CN1427069A - Lubricating oil composition for heavy diesel engine - Google Patents

Lubricating oil composition for heavy diesel engine Download PDF

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Publication number
CN1427069A
CN1427069A CN02157566A CN02157566A CN1427069A CN 1427069 A CN1427069 A CN 1427069A CN 02157566 A CN02157566 A CN 02157566A CN 02157566 A CN02157566 A CN 02157566A CN 1427069 A CN1427069 A CN 1427069A
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Prior art keywords
lubricating oil
compound
oil composition
diesel engine
heavy duty
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C·H·伯温顿
S·阿洛史密斯
R·C·卡斯特尔
P·兰奇
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/56—Boundary lubrication or thin film lubrication
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Abstract

The use of an effective amount of one or more compounds capable of reducing friction coefficients under mixed lubrication or boundary lubrication conditions in a heavy duty diesel engine lubricating oil composition for improving the fuel economy of a heavy duty diesel engine.

Description

The heavy duty diesel engine lubricating oil composition
The present invention relates in the lubricating oil composition of heavy duty diesel engine can be in the use of one or more compound of the condition decline low-friction coefficient of mixed lubrication or boundary lubrication.The invention still further relates to this lubricating oil composition, have now found that, the fuel combustion efficiency when this lubricating oil composition can improve heavy duty diesel engine work.
Because the life-span of diesel motor is long and special lube that developed can satisfy the harsh more performance requriements of heavy duty diesel engine, so general heavy truck all uses diesel motor as its preferred propulsion source.
In addition, need several testing of engine to confirm its heavily loaded performance, this is comprising the assessment valve train wearing and tearing relevant with carbon deposit, the Cummins M11 test of filter stoppage and greasy filth.
The fuel consumption of heavy duty diesel engine is very important for the operator of fleet, because fuel cost has constituted 30% of running expense.Therefore, use fuel lubricated efficiently oil compositions can help to reduce the consumption of fuel, even 1% reduction all will cause expense significantly to be saved.
R.I Taylor is at " Heavy Duty Diesel Engine Fuel Economy:Lubricant Sensitivities " 00FL-309, SAE2000 MillenniumPublication " Advances in Powertrain Tribology ", narrate among the SAE2000: because heavy duty diesel engine is in running under the hydrodynamic condition more compared with the passenger car engine, so low friction compound can not effectively reduce the frictional dissipation of heavy duty diesel engine.This conclusion has obtained people such as Stauffer in the lubricating oil engineering, and in December, 1984, people such as 744-751 page or leaf and Kagaya are in the support of SAE811412.
On the contrary, have now found that low friction compound can effectively improve the efficiency of combustion of heavy duty diesel engine fuel.
Therefore, thus a first aspect of the present invention provides the efficiency of combustion that can improve heavy duty diesel engine fuel in the use of one or more compound in the heavy duty diesel engine lubricating oil composition of the condition decline low-friction coefficient of mixed lubrication or boundary lubrication of significant quantity.
A second aspect of the present invention provides a kind of heavy duty diesel engine lubricating oil composition, and it comprises a large amount of lubricant viscosity oil and is added with therein:
(A) under the condition of mixed lubrication or boundary lubrication, can reduce one or more compound of the significant quantity of frictional coefficient;
(B) contain a small amount of detergent compositions of aromatic carboxylic acid's metal-salt; With
(C) paucidisperse agent addition agent; As long as having preferably by dispersant additives deutero-nitrogen content, lubricating oil composition is at least 0.06 quality % based on the quality of composition.
Third aspect present invention provides a kind of heavy duty diesel engine additive concentrate compositions, and it comprises a kind of thinner and one or more additive, and described additive comprises:
(A) one or more can be at the compound of mixed lubrication or condition of boundary lubrication decline low-friction coefficient;
(B) contain the detergent compositions of aromatic carboxylic acid's metal-salt; With
(C) dispersant additives; When lubricating oil composition contains the additive of 2～20 quality %, the heavy duty diesel engine lubricating oil composition that each proportion will can provide second aspect present invention to limit.
