CN100441667C - Lubricant oil composite - Google Patents
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- CN100441667C CN100441667C CNB021269912A CN02126991A CN100441667C CN 100441667 C CN100441667 C CN 100441667C CN B021269912 A CNB021269912 A CN B021269912A CN 02126991 A CN02126991 A CN 02126991A CN 100441667 C CN100441667 C CN 100441667C
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Abstract
To provide a lubricating oil composition which excels in fuel consumption saving performance at middle and high temperatures and, in addition, excels in wet clutch friction properties. The lubrication oil composition comprises a base oil and, based on the total weight of the composition, (A) 0.003-0.1 mass%, in terms of Mo element, organomolybdenum compound, (B) 0.08-0.3 mass%, in terms of N element, boron-containing succinimide and/or boron-free succinimide at a mass ratio of component (B) in terms of N element to component (A) in terms of Mo element of >=1.6, (C) 0.01-0.16 mass%, in terms of an alkaline earth metal, alkaline earth metal-based cleaning agent, (D) 0.01-0.1 mass%, in terms of zinc element, zinc dithiophosphate, (E) <=0.1 mass%, in terms of phosphorus element, phosphoric (phosphorous) esters and, simultaneously, with a sulfate ash in the composition of <=1 mass%.
Description
Technical field
The present invention relates to lubricating oil composition, relate to particularly in temperature therefrom and demonstrate the lubricating oil composition of excellent fuel consumption efficiency in the pyritous very wide temperature range, relate more specifically to except the fuel efficiency of excellence, also to have the lubricating oil composition that is suitable for four-stroke engine for motor cycle of the frictional behaviour of excellence.
Background technology
From nearest environment protection, particularly reduce the viewpoint of CO2 emissions measure and set out, it is one of important problem that a kind of automobile with low fuel consumption is provided.In order to reduce fuel consumption, studied and reduced tare, increase fuel combustion efficiency, reduce friction, the exploitation between the engine part and improve the driving mechanism of automobile and the engine lubrication wet goods measure of using low fuel consumption.Such as, for the measure that reduces to rub, be accompanied by the improvement of engine material, such as the improvement of valve actuating mechanism, the quantity that reduces piston ring and reduction sliding part surfaceness, the exploitation of lean-burn engine and direct injection ic engine has obtained progress.The trial that improves fuel consumption efficiency not only by reduce between manual transmission and the automatic transmission modulator material frictional force, and will be by development new technologies, make it possible to provide the motivating force transmission performance of excellence, such as sliding latch clutch coupling and metal banding pattern and ring-like constantly variable transmission are housed.Recently, transmission oil has been proposed requirement, it should have the low fuel consumption performance that causes owing to its low viscosity and low friction performance, and the suitable frictional behaviour that excellent power transmission performance can be provided for humid clutch or metal strip clutch coupling.
In four-stroke engine for motor cycle, the single axle box is supply engine not only, also will supply with its speed change and power transmission part, so the lubricating oil of Shi Yonging therein requires it to have simultaneously as engine oil and as the ability of transmission oil.This lubricating oil also requires to have the efficient of low fuel consumption.Above-mentioned engine and driving mechanism and four-stroke engine for motor cycle all further reduce on size and weight, and its power output is enhanced.Link mutually therewith, the thermal load of the lubricating oil that will use in this engine and mechanism will be than higher in the past.Therefore, not only in about 80 ℃ middle temperature, and the efficient of the low fuel consumption under higher temperature is just tended to more important.Particularly, owing to compare with motor car engine, under normal drive condition, motorcycle engine has wideer and higher engine speed range, and with the operational conditions difference, the temperature of engine oil can great changes have taken place from low temperature to high temperature.Therefore, require engine oil between low temperature and high temperature, to have the efficient of stable low fuel consumption.
On the other hand, gasoline engine car, particularly diesel-engined vehicle or motorcycle all tend to install waste gas purification apparatus, such as EGR (exhaust gas recirculatioon) device, three-way catalyst or an acidic catalyst and particulate filter (DPF).In order to safeguard the performance of these devices, progressively reduce the sulphur content in gasoline or the diesel fuel oil.In addition, from same insight recited above, begun to reduce the research of ash and phosphorus content in the engine oil.To add as good oxidation retarder and abrasion inhibitor metal cleaner by minimizing and be the consumption of zinc dithiophosphate, perhaps do not use these materials, realize such trial.Yet this trial may damage the performance of engine oil.Therefore reduce ash and phosphorus content is a very difficult problem.
An example as the low fuel consumption engine oil, Japanese patent laid-open publication gazette 8-302,378 disclose a kind of engine oil composition, said composition contains specific lubricating oil base oil and specific additive, such as alkaline-earth metal salicylate clean-out system and molybdenum dithiocarbamate, each all has specific content.Japanese patent laid-open publication gazette 2000-087,070 discloses the engine oil composition that a kind of 4 stroke motorcycle uses, said composition contains specific base oil and specific additive, such as metal cleaner and friction improver, make it possible to reduce oil consumption, and reaching 3 in motor speed, 000-13 still has the efficient of low fuel consumption during 000rpm.Yet, such engine oil is being used under the situation of 4 stroke motorcycle, because their existence, they can cause very frequent clutch slip, therefore can reduce the power transport property of clutch coupling, and the time make the stationarity variation, and cause the friction materials heating and burn, wear and tear and rupture in gearshift.In the middle of these possible failures, those skilled in the art's common understanding is, is difficult to provide a kind of engine oil, both had the performance of low fuel consumption, also has the sliding resistance energy in humid clutch.Therefore, the use of the engine oil of this low fuel consumption is limited in clutch slip has been taked in the specific motorcycle of measure.Requirement to four-stroke engine for motor cycle lubricating oil is to have very wide use range, all have excellent fuel consumption performance and have excellent frictional behaviour in humid clutch to high temperature in middle temperature.
As everyone knows, adding organic molybdenum in transmission oil can make the stiction performance in humid clutch extremely worsen.For driving mechanism, the low fuel consumption lubricating oil composition that contains organic molybdenum is actually non-existent.
The lubricating oil composition that uses for the engine of developing emission-control equipment, the inventor is in humid clutch, to as above-mentioned publication in open and use contain organic molybdenum and alkaline-earth metal salicylate traditional low fuel consumption engine oil, under the salicylate consumption reduces with the situation that reduces ash, study with regard to the efficient and the frictional behaviour of its low fuel consumption.Found that owing to thermal load increase recently is counted as very important middle gentle high temperature friction performance depreciation, cause the degradation in efficiency of fuel consumption, the frictional behaviour in humid clutch is the extreme variation also.Also finding, also is unsatisfactory in the efficient of above-mentioned conventional engines lubricating oil low fuel consumption at high temperature.
Have again, the inventor has found both have the low fuel consumption performance, also has sliding resistance energy in the humid clutch, and be classified as the four-stroke engine for motor cycle lubricating oil composition of MA level, this classification is to be a class that does not show clutch slip in the performance classification according to JASO T 903-98, and application (seeing Japanese patent application 2000-028,919) proposed in the patent of engine oil composition.Yet, find that also said composition promptly on the accelerated reaction index after startup and the gearshift, can also be improved at the stiction aspect of performance.And then also find, for the composition that low ash (the protosulfate ash type) type that has reduced metal cleaner is provided and the low ash, the low-phosphorous type composition that reduce the zinc dithiophosphate consumption can further be studied.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of lubricating oil composition that contains the low fuel consumption type of organic molybdenum, said composition is gentle because in the high temperature range that the thermal load increase causes in whole, even under the situation that has reduced the metal cleaner consumption, all has excellent fuel consumption performance.
Another object of the present invention also provides a kind of low fuel consumption type lubricating oil composition that contains organic molybdenum, and its vitriol ash and phosphorus content are suppressed, and are suitable for being equipped with the vehicle of above-mentioned waste gas purification apparatus.
A further object of the present invention provides a kind of low fuel consumption type lubricating oil composition that contains organic molybdenum, said composition all has excellent fuel consumption performance in middle temperature to high temperature, and, promptly on the accelerated reaction index after startup and the gearshift, improve in the stiction performance.
Another purpose of the present invention provides a kind of low fuel consumption type lubricating oil composition that contains organic molybdenum, said composition all improves on pyritous fuel consumption efficiency and the frictional behaviour in humid clutch therefrom warm, causes it to reach and be classified as the MA level that does not show slip in the defined performance classification in by JASO T 903-98.
