ethylene glycol, stearyl alcohol and hexalin; And amine, for example aniline, phenylenediamine, phenothiazine, Phenyl beta naphthylamine and lauryl amine.The preparation basic salt special effective means comprise makes acid mix with excess base earth metals neutralizing agent and at least a alcohols promotor, and the rising temperature such as 60-200 ℃ under make this mixture carbonatization.The TBN that over-based detergent has (total basicnumber, ASTM D-2896) is generally 150 or higher, for example 250-450.
The example of suitable metallic sanitising agent includes but not limited to the neutrality and the high alkalinity salt of following substances: calcium phenylate or phenol magnesium, and sulfurized calcium phenylate or phenol magnesium, wherein each aryl has one or more aliphatic groups so that it has the hydrocarbon solvability; Calcium sulphonate or sulfonic acid magnesium, wherein each sulfonic acid moieties links to each other with aromatic ring, and aromatic ring generally comprises one or more aliphatic substituting groups again, so that it has the hydrocarbon solvability; Calcium salicylate or magnesium salicylate, wherein aromatic moieties is generally replaced so that it has the hydrocarbon solvability by one or more aliphatic substituting groups; Hydrolysis have a 10-2, the salt of the phosphorus olefine sulfide of 000 carbon atom, or hydrolysis has 10-2, the salt of the phenolic compound that the phosphorus sulfurized alcohol of 000 carbon atom and/or aliphatic series replace; The cycloaliphatic carboxylic acid's that aliphatic carboxylic acid and aliphatic series replace calcium or magnesium salts; With many other oil soluble organic acid salt.Can use the neutrality of two or more different basic metal and/or alkaline-earth metal or the mixture of high alkalinity salt.Equally, also can use the neutrality of two or more different acid and/or the mixture (for example one or more high alkalinity calcium phenylates and one or more high alkaline calcium sulfonates) of high alkalinity salt.
Well-known, the high alkalinity metal sanitising agent generally is considered to comprise the mineral alkali of high alkalinity quantity, may be a differential prose style free from parallelism or colloidal suspension form.Thereby, the term " oil soluble " that is applied to metal detergent is meant and has comprised that wherein exist needn't be fully or really be dissolved in the metal detergent of the mineral alkali of oil from the stricti jurise of this term, because it shows to such an extent that fully and all be dissolved in oil much at one with them after this sanitising agent is sneaked into base oil.
The method of the sanitising agent of preparation oil soluble neutral and high alkalinity metal sanitising agent and alkaline including earth metal is well known to a person skilled in the art, and wide coverage in patent documentation.Referring to for example United States Patent (USP) 2,001,108,2,081,075,2,095,538,2,144,078 and 2,163,622 disclosure
Being preferred for calcium sanitising agent of the present invention is high alkaline calcium sulfonate and calcium phenylate and high alkalinity sulfurized calcium phenylate.
Though can use the over-based detergent of any significant quantity in the present invention, significant quantity is generally:, account for finished product fluidic 0.01-5.0 quality % based on a.i..Preferably, the processing rate in the described fluid is 0.05-3.0 quality %, most preferably 1.0-2.0 quality %.
Following embodiment specifies desired invention.But, it should be understood that the detail that the present invention is not limited to set forth among the embodiment.Except as otherwise noted, all umbers and per-cent are all based on weight.
Embodiment
Benefit has in order to demonstrate the invention prepared a kind of fluid that meets the requirement of invention that requires fully.This fluid, the composition of fluid A is shown in following table:
Table 1
Fluid A forms
Composition A.i. weight % in the oil
(a) derived from the zinc dialkyl dithiophosphate of primary alconol 0.45
(b) derived from the zinc dialkyl dithiophosphate of secondary alcohol 0.08
(c) alkyl thiadiazoles 0.25
(d) oleylamide 0.09
(e) phosphamide antiwear agents 0.68
(f) PIBSA/PAM dispersion agent 1.04
(g) diphenylamine-antioxidant 0.25
(h) calcium sulphonate TBN 300 1.65
(i) mineral oil based, viscosity modifier and other conventional additives of＜1% Surplus
Fluid A tests with two types metal synchronizer.Two tests are all carried out in traditional Hurth type synchronizer test equipment under the condition that is fit to used synchronizer.
The brass synchronizer
Under the specified condition of Reynolds, use the brass synchronizer (label is J63D) that is installed in the Reynolds manual shifted transmission to carry out an assessment.100,000 engagements have been carried out in assessment under the Reynolds condition, last 100,000 engagements, and synchronizer still provides sufficient frictional force for engagement.Total wearing and tearing of brass awl are less than 0.4mm.The result shows that desired composition---fluid A controls the ability of wearing and tearing on the brass synchronizer.
The sintered bronze synchronizer
Another assessment is used and to be coated with the sintered bronze synchronizer that is designated as the agglomerated material of HS45 by Hoerbiger and to carry out.These synchronizers (label BK 117) are installed in the manual shifted transmission of being made by ZF, and test under the specified condition of ZF (ZF Friedrichshafen AG).Test under the ZF condition uses fluid A to carry out 150,000 engagements.Last 150,000 engagements, synchronizer is in good condition and acceptable engagement still is provided.Friction level is 0.097, far above minimum requirements 0.07.This result shows that desired composition provides the ability of abundant friction level on the sintered bronze synchronizer.

Claims (9)

1. lubricated method with manual shifted transmission and automated manual transmissions device of metal synchronizer, this method comprises the lubricating composition that the lubricant viscosity oil that comprises main amount is provided to described variator, and described lubricating composition comprises significant quantity:
(a) by primary alconol deutero-ZDDP (zinc dialkyl dithiophosphate),
(b) by 50 weight % or more secondary alcohol deutero-ZDDP,
(c) be 2,5-dimercapto-1,3, the thiadiazoles corrosion inhibitor of 4-thiadiazoles or derivatives thereof and optionally,
(d) have active lipid acid primary amide friction modifiers at low temperatures,
(e) at least a auxiliary antiwear agents,
(f) at least a lubricating oil dispersant,
(g) at least a antioxidant and
(h) at least a metal detergent.
2. the method for claim 1, wherein said synchronizer is brass or sintered bronze synchronizer.
3. wherein there is (a) component of 0.1-1.0 weight % in the method for claim 1.
4. wherein there is (b) component of 0.01-0.5 weight % in the method for claim 1.
5. the method for claim 1, wherein (a) and (b) alkyl in the component have 3-12 carbon atom.
6. wherein there is (c) component of 0.01-1.0 weight % in the method for claim 1.
7. method as claimed in claim 6, wherein (c) component is 2,5-two (nonyl dithio)-1,3,4-thiadiazoles.
8. wherein there is (d) component of 0.01-1.0 weight % in the method for claim 1.
9. method as claimed in claim 8, wherein (d) component is an oleylamide.
CNA2005101051054A 2004-09-22 2005-09-22 Lubricant for manual or automated manual transmissions Pending CN1772855A (en)

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