A fourth aspect of the present invention provides the combination of the lubricating oil composition that heavy duty diesel engine in the continental rise vehicle and second aspect present invention limited, and the engine that uses in the continental rise vehicle has at least 6.5 liters total flow rate and the discharge capacity of each cylinder is at least 1.0 liters/cylinder.
A fifth aspect of the present invention provides the method for the medium and heavy diesel motor of a kind of lubricated continental rise vehicle, the engine that uses in the continental rise vehicle has at least 6.5 liters total flow rate and the discharge capacity of each cylinder is at least 1.0 liters/cylinder, and this method comprises to engine supplies with lubricating oil composition as second aspect present invention limited.
API (API), Association des ConstructeurEuropeend ' Autombile (ACEA) and Nippon Standard tissue (JASO) have been stipulated the standard of performance that lubricating oil composition is required.Also has known performance specification Global in addition, comprising coming from ACEA, test and performance index in API and the JASO standard.
Therefore, HD lubricating oil composition of the present invention preferably will satisfy the performance requriements of heavy duty diesel engine lubricating oil at least, for example is at least API CF-4 or API CG-4; Preferably be at least API CH-4; Especially at least be API CI-4.In another embodiment, lubricating oil composition of the present invention is not satisfied the restriction of API performance requriements, preferably satisfies ACEAE2-96 at least; More preferably satisfy ACEA E3-96 at least; Especially at least to satisfy ACEA E4-99; Advantageously to satisfy ACEA E5-99 at least.In another embodiment, lubricating oil composition of the present invention is not satisfied the restriction of API and ACEA performance requriements, preferably will satisfy JASODH-1 or Global DHD-1.
Feature of the present invention is discussed now in further detail.
Heavy duty diesel engine
Heavy duty diesel engine of the present invention can be used on the continental rise vehicle, preferably is used in large-scale road vehicle, for example on the large truck.The weight of road vehicle generally all surpasses 12 tons.The engine that uses in this vehicle generally is tending towards having at least 6.5, and preferably at least 8, more preferably be at least 10, for example at least 15 liters total flow rate; Preferred engine has 12～20 liters total flow rate.Usually, the engine that has greater than 24 liters of total flow rates is not considered to the continental rise vehicle.The discharge capacity of each cylinder is at least 1.0 or be at least 1.5 in the engine of the present invention, for example is at least 1.75, is preferably at least 2 liters/cylinder.Usually each cylinder of the heavy duty diesel engine that uses in road vehicle has at the most 3.5, and for example at the most 3.0, preferred 2.5 liters discharge capacity at the most.The term relevant with oil engine " heavy type " is known on technology: referring to ASTM D4485 3.17 in, wherein the running of heavy duty engine characterizes with output of V-bar, power and internal temperature, they are usually near the potential maximum value; Therefore, can think that usually heavy duty diesel engine turns round under this condition.
Here the term of Shi Yonging " total flow rate " and " discharge capacity/cylinder " are known (editors by B.Challen and R.Baranescu referring to " Diesel Engine Reference Book " for the technician of field of internal combustion engine, second edition, 1999, publish) by SAEinternational.In brief, term " discharge capacity " is equivalent to the volume of cylinder in the engine, and this can be measured by the motion of piston, and therefore, " total flow rate " is just for depending on number of cylinders purpose cumulative volume; Term " discharge capacity/cylinder " be total flow rate with engine in the ratio of number of cylinders.
The thin compound of lubricating oil
Of the present invention aspect each in, lubricating oil composition preferably will have less than 0.13 or less than 0.1, or less than 0.09 or less than 0.08 or less than 0.07 or less than the phosphorus of 0.06 quality %, quality in lubricating oil composition, more preferably have at the most 0.05, or at the most 0.04, or 0.03 quality % at the most, for example at 0.001～0.03 quality %; For example at the most 0.02 or the phosphorus of at the most 0.01 quality %.In the preferred embodiment every-way, the phosphorus content of lubricating oil composition is zero.