A further object of the invention just provides a kind of lubricating oil composition that four-stroke engine for motor cycle uses that is suitable for, improve aspect the frictional behaviour of said composition in humid clutch, make its frictional behaviour with therefore do not contain organic molybdenum compound and do not have the four-stroke engine for motor cycle lubricating oil of low fuel consumption performance suitable, and have the fuel consumption performance of excellence to the pyritous temperature range in temperature therefrom.
As found that of broad research, just mix and to address the above problem by following material: (A) organic molybdenum lubricant base and each specified quantitative and specific ratio; (B) succinimide ashless dispersants; (C) alkaline-earth metal clean-out system; (D) zinc dithiophosphate; And (E) Type Phosphate Antiwear Additives.
The invention provides a kind of lubricating oil composition, said composition contains: mineral and/or the synthetic base oil; (A) organic molybdenum, its content in molybdenum is 0.003-0.1 quality %; (B) boracic and/or do not have the boron succinimide, its content in nitrogen is 0.08-0.3 quality %, the mass ratio of molybdenum content is 1.6 or bigger in nitrogen and the component (A); (C) alkaline-earth metal clean-out system, its content in alkaline-earth metal is 0.01-0.16 quality %; (D) zinc dithiophosphate, its content in zinc is 0.01-0.1 quality %; And (E) at least a compound that is selected from phosphoric acid ester, phosphorous acid ester and salt thereof, its content in phosphorus is 0.1 quality % or still less, above-mentioned content all is based on the gross weight of composition, is 1 quality % or littler based on the vitriol the ash content of coal of its gross weight.
In the present invention, component (A) molybdenum dithiocarbamate preferably.
In the present invention, component (B) preferably includes the succinimide of boracic and/or the not list and/or two succinimides of boracic, and based on the gross weight of composition, it is 0.005-0.2 quality % that the consumption of boracic succinimide preferably makes the content in boron.
In the present invention, based on the gross weight of composition, the content of component (C) is preferably 0.01-0.07 quality % in alkaline-earth metal.
In the present invention, based on the gross weight of composition, the content of component (D) is preferably 0.01-0.06 quality % in zinc.
In the present invention, based on the gross weight of composition, the vitriol the ash content of coal is preferably 0.7 quality % or still less in composition.
In the present invention, based on the gross weight of composition, phosphorus content is preferably 0.08 quality % or still less in composition.
Lubricating oil composition of the present invention is preferably used as the engine oil of the automobile that emission-control equipment is housed.
Lubricating oil composition of the present invention is preferably used as the engine oil that 4 stroke motorcycle is used.
Embodiment
To narrate the lubricating oil that has improved frictional behaviour that has of the present invention below.
The lubricant base that lubricating oil composition of the present invention uses can be the base oil of any kind, as long as it can be as the base oil of normal engine lubricating oil composition, they can be mineral base oil or synthetic base oil.
The example of mineral base oil is paraffin base oil and naphthenic base oils, they can carry out for two steps by the lubricating oil distillate that crude oil is obtained through normal pressure rectifying or rectification under vacuum or the multistep refining obtains, such as through solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrofining, sulfuric acid scrubbing and clay treatment.
The example of synthetic base oil is a poly-alpha olefins, such as polybutene, 1-octene oligopolymer, 1-decene oligopolymer and ethylene-propylene oligopolymer and their hydrogenation products; Isobutylene oligomer and hydrogenation products thereof; Isoparaffin; Alkylbenzene; Alkylnaphthalene; The diester class is such as dibutyl maleinate, pentanedioic acid two (tridecane) ester and hexanodioic acid 2-ethylhexyl; The multipolymer of alpha-olefin and diester class; The ester of polyvalent alcohol is such as sad trishydroxymethyl propyl ester, n-nonanoic acid trishydroxymethyl propyl ester, caproic acid tetramethylolmethane-2-base ethyl ester and n-nonanoic acid pentaerythritol ester; Dialkyl diphenyl ether and many phenyl ethers.
The lubricant base of Shi Yonging can be mixture or the mixture of two or more synthetic oils or the mixture of mineral oil and synthetic oil of a kind of, two or more mineral oil in the mineral oil that exemplifies above or the synthetic oil in the present invention.The ratio of mixture of two or more base oils can at random be selected.Though the aromaticity content to base oil does not give specific restriction, 15 quality % or lower preferably, more preferably 10 quality % or lower, further more preferably 5 quality % or lower, perhaps 2 quality % or higher.Term " aromaticity content " refers to the content of the aromatic fraction of measuring according to ASTMD2549.
Basic oil viscosity is had no particular limits.Yet, be preferably 2mm at the lower limit of 100 ℃ of following kinetic viscosities
2/ s, more preferably 3mm
2/ s, and the upper limit is preferably 10mm
2/ s, more preferably 8mm
2/ s.Use is at 100 ℃ of following kinetic viscosity 2mm
2/ s or higher base oil help to produce the lubricating oil composition of lubricity excellence, because the ability of enough formation oil films is arranged, the vaporization losses of base oil is less under hot conditions, i.e. the fuel consumption excellent performance.Be 10mm and use 100 times kinetic viscosities
2/ s or lower base oil can produce the low lubricating oil composition of resistance to flow, therefore at the oiling point rub resistance, cause excellent fuel consumption performance.
Though the viscosity index of the base oil that will use the present invention does not have specific restriction, it is preferably 80 or bigger, more preferably 100 or bigger.The content that lubricating oil contains viscosity index 120 or higher base oil is 15 quality % or higher.Base oil especially preferably has 120 or bigger viscosity index.Use viscosity index 80 or bigger base oil to make it can access the low fuel consumption excellent performance and the little lubricating oil composition of vaporization losses under hot conditions.
The base oil that will use among the present invention, its NOACK volatility is preferably 20 quality % or lower, more preferably 16 quality % or lower, preferred especially 10 quality % or lower.Use NOACK volatility 20 quality % or lower base oil can access the less lubricating oil composition of vaporization losses under hot conditions, owing to can accumulate in the emission-control equipment, with regard to the disadvantageous effect on the piston and the combustion chamber.Here the term of Shi Yonging " NOACK volatility " refers to the L-40-T-87 according to CEC, 250 ℃ and-volatile quantity of 20mmHg during with 60g oil product sample evaporation 1hr.
Component in the lubricating oil composition of the present invention (A) is an organic molybdenum.Component (B) is boracic succinimide and/or boracic succinimide not.Component (C) is the alkaline-earth metal clean-out system.Component (D) is a zinc dithiophosphate.Component (E) is phosphoric acid ester, phosphorous acid ester and salt thereof, is called phosphoric acid ester or bi-ester of phosphite in the back.
The example of component (A) is molybdenum dithiocarbamate and molybdenum dithiophosphate.The object lesson of molybdenum dithiocarbamate is the compound by following general formula (1) expression, and the object lesson of molybdenum dithiophosphate is following compound by general formula (2) expression:
R wherein
1, R
2, R
3And R
4Expression independently of one another has the alkyl of 1-24 carbon atom, and a is the integer of 0-4, and b is the integer of 0-4, and a+b=4; And
R wherein
5, R
6, R
7And R
8Expression independently of one another has the alkyl of 1-24 carbon atom, and c is the integer of 0-4, and d is the integer of 0-4, and c+d=4; And
R for general formula (1)
1, R
2, R
3And R
4And the R of general formula (2)
5, R
6, R
7And R
8Preferred example is the alkaryl of the alkyl-cycloalkyl of the alkyl with straight or branched of 1-24 carbon atom, the cycloalkyl with 5-13 carbon atom or straight or branched, the thiazolinyl with straight or branched of 3-24 carbon atom, the aryl with 6-18 carbon atom or straight or branched and the aralkyl with 7-19 carbon atom.Alkyl and thiazolinyl can be primary, the second month in a season or uncle's isomer.
The object lesson of alkyl is 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 and tetracosyl, and it can be a straight or branched.
The object lesson of cycloalkyl and alkyl-cycloalkyl, cycloalkyl is such as cyclopentyl, cyclohexyl and suberyl, alkyl-cycloalkyl is such as methylcyclopentyl, dimethylcyclopentyl, the ethyl cyclopentyl, the propyl group cyclopentyl, the ethyl-methyl cyclopentyl, the trimethylammonium cyclopentyl, the diethyl cyclopentyl, the ethyl dimethylcyclopentyl, the propyl group methylcyclopentyl, propyl group ethyl cyclopentyl, the dipropyl cyclopentyl, propyl group ethyl-methyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, the ethyl cyclohexyl, the propyl group cyclohexyl, the ethyl-methyl cyclohexyl, trimethylcyclohexyl, the diethyl cyclohexyl, the ethyl Dimethylcyclohexyl, the propyl group methylcyclohexyl, propyl group ethyl cyclohexyl, the dipropyl cyclohexyl, propyl group ethyl-methyl cyclohexyl, the methyl suberyl, the dimethyl suberyl, the ethyl suberyl, the propyl group suberyl, the ethyl-methyl suberyl, the trimethylammonium suberyl, the diethyl suberyl, ethyl dimethyl suberyl, propyl group methyl suberyl, propyl group ethyl suberyl, dipropyl suberyl and propyl group ethyl-methyl suberyl, alkyl wherein can be straight chain or side chain, can be bonded in any position of cycloalkyl.
The object lesson of thiazolinyl be propenyl, pseudoallyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base such as oleyl, 19 thiazolinyls, icosa alkene base, two hendecene bases, docosene base, tricosene base with regard to two tetradecene bases, it can be straight chain or side chain, and the position of its pair key can change.
The object lesson of aryl and alkaryl is aryl and alkaryl, aryl such as phenyl and naphthyl, alkaryl such as tolyl, xylyl, ethylphenyl, propyl group phenyl, ethyl methyl phenyl, trimethylphenyl, butyl phenyl, propyl group aminomethyl phenyl, diethyl phenyl, ethyl 3,5-dimethylphenyl, tetramethylphenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl and dodecylphenyl, alkyl wherein can be straight chain or side chain, can be bonded to any position of aryl.
The object lesson of aralkyl is benzyl, methyl-benzyl, dimethyl benzyl, phenelyl, methyl phenelyl and dimethyl phenelyl, wherein alkyl can be straight chain or side chain, can be bonded to any position of aryl.
Each R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Preferred example be to have the alkyl of 1-18 carbon atom or have the aryl of 6-18 carbon atom or the alkaryl of straight or branched.
The preferred molybdenum dithiocarbamate of the component of Shi Yonging (A) is the molybdenum dialkyldithiocarbamacompositions as general formula (1), wherein R in the present invention
1, R
2, R
3And R
4Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, a=4, b=0; The molybdenum dialkyldithiocarbamacompositions of sulfurized general formula (1), wherein R
1, R
2, R
3And R
4Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, a=0, b=4; The dialkyldithiocarbamacompositions oxygen molybdenum of sulfurized general formula (1), wherein R
1, R
2, R
3And R
4Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, a=1-3, b=1-3, and a+b=4; And two or more of arbitrary proportion are selected from the mixture of the compound of molybdenum dialkyldithiocarbamacompositions, sulfurized dithio dialkyl amido formic acid molybdenum and sulfurized dialkyl amido formic acid oxygen molybdenum etc.These mixtures can have several alkyl of different carbonatomss and different structure in a molecule.
The object lesson of the molybdenum dithiophosphate of particularly preferred general formula (2) is the molybdenum dialkyl-dithiophosphate as general formula (2), wherein R
5, R
6, R
7And R
8Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, c=4, d=0; The molybdenum dialkyl-dithiophosphate of sulfurized such as general formula (2), wherein R
5, R
6, R
7And R
8Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, c=0, d=4; The dialkyl dithiophosphoric acid oxygen molybdenum of sulfurized such as general formula (2), wherein R
5, R
6, R
7And R
8Representing butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or tridecyl independently of one another, wherein is straight or branched all, c=1-3, d=1-3, and c+d=4; And with the arbitrary proportion blended two or more are selected from the mixture of compounds such as molybdenum dialkyl-dithiophosphate, sulfurized molybdenum dialkyl-dithiophosphate and dialkyl dithiophosphoric acid oxygen molybdenum.These mixtures can have several alkyl of different carbonatomss and different structure in a molecule.
In the compound beyond above-mentioned giving an example, the organic molybdenum of Shi Yonging also can be enumerated the example of organic molybdenum complex compound in the present invention, and this is the product of basic nitrogen compound such as succinimide, acid molybdenum compound such as molybdic oxide and sulfide such as hydrogen sulfide and thiophosphoric anhydride reaction.
In lubricating oil composition of the present invention, based on the gross weight of composition, the lower limit of component (A) content is counted 0.003 quality % with molybdenum, preferred 0.01 quality %.Based on the gross weight of composition, the upper limit of component (A) content is counted 0.1 quality % with molybdenum, preferred 0.08 quality %, preferred especially 0.06 quality %.Component (A) is lower than lower limit can not obtain enough fuel consumption efficiency, and component (A) surpasses the upper limit, can not considerably improve the fuel consumption performance with consumption, and the frictional behaviour in humid clutch will worsen.
The preferred ingredient of Shi Yonging (A) is molybdenum dithiophosphate and molybdenum dithiocarbamate in the present invention.Yet, particularly preferably be molybdenum dithiophosphate because they can improve in middle temperature to the efficient of pyritous low fuel consumption, and with other components synergies, obviously improved the frictional behaviour in humid clutch.
Component (B) is the boracic succinimide and/or the succinimide of boracic not.
The example of boracic succinimide is the single succinimide with following general formula (3) expression, two succinimides of representing with following general formula (4), and with the succinimide of oxygen-containing organic compound modification:
In general formula (3) and (4), R
10, R
11And R
12Represent polybutylene-basedly independently of one another, n is the integer of 2-7.
R
10, R
11And R
12Polybutylene-based number-average molecular weight be preferably 700 or bigger, more preferably 900 or bigger, be preferably 3,500 or littler, more preferably 1,500 or littler.Number-average molecular weight 700 or bigger polybutylene-basedly can access lubricating oil composition with excellent cleaning performance and dispersing property.Number-average molecular weight 3500 or littler polybutylene-basedly then can produce lubricating oil composition with excellent low-temperature fluidity.From the viewpoint of the effect that suppress to form mud, the lower limit of n is 2, preferably 3, and the upper limit of n is 7, preferably 6.By using catalyzer can access polybutylene-based from the polybutene (polyisobutene) that 1-butylene and iso-butylene or high-purity isobutylene polymerization obtain such as aluminum chloride or boron fluoride.In the polybutene mixture, the general polymkeric substance that exists 5-10mol% in the end with vinylidene structure.Can contain the residual fluorine and the chlorine that come in the catalyzer that in method, uses on a small quantity in the polybutene (polyisobutene), can be removed with suitable processing.Therefore, be preferably 50ppm (quality) or still less as the content of halogen atoms such as fluorine and chlorine, 5ppm (quality) or still less more preferably is preferably 1ppm (quality) or still less especially.
The manufacture method of the succinimide of mutual-through type (3) or (4) expression does not have specific restriction.Such as obtaining succinimide by reacting such as diethylenetriamine, Triethylenetetramine (TETA), tetren or penten by polybutylene-based succinimide and polyamine, and this polybutylene-based succinimide is to be reacted under 100-200 ℃ temperature by polybutene and maleic anhydride to obtain, and this polybutene is by the above-mentioned polybutene of chlorination, and the polybutene of preferably therefrom having removed chlorine and fluorine obtains.Under the situation of making two succinimides, can react with it with the polybutylene-based succinimide that reaches polyamine doubling dose (mol ratio).Under the situation of making single succinimide, react with it with the same polybutylene-based succinimide of measuring of polyamine.
The succinimide of boracic can not be by with the compound of general formula (3) or (4) and oxygen-containing organic compound reaction, neutralization or the part or all of remaining amino of amidation and/or imide and the compound that obtains.