Of the present invention aspect each in, lubricating oil composition preferably has, and is irrelevant with phosphorus content, and at the most 1.0, or at the most 0.75 or at the most 0.50 or at the most 0.45 or at the most 0.4 or at the most 0.35 or at the most 0.3 or the sulphur of at the most 0.25 quality %, in the quality of lubricating oil composition; Especially preferred its has 0.2 or at the most 0.15 quality % at the most; The sulphur of 0.001～0.1 quality % for example.In the preferred embodiment every-way, the sulphur content of lubricating oil composition is zero.
The content of p and s is measured according to ASTM D5185 in lubricating oil composition.
In the embodiment of the present invention aspect each, the content of p and s is by wear preventive additive, for example the zinc dithiophosphate deutero-.
Lubricating oil composition of the present invention can be SAE 20W-X, SAE 15W-X, and SAE 10W-X, any viscometric form among SAE 5W-X and the SAE 0W-X, wherein X represents 20,30, any one in 40 and 50; In SAE J300 classification, can find the different characteristics of measuring viscosity grade.In the embodiment of the present invention aspect each, irrelevant with other embodiment, lubricating oil composition is the form of SAE 5W-X or SAE 0W-X lubricating oil composition, and wherein X represents 20,30, any one in 40 and 50.Preferred X is 20 or 30.
Also find lubricating oil composition of the present invention, for example the requirement of testing by the Cummins M11 that satisfies the assessment valve train wearing and tearing relevant with carbon deposit can provide heavy duty diesel engine required abrasionproof.Therefore, heavy duty diesel engine lubricating oil composition, particularly low-viscosity lubricating oil composition of the present invention, for example SAE 5W-X or SAE 0W-X lubricating oil, wherein X is with as defined above identical, improved the efficiency of combustion of fuel and improved the wear protection of heavy duty diesel engine.
Therefore, in the preferred embodiment aspect the present invention is every, the heavy duty diesel engine lubricating oil composition, be preferably the form of a kind of SAE 5W-X or a kind of SAE 0W-X lubricating oil composition, comprise that one or more can reduce the compound of frictional coefficient under mixed lubrication or condition of boundary lubrication, and its base-material mixes viscosity (base blend viscosity) and be at least 8.2 in the time of 100 ℃, for example 8.5～30, be preferably 8.5～10mm 2s -1
Here the term of Shi Yonging " base-material mixing viscosity " refers to the composition that recorded by ASTM D445 or the viscosity of mixture in the time of 100 ℃, the included component of said composition or mixture has Newtonian behaviour, these components are to comprise carrier oil (carrier oil) in the present invention, for example oil base stock is in those interior components, but " activeconstituents " that does not comprise solid polymer or viscosity modifier is because they are considered to not have Newtonian behaviour.Therefore, base-material mixes viscosity and refers to and contain oil base stock, dispersion agent, and washing agent, ZDDP, oxidation inhibitor, all carrier oil and thinning oil in the component, pour point depressant and any other demonstrate the component of Newtonian behaviour, for example the viscosity of the composition of defoamer.
Computer simulation system can be used to also to predict that the base-material of lubricating oil composition mixes viscosity, and it is based on the viscosity of the component that exists therein.Perhaps base-material mixing viscosity can be measured the viscosity of resultant composition and measure afterwards by the polymkeric substance in the viscosity modifier is removed from lubricating oil composition.Perhaps, base-material mixing viscosity can be measured by the viscosity of measuring lubricating oil composition under high shear rate.Described shearing rate refers in the speed that does not influence under the lubricating oil composition viscosity, and this speed is greater than 10 usually 7s -1
Have now found that, have definite base-material mixing viscosity parameter and one or more determine the lubricating oil composition of compound can improve fuel efficiency of combustion and at least can be for 200 hours pinblock wearing tests of Cummins M11 by the specification limits of ACEA E5-99 and/or API CH-4.
In the preferred embodiment of the present invention aspect each, record according to ASTM D874 method, oil compositions has the ash less than 2 quality %, preferably less than 1.5 quality %, especially less than 1 quality %, for example at the ash of 0～0.5 quality %.