The example of this oxygen-containing organic compound is the monocarboxylic acid with 1-30 carbon atom, such as formic acid, acetate, oxyacetic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, hendecoic acid, lauric acid, ficocerylic acid, tetradecanoic acid, 15 carbonic acid, palmitinic acid, pearl acid, stearic acid, oleic acid, 19 carbonic acid and 20 carbonic acid; Polyprotonic acid with 2-30 carbon atom is such as oxalic acid, phthalic acid, trimesic acid and pyromellitic acid and their acid anhydrides and ester; Have the polyoxy alkylidene of 2-6 carbon atom and the carbonic ether of hydroxyl (gathering) oxyalkylene.By reacting, suppose that part or all of amino or the imido grpup in general formula (3) or (4) all had as the represented structure of general formula (5) with these oxygen-containing organic compounds.
Wherein, R
13Be hydrogen, have alkyl, thiazolinyl or an alkoxyl group of 1-24 carbon atom, or by-O-(R
14O)
mThe hydroxyl that H represents (gathering) oxyalkylene, R herein
14Be the alkylidene group with 1-4 carbon atom, m is the integer of 1-5.
The boracic succinimide is the compound that is obtained by the compound of general formula (3) or (4) and boron-containing compound reaction.
The example of boron-containing compound is boric acid, borate and boric acid ester.The object lesson of boric acid is ortho-boric acid, metaboric acid and tetraboric acid.Boratory example is an alkali metal salt, alkaline earth salt or the ammonium salt of boric acid.Example is a lithium tetraborate more specifically, such as lithium metaborate, lithium tetraborate, five lithium tetraborates and peroxyboric acid lithium; Sodium Tetraborate is such as sodium metaborate, hypoboric acid sodium, sodium tetraborate, sodium pentaborate, six Sodium Tetraboratees and eight Sodium Tetraboratees; Potassium borate is such as potassium metaborate, potassium tetraborate, potassium pentaborate, six potassium borates and eight potassium borates; Lime borate is such as calcium metaborate, hypoboric acid calcium, tetraboric acid DFP, tetraboric acid five calcium and six lime borates; Magnesium borate is such as magnesium metaborate, hypoboric acid magnesium, tetraboric acid three magnesium, tetraboric acid five magnesium and magnesium hexaborate; Ammonium borate is such as ammonium metaborate, tetraboric acid ammonium, ammonium pentaborate and eight ammonium borates.The example of boric acid ester is boric acid and the ester with fatty alcohol of 1-6 carbon atom, more specifically is boric acid mono-methyl, trimethyl borate, trimethyl borate, boric acid mono ethyl ester, boric acid diethyl ester, triethyl borate, boric acid list propyl ester, boric acid dipropyl, tripropoxy-boron, boric acid mono, boric acid dibutylester and tributyl borate.
The present invention is had no particular limits the mass ratio (B/N ratio) of boron in the boracic succinimide that uses and nitrogen.Yet the lower limit of this ratio is 0.2, preferably 0.3, be more preferably 0.5, and the upper limit is 1.2, and preferably 1, be more preferably 0.9.This ratio will cause the relatively poor lubricating oil composition of effect less than lower limit, and this ratio will cause very poor oxidative stability above the upper limit.
Though above-mentioned boracic succinimide and single succinimide of boracic or two succinimides can not distinguished separately and use as component (B), preferably use the boracic succinimide separately or use, because expection can further improve the frictional behaviour in the humid clutch with the not single succinimide or two succinimides of boracic.Above-mentioned boracic succinimide is preferably 100 with the ratio of mixture of boracic succinimide (mass ratio) not: 0-20: 80, more preferably 90: 10-40: 60, be preferably 70 especially: 30-45: 55.
Based on the total mass of the present composition, the content of component (B) is 0.08 quality % in the nitrogen lower limit, preferably 0.09 quality %.Based on the total mass of the present composition, the content of component (B) is 0.3 quality % in the nitrogen upper limit, preferably 0.2 quality %.The content of component (B) is lower than down in limited time, is created in the lubricating oil composition that temperature therefrom can not substantially improve to high-temperature fuel consumption efficiency and the frictional behaviour in humid clutch.And the content that uses component (B) is higher than in limited time, and the fuel consumption efficiency of the lubricating oil composition that obtains, low temperature viscosity and demulsification performance all worsen.For the same reason, total mass based on composition, content lower limit in the boracic succinimide of boron is 0.005 quality %, preferably 0.01 quality % is more preferably 0.02 quality %, and based on the total mass of composition, upper content limit in the boracic succinimide of boron is 0.2 quality %, preferably 0.1 quality % is more preferably 0.08 quality %, especially preferably 0.05 quality %.The boracic succinimide surpasses the upper limit will have adverse influence to emission-control equipment.
In lubricating oil composition of the present invention, in the component (B) of nitrogen with in the mass ratio of the component (A) of molybdenum, its lower limit is 1.6, preferably 1.8, especially preferably 2.1, and the upper limit of this mass ratio is 100, preferably 10, be more preferably 5, especially preferably 4.Mass ratio will cause lubricating oil composition not good to pyritous fuel consumption efficiency and the frictional behaviour in humid clutch in middle temperature less than lower limit, and mass ratio can not provide enough fuel consumption efficiency above the upper limit.
Be described in detail the alkaline-earth metal clean-out system below, i.e. component (C).Component (C) can be alkaline earth metal sulfonate, alkaline-earth metal phenates and alkaline-earth metal salicylate.In the present invention, qualified alkaline-earth metal clean-out system is exactly one or more compounds from wherein choosing.
Preferred alkaline earth metal sulfonate is by sulfonation molecular weight 300-1,500, and the salt of the alkaline-earth metal of the alkyl aryl sulfonate that the alkyl aromatic compound of preferred 400-700 obtains, preferably magnesium salts and/or calcium salt, especially preferably calcium salt.
The object lesson of alkyl aryl sulfonate is mahogany acid and synthetic sulfonic acid.
Mahogany acid can be the mahogany acid that the alkyl aromatic compound that contains in the lubricating oil distillate of mineral oil lubricating oil distillate when making white oil or by-product obtains through sulfonation.Synthetic sulfonic acid can be that the alkylbenzene with straight or branched alkyl obtains through sulfonation, the alkylbenzene here can be by the byproduct of making detergent use alkylbenzene factory, perhaps has the alkene of 1-12 carbon atom by alkylation such as the oligopolymer of ethene and propylene obtains to benzene or sulfonation dinonyl naphthalene.Though do not limit, can use oleum and sulphuric anhydride as sulphonating agent.In the present invention, petroleum-based alkaline earth metal sulfonate have in the improvement temperature to the pyritous fuel consumption efficiency and in humid clutch the effect of stiction performance, and the synthetic alkaline earth metal sulfonate has and particularly improves at high temperature fuel consumption efficiency and braking time exponential effect.Therefore, they can optionally be used as required.
The example of alkaline-earth metal phenates is alkaline earth salt, particularly magnesium salts and the calcium salt of alkylphenol, alkylphenol thioether or alkylphenol mannich reaction product.Concrete example is the compound of general formula (6)-(8) expression:
In general formula (6), (7) and (8), R
21, R
22, R
23, R
24, R
25And R
26Can be identical or different, expression independently of one another has 4-30 carbon atom, preferably has the alkyl of the straight or branched of 6-18 carbon atom, M
1, M
2And M
3Represent alkaline-earth metal independently of one another, preferably calcium and magnesium, x is 1 or 2 integer.
Alkyl R
21, R
22, R
23, R
24, R
25And R
26Object lesson be 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.These alkyl can be straight chain or side chain, can be primary alkyl, secondary alkyl or tertiary alkyl.In the present invention, preferably use the alkaline-earth metal phenates, because they can improve in middle temperature to pyritous fuel consumption efficiency and the frictional behaviour in humid clutch.
The alkaline-earth metal salicylate example be the alkaline earth salt of alkyl salicylate, preferably magnesium salts and calcium salt.Object lesson is the compound of general formula (9) expression:
In general formula (9), R
27Be to have 4-30 carbon atom, the straight or branched alkyl of preferred 6-18 carbon atom, M
4Be alkaline-earth metal, preferably calcium or magnesium.
R
27Object lesson be 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.These alkyl can be straight chain or side chain, can be primary alkyl, secondary alkyl or tertiary alkyl.In the present invention, preferably use the alkaline-earth metal salicylate, because they can improve fuel consumption efficiency and the frictional behaviour in humid clutch.
Component (C) can be by alkyl aryl sulfonate, alkylphenol, the alkylphenol thioether, alkaline-earth metal alkali reactions such as the oxide compound of the mannich reaction product of alkylphenol thioether or alkyl salicylate and alkaline-earth metal such as magnesium and/or calcium or oxyhydroxide, perhaps by being converted into an alkali metal salt, as the substituted alkyl aromatic sulphonic acid of sodium salt and sylvite, alkylphenol, the alkylphenol thioether, the neutral alkaline earth metal sulfonate that Manny phase (Mannich) reaction product of alkylphenol thioether or alkyl salicylate and alkaline-earth metal reactant salt obtain, alkaline-earth metal phenates and alkaline-earth metal salicylate.In addition, component (C) can be in the presence of water, neutral alkaline earth metal sulfonate, alkaline-earth metal phenates or alkaline-earth metal salicylate is heated together with excessive alkaline earth salt or alkaline earth metal alkali and the basic alkaline earth metal sulfonate, alkaline-earth metal phenates and the alkaline-earth metal salicylate that obtain.Have again, component (C) can be under neutral alkaline earth metal sulfonate, alkaline-earth metal phenates or alkaline-earth metal salicylate exist, the high alkaline alkaline earth metal sulfonate, alkaline-earth metal phenates and the alkaline-earth metal salicylate that obtain by alkaline earth metal hydroxides and carbonic anhydride or acid reaction.
In the present invention, can use aforesaid alkaline earth salt, neutral alkaline earth salt, basic alkaline earth metal salt, high-alkaline base earth metal salt and their mixture.
The commercial metal clean-out system is generally with the dilution of light lubricant base oil.Preferably use its metal content to be 1.0-20 quality %, the metal matrix clean-out system of preferred 2.0-16 quality %.
Total alkalinity to component (C) has no particular limits.Yet in order to obtain excellent clean-out system, the total alkalinity of component (C) is 500mgKOH/g or littler, is preferably 150-450mgKOH/g.The term of Shi Yonging " total alkalinity " refers to according to JIS K2501 (1992) the 7th joint " petroleum products and lubricating oil degree of neutralization are measured " (Petroleum products andlubricants-Determination of neutralization number), with the total alkalinity of perchloric acid potentiometric titration measurement herein.
The lower limit of component in lubricating oil composition of the present invention (C) content is 0.01 quality %, and preferably 0.02 quality % is more preferably 0.04 quality %.The upper limit of component (C) is 0.16 quality %, can successfully reduce the formation of ash like this, but 0.13 quality % preferably is more preferably 0.07 quality %.The content of component (C) is lower than lower limit, in middle temperature frictional behaviour variation all in pyritous fuel consumption efficiency and the humid clutch, and component (C) surpasses the upper limit and can improve frictional behaviour for humid clutch, can not make lubricating oil, cause ash in emission-control equipment or combustion chamber, to be assembled with low ash formation performance.
The object lesson of component (D), promptly zinc dithiophosphate is the compound with general formula (10) expression:
In general formula (10), R
31, R
32, R
33And R
34Expression independently of one another has the alkyl of 1-24 carbon atom.
For R
31, R
32, R
33And R
34The alkyl with 1-24 carbon atom and general formula (1) in the above in the R of narration
1, R
2, R
3And R
4Be identical.
Preferably the compound with general formula (10) expression is a zinc dialkyl dithiophosphate, alkyl wherein can be straight chain or side chain, such as Methyl disulfide for zinc phosphate, diethyldithiophosphoric acid zinc, the dipropyl zinc dithiophosphate, zinc dibutyldithiophosphate, diamyl disulfide is for zinc phosphate, the dihexyl zinc dithiophosphate, the diheptyl zinc dithiophosphate, the dioctyl zinc dithiophosphate, the dinonyl zinc dithiophosphate, the didecyl zinc dithiophosphate, two (undecyl) zinc dithiophosphate, two (dodecyl) zinc dithiophosphate, two (tridecyl) zinc dithiophosphate, two (tetradecyl) zinc dithiophosphate, two (pentadecyl) zinc dithiophosphate, two (hexadecyl) zinc dithiophosphate, two (heptadecyl) zinc dithiophosphate, two (octadecyl) zinc dithiophosphate; The phenylbenzene zinc dithiophosphate; The dialkyl phenyl organic zinc dithiophosphate, alkyl wherein can be straight chain or side chain, can be bonded to any position of phenyl, such as the xylyl zinc dithiophosphate, the bixylyl zinc dithiophosphate, diethyl phenyl zinc dithiophosphate, dipropyl phenyl zinc dithiophosphate, dibutyl phenyl zinc dithiophosphate, diamyl phenyl zinc dithiophosphate, dihexyl phenyl zinc dithiophosphate, diheptyl phenyl zinc dithiophosphate, dioctyl phenyl zinc dithiophosphate, dinonyl phenyl zinc dithiophosphate, didecyl phenyl zinc dithiophosphate, two (undecyl phenyl) zinc dithiophosphate and two (dodecylphenyl) zinc dithiophosphates; And with the mixture of two or more these compounds of suitable proportion blended.These zinc dialkyl dithiophosphates and dialkyl phenyl organic zinc dithiophosphate can have the alkyl of different carbonatomss and different structure in a molecule.
In the present invention, component (D) preferably has the zinc dithiophosphate (uncle ZDTP) of primary alkyl and has the mixture of the zinc dithiophosphate (secondary ZDTP) of secondary alkyl.The ratio of mixture (mass ratio) of uncle ZDTP and secondary ZDTP is preferably 5: 95-50: 50, more preferably 10: 90-40: 60.Ratio of mixture in this scope can obtain the lubricating oil composition with excellent abrasion resistance of desired result of the present invention.
In lubricating oil composition of the present invention, based on the total mass of composition, the content of component (D) is 0.1 quality % in the zinc upper limit, and preferably 0.08 quality % is more preferably 0.06 quality %.Based on the total mass of composition, the content of component (D) is 0.01 quality % in the zinc lower limit, preferably 0.02 quality %.Component (D) content surpasses the upper limit, because phosphorus or zinc have disadvantageous effect to frictional behaviour in high-temperature fuel consumption efficiency and the humid clutch, thereby emission-control equipment is had adverse influence.Component (D) content is lower than down in limited time, will obtain the not good lubricating oil of abrasion resisting performance and fuel consumption efficiency, and this is owing to sulphur source minimizing in the composition causes that the molybdenumdisulphide amount descends on sliding part.Component (D) just can access at low temperature all excellent to the high-temperature fuel consumption efficiency in the scope of as above stipulating, particularly the improved lubricating oil composition of frictional behaviour in the humid clutch.
Component (E) is described below, i.e. phosphoric acid ester or bi-ester of phosphite.
The example of component (E) is phosphate monoester, phosphodiester, phosphotriester, phosphorous acid monoesters, phosphorous acid diester, tris phosphite, thiophosphatephosphorothioate, phosphorodithioate, phosphorotrithioate, thiophosphite, dithio phosphorous acid ester, trithiophosphite and their salt.These compounds all have the alkyl that preferably contains 3-20 carbon atom.
Example with alkyl of 3-20 carbon atom is alkyl, cycloalkyl, thiazolinyl, aryl and alkaryl, and they all can have substituting group.
The example of alkyl is ethyl, propyl group, butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, they can be straight chain or side chain.
The example of cycloalkyl is the cycloalkyl with 5-7 carbon atom, such as cyclopentyl, cyclohexyl and suberyl.
The example of the cycloalkyl that alkyl replaces is the group with 6-11 carbon atom, such as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl, wherein the position of alkyl is changeable.
The example of thiazolinyl is butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls and octadecylene base, they can be straight chain or side chain, the position of its pair key can change.
The example of aryl is phenyl and naphthyl.The example of the aryl that alkyl replaces is the substituted aryl with 7-18 carbon atom, such as tolyl, xylyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl and dodecylphenyl, alkyl wherein can be straight chain or side chain, its position on aryl can change.
The example of aralkyl is the aralkyl with 7-12 carbon atom, such as benzyl, phenylethyl, phenyl propyl, phenyl butyl, phenylpentyl and phenyl hexyl, alkyl wherein can be straight chain or side chain.
The example of preferred ingredients (E) is: the mono alkyl ester of phosphoric acid, such as mono phosphoric acid ester propyl ester, mono phosphoric acid ester butyl ester, phosphoric acid single fifth ester, the own ester of mono phosphoric acid ester, mono phosphoric acid ester heptyl ester and mono-octyl phosphate, alkyl wherein can be straight chain or side chain; Mono phosphoric acid ester (alkyl) aryl ester is such as mono phosphoric acid ester phenyl ester and mono phosphoric acid ester cresols ester; Di(2-ethylhexyl)phosphate (alkyl) aryl ester, such as di(2-ethylhexyl)phosphate propyl ester, dibutyl phosphate, di(2-ethylhexyl)phosphate pentyl ester, phosphoric acid dihexyl, di(2-ethylhexyl)phosphate heptyl ester and dioctylphosphoric acid ester, alkyl wherein can be a straight or branched; Di(2-ethylhexyl)phosphate (alkyl) aryl ester is such as diphenyl phosphate and di(2-ethylhexyl)phosphate cresols ester; Trialkylphosphate, such as tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate and trioctyl phosphate, alkyl wherein can be straight chain or side chain; Tricresyl phosphate (alkyl) aryl ester is such as triphenylphosphate and tritolyl phosphate; The phosphorous acid mono alkyl ester, such as phosphorous acid list propyl ester, phosphorous acid mono, phosphorous acid list pentyl ester, the own ester of phosphorous acid list, phosphorous acid list heptyl ester and phosphorous acid mono octyl ester, alkyl wherein can be a straight or branched; Phosphorous acid list (alkyl) aryl ester is such as phosphorous acid monophenyl and phosphorous acid list cresols ester; Dialkyl phosphite, such as phosphorous acid dipropyl, dibutyl phosphite, phosphorous acid diamyl ester, phosphorous acid dihexyl, phosphorous acid two heptyl esters and dioctyl phosphite, alkyl wherein can be a straight or branched; Phosphorous acid two (alkyl) aryl ester is such as phosphorous acid diphenyl ester and phosphorous acid diformazan phenolic ester; Trialkyl phosphite, such as tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite heptyl ester and tricresyl phosphite monooctyl ester, alkyl wherein can be a straight or branched; Tricresyl phosphite (alkyl) aryl ester is such as triphenyl phosphite and tricresyl phosphite cresols ester; And their mixture.
The object lesson of the salt of phosphoric acid ester or phosphorous acid ester is to be reacted such as the amine compound with 1-8 carbon atom that only has hydrocarbon or hydroxyl in ammonia or the molecule by phosplate, bisphosphate, triguaiacyl phosphate, single phosphorous acid ester, diphosphites or GW-540 and nitrogenous compound, makes all or part of remaining acid hydrogen atom be neutralized resulting compound.Phosphoric acid ester or phosphorous acid ester salt can be the salt of divalent metal such as zinc or iron.
The object lesson of nitrogenous compound is an ammonia; Alkylamine, wherein alkyl can be a straight or branched, such as single methylamine, mono aminoethane, single propylamine, dibutyl amine, monoamylamine, single hexylamine, single heptyl amice, single octylame, dimethylamine, methylethyl amine, diethylamine, methyl-propyl amine, ethyl propyl amine, dipropyl amine, methyl butyl amine, N-Ethylbutylamine, propyl group butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; Alkyl alcoholamine, silane alcohol base wherein can be a straight or branched, such as 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; And their mixture.
Component (E) may be used singly or in combin.In the present invention, component (E) preferably is selected from least a in phosplate, bisphosphate, single phosphorous acid ester, diphosphites, thiophosphatephosphorothioate, thiophosphite and their salt, is more preferably to be selected from least a in single phosphorous acid ester, diphosphites and their salt.The carbonatoms of these alkyl is 4-20 preferably, is more preferably 6-18.
Do not use component (E), cause the further content that reduces phosphorus, lubricating oil composition can obtain expected effect.Yet performance test is confirmed on the road that the use 4 stroke motorcycle carries out, when the rotating ratio of engine hangs down, such as 1, during 000rpm and when higher, such as 10, during 000rpm, because the existence of component (E) can realize the further improvement of fuel consumption efficiency.Therefore, under these circumstances, lubricating oil composition of the present invention preferably contains component (E).The lower limit of component in lubricating oil composition of the present invention (E) content based on the total mass of composition, in phosphorus 0.005 quality % preferably, is more preferably 0.01 quality %.And based on the composition total mass, be 0.1 quality % in the upper limit of the component (E) of phosphorus, preferably 0.08 quality % is more preferably 0.04 quality %.Component (E) surpasses last effect that just can not obtain expecting and that phosphorus content is reached when hanging down in lubricating oil composition in limited time.
Though lubricating oil composition of the present invention is excellent aspect fuel consumption efficiency, promptly low friction performance and the frictional behaviour in humid clutch can be added conventional additive in order further to strengthen these performances in composition.These additives can be except component (A) friction modifiers, the ashless dispersant except component (B), the metal cleaner except component (C), except component (D) with the extreme-pressure additive (E) and anti-wear agent, oxidation retarder, rust-preventive agent, corrosion inhibitor, viscosity index improver, pour point depressant, the agent of rubber swelling, defoamer and tinting material.
Friction improver except component (A) is fatty alcohol, lipid acid, fatty acid metal salt, fatty acid ester, fatty amine, aliphatics amine salt and aliphatic amide.Though these friction improvers are effective not as molybdenum compound aspect fuel consumption efficiency, but use these friction improvers to replace the molybdenum compound that will use in the present invention or be used in combination, can provide to have excellent fuel consumption efficiency and the lubricating oil composition of frictional behaviour in humid clutch with molybdenum compound.
Ashless dispersant except component (B) is the product of benzyl amine, alkyl polyamine, polybutene amine and their boron or sulphur modification, and the succsinic acid alkenyl esters.
Metal cleaner except component (C) is sulfonate, phenates and the salicylate of basic metal base, and the naphthoate of basic metal base and alkaline-earth metal-based, and they may be used singly or in combin.Basic metal can be sodium or potassium.
Except component (D) and extreme-pressure additive and anti-wear agent (E) be sulfur-based compound, the object lesson of this sulfur-based compound is the oil or the fat of disulphide, alkene sulfide and sulfide.
The example of oxidation retarder is phenolic group or the amino-complex that uses in lubricating oil usually.The object lesson of such oxidation retarder is an alkylphenol, such as 2, and 6-di-t-butyl-4-cresols; Bis-phenol, such as methylene radical-4,4-biphenol-(2,6-di-t-butyl-4-cresols); ALPHA-NAPHTHYL AMINE is such as phenyl-; Dialkyl group diphenylamine and phenothiazine.
The example of rust-preventive agent is ester, sulfonated petro-leum and the dinonylnaphthalene sulfonic acid salt of alkenyl succinic acid, alkenyl succinic acid ester, polyhydroxy-alcohol.
The example of corrosion inhibitor is benzotriazole, thiadiazoles and imidazolium compounds.
Viscosity index improver can be the index improving agent of non-dispersion liquid type or dispersion liquid type.Concrete example is polymethacrylate and olefin copolymer, polyisobutene, polystyrene, ethylene propylene copolymer and vinylbenzene-diene copolymers and their the hydrogenation thing of non-dispersion liquid type or dispersion liquid type.The weight-average molecular weight of these viscosity index improvers is 5,000-1,000,000.Yet wish that using weight-average molecular weight is 10,000-1,000,000, be preferably 200,000-900,000, be preferably 400 especially, 000-800,000 viscosity index improver is with further enhancing fuel consumption efficiency.Use in 4 stroke motorcycle under the lubricated oil condition of the present invention, particularly preferably be styrene diene copolymer and hydrogenation products thereof, purpose is to strengthen shear stability.
The example of pour point depressant is the polymkeric substance of polyacrylate based, alkylating aromatics, fumarate-acetate ethylene copolymer and ethylene-vinyl acetate copolymer.
The example of defoamer is a polysiloxane, such as dimethyl polysiloxane and fluorinated polysiloxane.
Each consumption in these additives all there is not specific restriction.Yet, the add-on of defoamer is 0.005-0.01 quality %, and the add-on of viscosity index improver is 0.05-20 quality %, and the add-on of corrosion inhibitor is 0.005-0.2 quality %, and the add-on of other additives is 0.05-10 quality %, and all are all based on the total mass of composition.
Lubricating oil composition of the present invention is excellent in middle temperature on the frictional behaviour in pyritous fuel consumption efficiency and the humid clutch not only, also be excellent on abrasion resisting performance, high temperature oxidation stability and scourability, its quality further also enough satisfies the standard by the defined four-stroke engine for motor cycle lubricating oil of JASO (JASO T903-98).Requiring the vitriol ash content of engine oil one of in this standard is 1.2 quality % or littler.The present invention can make the lubricating oil of low grey type, its vitriol ash content is 1.0 quality % or lower, further be 0.8 quality % or lower, 0.7wt or lower particularly, middle temperature have an excellent fuel consumption efficiency to high temperature and the humid clutch that very improved in frictional behaviour.The term of Shi Yonging " vitriol ash content " refers to the ash content of the sulphating of measuring according to JIS K2272 herein, promptly by measuring the burning sample and to the resulting ash content of constant weight that wherein adds the carbonization residue that sulfuric acid obtains.
Lubricating oil composition of the present invention, based on the composition total mass, phosphorus content is 0.12 quality %.Yet, can be reduced to 0.1 quality % to phosphorus content by regulating the amount of forming each component of lubricating oil composition of the present invention, further be reduced to 0.08tw%, particularly be reduced to 0.07 quality %.If the component of dispensing (E) can further be reduced to 0.05 quality % to phosphorus content, make this composition on fuel consumption efficiency and humid clutch internal friction performance, further improve.In four-stroke engine for motor cycle, use under the situation of the present composition, preferably contain component (E) because as when component (E) is described say that fuel consumption efficiency can further improve.
The so low ash that is obtained by the present invention and the lubricating oil composition of phosphorus content can fully reduce the harmful effect to emission-control equipment, and it is very favourable therefore using on the automobile that three-way catalyst, oxide catalyst, egr system, DPF etc. are housed.
Lubricating oil composition of the present invention is at 100 ℃ kinetic viscosity 5.6mm preferably
2/ s or higher is more preferably 9.3mm
2/ s or higher, preferably 21.9mm
2/ s or lower is more preferably 16.3mm
2/ s or lower, especially preferably 12.5mm
2/ s or lower.The specified range of this kinetic viscosity can give lubricating oil composition stronger fuel consumption efficiency under 100 ℃.
Lubricating oil composition of the present invention is suitable for I. C. engine, such as petrol engine, diesel motor and gas blowing engine, be particularly suitable for having exhaust additional processing device, the oil engine of the power transmission mechanism of humid clutch and 4 stroke motorcycle etc. is housed.Yet this lubricating oil composition also can use the lubricating oil that has fuel consumption efficiency and the friction regulating power is arranged as requiring, such as shock absorber oil.
Embodiment
Describe the present invention in more detail below by the following examples and Comparative Examples, but they should not constitute limitation of the scope of the invention.
[
Embodiment1-14 and
Comparative Examples1 and 2]
According to as the lubricating oil composition of the present invention of the formulation in the following table 2 (embodiment 1-14) be used for the lubricating oil composition (Comparative Examples 1 and 2) of comparison.The composition of embodiment 1-14 is to have reduced the sulphating ash and contained the boracic of arbitrary combination or the composition of boracic succinimide not.The composition of Comparative Examples 1 is the fuel saving h type engine h lubricating oil of common alkaline-earth metal Whitfield's ointment alkali, reduce the alkaline-earth metal salicylate and the composition that obtains and the composition of Comparative Examples 2 is compositions by Comparative Examples 1, caused wherein the sulphating ash to be reduced to 0.6 quality % or still less.Carry out following SRV friction testing and clutch friction performance test, to estimate each composition in 80-120 ℃ conservation of fuel performance and the frictional behaviour in humid clutch.The result is as shown in the table 1.
[SRV friction testing]
Use SRV friction testing device to carry out this test, this equipment generally is used for the engine evaluated lubricating oil composition provides the ability of fuel consumption efficiency.The frictional coefficient of finding engine oil is low more, and fuel consumption efficiency is just good more.At the load of 400N, under the frequency of 50Hz, the amplitude of 1.5mm, (10 ℃ at every interval) measures the frictional coefficient of each composition under 80-120 ℃ temperature.
[clutch friction performance test]
JASO motorcycle four-stroke engine lubricating oil standard (JASO T 903-98) has stipulated to be suitable for the physical and chemical performance of the engine oil that motorcycle four-stroke engine uses and based on the performance classification of frictional behaviour.More specifically say, measure dynamic friction coefficient, static friction coefficient and braking time, make and determine kinetic friction coefficient index, static friction coefficient exponential sum braking time index according to the method for calculation of narrating below according to the test condition of JASO T 904-98.
According to the numerical value that is displayed in Table 1 out the index classification that obtains is organized to MA group or MB.It all is excellent that the MA group is illustrated in kinetic friction coefficient, static friction coefficient and this lubricating oil composition of braking time aspect.And any index of MB group expression all is lower than standard, and the ability of avoiding clutch slip is very poor.
Table 1
The performance of motorcycle four-stroke engine lubricating oil and designation number
Method of calculation: (example: the kinetic friction index)
Kinetic friction index=1+ (μ d (s)-μ d (B))/(μ d (A)-μ d (B))
Wherein:
μ d (s): the kinetic friction coefficient of sample oil;
The kinetic friction coefficient of μ d (A): JAFRE-A (high frictional behaviour standard oil);
The kinetic friction coefficient of μ d (B): JAFRE-B (the low friction performance standard oil that contains friction improver);
Stiction exponential sum braking time index is determined with same method of calculation.
*1: fragrant content: 6.3 quality %; Viscosity index: 122; Kinetic viscosity (100 ℃): 4.11mm
2/ s; NOACK volatility: 14.5 quality %;
*2: fragrant content: 8.1 quality %; Viscosity index: 130; Kinetic viscosity (100 ℃): 6.56mm
2/ s; NOACK volatility: 6.9 quality %;
*3: alkyl: C8; Molybdenum content: 7.2 quality %; Phosphorus content: 5.5 quality %;
*4: alkyl: C8; Molybdenum content: 4.5 quality %;
*5: nitrogen content: 1.8 quality %; Boron content: 0.47 quality %; B/N ratio: 0.26;
*6: nitrogen content: 1.5 quality %; Boron content: 0.5 quality %; B/N ratio: 0.33;
*7: nitrogen content: 1.5 quality %; Boron content: 1.3 quality %; B/N ratio: 0.86;
*8: nitrogen content: 2.1 quality %; Boron content: 0 quality %; The B/N ratio: 0, monotype;
*9: nitrogen content: 1.8 quality %; Boron content: 0 quality %; The B/N ratio: 0, dimorphism;
*10: calcium contents: 6.4 quality %; Total alkalinity: 170mgKOH/g;
*11: calcium contents: 9.0 quality %; Total alkalinity: 255mgKOH/g;
*12: petroleum base calcium sulphonate, calcium contents: 120 quality %; Total alkalinity: 320mgKOH/g;
*13: ethylene low polymer-alkylating calcium sulphonate, calcium contents: 11.8 quality %; Total alkalinity: 310mgKOH/g;
*14: alkyl: C3-C8, the secondary ZDTP mass ratio of uncle ZDTP/: 20/80.Zinc content: 8.2 quality %, total phosphorous: 7.1 quality %;
*15: alkylphosphonic acid carboxylic acid amine salt, phosphorus content 2.4 quality %;
*16: comprise SDC/PMA viscosity index improver, phenol/amido oxidation retarder and defoamer.
By the result who is displayed in Table 2 as can be seen, the Comparative Examples 1 that contains calcium salicylate with calcium contents 0.18 quality % is a kind of traditional engine oil, it is excellent on fuel consumption efficiency under 80 ℃, but the fuel consumption efficiency under 100 ℃ or higher temperature is just very poor.Have, said composition represents that the stiction performance index of frictional behaviour in the humid clutch is low especially again, may cause slipping of clutch when starting or shift gears.Reduced the composition of the Comparative Examples 2 that calcium salicylate content obtains later in Comparative Examples 1, made the content of sulphating ash reach 0.6 quality %, but compare, in the fuel consumption efficiency variation of middle temperature to high temperature (80-120 ℃) with Comparative Examples 2.Find that also the stiction performance index that Comparative Examples 2 compositions table are shown in frictional behaviour in the humid clutch is very low, cause starting and the gearshift poor performance that kinetic friction performance index and braking time index are poor, cause the power transmission performance poor.
By the result who is displayed in Table 2 as can be seen, the composition that contains the embodiment 1-9 of boracic succinimide (B/N is than being 0.2-0.9) and no boron succinimide, its sulphating ash is all identical, and it is approximate or lower with Comparative Examples 2, but compare with Comparative Examples 2, their middle temperature frictional behaviour in high-temperature fuel consumption efficiency and the humid clutch all improves.Particularly, contain embodiment 1 composition of calcium salicylate, compare with Comparative Examples 2, wherein temperature has had great improvement to the high-temperature fuel consumption efficiency.The composition that contains the embodiment 2-9 of calcium sulphonate and/or calcium phenylate, frictional behaviour all improves in fuel consumption efficiency at high temperature and the humid clutch especially.In these compositions, contain respectively from the petroleum base calcium sulphonate of mineral oil based alkyl aromatic sulfonated products and high B/N than (0.5-0.9) boracic succinimide embodiment 4,8 and 9, be effective improving aspect the stiction performance index.The embodiment 6 that contains useful ethylene low polymer alkylation calcium sulphonate is effective strengthening under the high temperature aspect fuel consumption efficiency, kinetic friction performance index and the braking time index.Using low N/B than the boracic succinimide of (0.2-0.5) and be used in combination under the situation of single succinimide, preferably use above-mentioned petroleum base calcium sulphonate.In the composition of embodiment 5, the content in alkaline-earth metal petroleum base calcium sulphonate based on the composition total mass is 0.07 quality %, the content of sulphating ash is lowered to 0.5 quality % or lower, wherein temperature is excellent to the high-temperature fuel consumption efficiency, to the MA level, obtain excellent humid clutch frictional behaviour according to the JASO criteria classification of four-stroke engine for motor cycle lubricating oil.
Contain B/N than the composition that does not have the embodiment 10-14 of boron succinimide for the boracic succinimide of 0.5-0.9 and dimorphism, it all is excellent in middle temperature to pyritous fuel consumption efficiency and humid clutch frictional behaviour.The embodiment 11-13 composition that contains useful ethylene low polymer alkylation calcium sulphonate is the MA level according to the JASO criteria classification of four-stroke engine for motor cycle lubricating oil, and finds that the anti-performance of skidding to humid clutch is excellent.Wherein component (D) is lowered to zinc content and counts 0.06 quality %, causes phosphorus content to be reduced to the composition of the embodiment 12 of 0.1 quality %, and special fuel consumption efficiency at high temperature improves.Use MoDTC to replace MoDTP therein, feasible embodiment 13 compositions that are reduced to 0.07 quality % based on the phosphorus content of whole compositions, compare with the standard oil that does not contain organic molybdenum compound, the performance of anti-slipping of clutch has had unexpected improvement, this standard oil is exactly the JAFRE-A standard oil, and each frictional behaviour index of its humid clutch all is 2.0.
Use calcium salicylate to replace the composition of the embodiment 14 of calcium sulphonate therein, wherein temperature is very excellent to the pyritous fuel consumption efficiency, and it is very stable, JASO standard according to four-stroke engine for motor cycle lubricating oil is classified as the MA level, obtains the anti-performance of skidding of excellent humid clutch.
Though table 2 is not pointed out, embodiment 12,13 and 14 SRV frictional coefficient all are low, promptly be respectively 0.038-0.042,0.040-0.042 and 0.37-0.38, even under 50-70 ℃ high temperature, discovery is suitable with Comparative Examples 1 and 2, perhaps better, the latter is respectively 0.038-0.041 and 0.040-0.042.
The middle temperature of lubricating oil composition of the present invention all is excellent to high-temperature fuel consumption efficiency and humid clutch frictional behaviour.Particularly, even under the situation that has reduced sulphating the ash content of coal and phosphorus content, also can keep such excellent properties.Therefore, this lubricating oil composition can suitably be used for I. C. engine, the four-stroke engine for motor cycle lubricating oil that requirement has the fuel consumption efficiency that is caused by nearest thermal load increase, and the used engine oil of motor car engine that emission-control equipment is housed.
Claims (17)
1. lubricating oil composition, said composition contains mineral and/or synthetic base oil, (A) organic molybdenum, its content in molybdenum is 0.003-0.1 quality %, (B) boracic and/or do not have the boron succinimide, its content in nitrogen is 0.08-0.3 quality %, the mass ratio of molybdenum content is 1.6 or bigger in nitrogen and the component (A), (C) alkaline-earth metal clean-out system, its content in alkaline-earth metal is 0.01-0.16 quality %, (D) zinc dithiophosphate, its content in zinc is 0.01-0.1 quality %, and (E) at least a phosphoric acid ester that is selected from, the compound of phosphorous acid ester and salt thereof, its content in phosphorus is 0.1 quality % or littler, above-mentioned content all is based on the gross weight of composition, is 1 quality % or littler based on the vitriol the ash content of coal of its gross weight.
2. lubricating oil composition as claimed in claim 1, wherein component (A) is a molybdenum dithiocarbamate.
3. lubricating oil composition as claimed in claim 1, wherein component (B) contains the boracic succinimide and/or does not have boron list and/or double amber imide, and based on the total mass of composition, the boracic succinimide is 0.005-0.2 quality % in boron content.
4. lubricating oil composition as claimed in claim 1, wherein based on the total mass of composition, component (C) is 0.01-0.07 quality % in alkaline-earth metal content.
5. lubricating oil composition as claimed in claim 1, wherein based on the total mass of composition, component (D) is 0.01-0.06 quality % in zinc content.
6. lubricating oil composition as claimed in claim 1, wherein based on the total mass of composition, the content of sulphating ash is 0.7 quality % or lower in the composition.
7. lubricating oil composition as claimed in claim 1, wherein based on the total mass of composition, the phosphorus content in the composition is 0.08 quality % or lower.
8. lubricating oil composition as claimed in claim 1, the B/N of wherein said boracic succinimide is than being 0.2-0.9.
9. lubricating oil composition as claimed in claim 1, wherein component (C) is to be selected from alkaline earth metal sulfonate, alkaline earth phenolates and the alkaline-earth metal salicylate one or more.
10. lubricating oil composition as claimed in claim 1, wherein the stiction performance index of this lubricating oil composition is 1.15 or bigger.
11. lubricating oil composition as claimed in claim 1, wherein the stiction performance index of this lubricating oil composition is 1.40 or bigger.
12. lubricating oil composition as claimed in claim 1, wherein the kinetic friction performance index of this lubricating oil composition, stiction performance index and braking time index are respectively 1.7 or bigger.
13. lubricating oil composition as claimed in claim 1, wherein according to JASO T 903-98 standard, said composition is classified as the MA level.
14. lubricating oil composition as claimed in claim 1, wherein said composition is the engine oil that is used to be equipped with the automobile of emission-control equipment.
15. lubricating oil composition as claimed in claim 1, wherein said composition is the lubricating oil that is used for four-stroke engine for motor cycle.
16. lubricating oil composition as claimed in claim 1, wherein said molybdenum dithiocarbamate is represented with following general formula:
R wherein
1, R
2, R
3And R
4Expression independently of one another has the alkyl of 1-24 carbon atom, and a is the integer of 0-4, and b is the integer of 0-4, and a+b=4.
17. an improvement is in the method for middle temperature performance of frictional behaviour in pyritous fuel consumption efficiency and/or the humid clutch, this method is used as any one lubricating oil composition among the claim 1-16.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001232827 | 2001-07-31 | ||
| JP2001232827A JP4931299B2 (en) | 2001-07-31 | 2001-07-31 | Lubricating oil composition |
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| Publication Number | Publication Date |
|---|---|
| CN1400295A CN1400295A (en) | 2003-03-05 |
| CN100441667C true CN100441667C (en) | 2008-12-10 |
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ID=19064681
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021269912A Expired - Fee Related CN100441667C (en) | 2001-07-31 | 2002-07-30 | Lubricant oil composite |
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| Country | Link |
|---|---|
| JP (1) | JP4931299B2 (en) |
| CN (1) | CN100441667C (en) |
| TW (1) | TW583308B (en) |
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| JP2003041283A (en) | 2003-02-13 |
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| TW583308B (en) | 2004-04-11 |
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