Lubricant viscosity oil
Lubricating oil can be the synthetic oil or the mineral oil of lubricant viscosity, and it is selected from the I group, II group, III group, oil base stock or its mixture of IV group or V group.
Oil base stock can be produced with various method, and it includes but not limited to distillation, solvent treatment, hydrogen processing, oligomerization, esterification and re-refining.
API 1509 " Engine Oil Licensing and Certification System " the 14th edition, narrates all oil base stock is divided into five big classes in December, 1996.
I group oil base stock contain less than 90% saturates and/or greater than 0.03% sulphur and its viscosity index more than or equal to 80 and less than 120;
II group oil base stock contain more than or equal to 90% saturates and be less than or equal to 0.03% sulphur and its viscosity index more than or equal to 80 and less than 120;
III group oil base stock contain more than or equal to 90% saturates and be less than or equal to 0.03% sulphur and its viscosity index more than or equal to 120;
IV group oil base stock contain poly-alpha olefins (PAO) and
V group oil base stock contain all other be not included in I group, II group, the oil base stock in III group or the IV group.
IV organizes oil base stock, and promptly poly-alpha olefins (PAO) comprises the hydrogenant alpha-olefin low polymers, and the most important method of oligomerization is a free radical method, Ziegler catalysis, positively charged ion and friedel-crafts catalysis.
Preferred lubricating oil is selected from any one in I～V group oil base stock.
Especially preferred is the II group, the III group, and IV group or V group oil base stock or its be two or more mixture arbitrarily, or the I of IV group oil base stock and 5～80 quality %, II, the mixture of III or V group oil base stock, for example complete synthetic mixture of IV group oil base stock and V group oil base stock.
One of be used to define the ASTM D2007 that above-mentioned group method is useful on saturated compound, be used for the ASTM D2270 of viscosity index, and the ASTM D2622 that is used for sulphur, 4294,4927 and 3120.
Compound
Under mixed lubrication or condition of boundary lubrication, such as the compound that can reduce frictional coefficient in high pressure and the sliding contact, be known low friction compound, utilize testing method those of ordinary skill as known in the art just can determine this compound, for example test can back and forth be carried out in the equipment at high frequency.The example of the contact position that high pressure and sliding condition occur is at valve train, in piston ring lining and the shaft bearing.
One based friction reducing agent is provided by polar compound, and this polar compound can be adsorbed on the metallic surface, and this compound has polar head group and lipophilic hydrocarbon chain.They can probably be divided into two classes, i.e. (A) nitrogenous compound, amine for example, imide and acid amides and (B) oxygenatedchemicals, for example lipid acid and its full ester (full esters) or partial ester.
Nitrogenous compound (A) is selected from (i) alkylene amines suitably, especially single Alkylenediamine, and two alkylene triamine and/or polyalkylene polyamine, N, N '-dimethyl-ethylenediamine, it can have more alkyl and/or hydroxyl substituent successively; (ii) alkanolamine, especially the N-alkyl derivative of alkanolamine, thanomin for example, Propanolamine, Yi Bingchunan and butanolamine, wherein the N-alkyl has 1～20 carbon atom, preferred 12～18 carbon atoms, N, N-two alkanolamines, N-alkylidene amino alkyl two alkanolamines and two (polyalkylene oxygen base) alkanolamine; (iii) alkylamide, wherein the N-alkyl has 1～25 carbon atom, preferred 12～22 carbon atoms; The (iv) list of alkanolamide, especially alkyl carboxylic acid and two alkanolamides and (polyalkylene oxygen base) alkanolamide.The specific examples of the nitrogenous organic low friction compound in above-mentioned classification is:
(i) single ethylene diamine, diethylenetriamine, Triethylenetetramine (TETA) and tetren with and the derivative of N-alkyl, for example Duomeen  T and N, N '-two (1-hydroxyl-1,1-dimethyl methyl) ethylene diamine, i.e. Kaneda  No.6;
(ii) thanomin, diethanolamine, Propanolamine, Yi Bingchunan, the N-alkyl of butanolamine or suitable N, the derivative of N-dialkyl group, wherein alkyl has the N-alkylidene amino alkyl ethanol amine of 10～20 carbon atoms, wherein alkylidene group oxygen base add up to 2～20, be preferably 5～15 two (polyalkylene oxygen base) alkanolamine, especially N-Mono Methyl Ethanol Amine (Kaneda  No.1), N-alkyl diethanolamine (Kaneda  No.2B), N, N-dibutyl thanomin (Kaneda  No.4), N-lauryl diethanolamine (Ethomeen  C12), N-alkyl diethanolamine (Ethomeen  S12), N-trimethylene aminoalkyl group diethanolamine, alkyl wherein have 12～18 carbon atoms (Ethoduomeen ), N-alkyl-two (polyalkylene oxygen base) diethanolamine, it has 5 respectively, 10 and 15 polyethylene oxygen groups (being respectively Tamno -5 ,-10 and-15) and N, N '-dihydroxy ethyl ethylene diamine (Kaneda  No.5);
(iii) alkylamide, alkyl wherein has 1～30 carbon atom, preferred 5～20 carbon atoms, and alkyl wherein can be the group of straight or branched, for example Armoslip  CP-P and Armoslip  E, alkyl wherein has 17 and 21 carbon atoms respectively;
(iv) glycollic amide; diglycollic amide and (polyalkylene oxygen base) glycollic amide and its N-alkyl derivative; wherein the N-alkyl has 1～25 carbon atom; preferred 5～20 carbon atoms; and under the situation of (polyalkylene oxygen base) glycollic amide; described acid amides has 5～20 polyoxy alkylidene groups; N-acyl ethanol amine for example; as Kaneda  No.9 (wherein alkyl has 12 carbon atoms in acyl moiety); diethanolamine; Amizole  ISDE (wherein the alkyl in acyl moiety has 18 carbon atoms) for example; Kaneda  No.10 (wherein the alkyl in acyl moiety has 12 carbon atoms); two (polyethylene oxygen base) glycollic amide, wherein the acyl group in acyl moiety has 5 (for example Tamdo -5) that add up to of 17 carbon atoms and the polyethylene oxygen groups in molecule.
Especially preferred example is the compound of oleic acid and tetren, the butter aliphatic ether amine of the tallow amine of ethoxylation and ethoxylation.Can also use the organometallic compound of alkylamine compound, for example at disclosed in the GB-A-882295 those.Amine can use with adducts or with the form of the reaction product of boron compound, and described boron compound for example is a boron oxide, halogenation boron, metaborate, boric acid or one, two or the trialkylboron acid esters.
The example that contains the organic low friction compound of oxygen (B) is the carboxylic acid with 1～25 carbon atom, and for example stearic acid and oleic acid preferably have 12～17 carbon atoms; The full ester and the partial ester of dibasic alcohol and/or polyvalent alcohol, glycerine for example, TriMethylolPropane(TMP), tetramethylolmethane and poly-hydroxy pyrans; And metal-salt, for example stearic metal-salt and oleic metal-salt, wherein metal is selected from transition metal (for example zinc), 1 family's metal and 2 family's metals (for example calcium).The specific examples that contains the organic low friction compound of oxygen (B) is glycerine and alkyl carboxylic acid, oleic acid for example, monoesters, diester and three esters; Corresponding pentaerythritol ester, for example oleic acid ester, especially monoleate; With 1-methylene radical hydroxyl-2,3,4-trihydroxy-pyrans, wherein the methylene radical hydroxyl has been used acid esterification.The ester of carboxylic acid and acid anhydrides and alkanol is described among the US4702850.
The example of other conventional low friction compound is disclosed in " Journal of Tribology " (1992) by M.Belzer, Vol.114, in the 675-682 page or leaf and " Lubrication Science " (1988) that are disclosed in M.Belzer and S Jahanmir, Vol is in the 3-26 page or leaf.
The oil soluble additive of deposition molybdenumdisulphide also is effective low friction compound, for example oil soluble or oily dispersible molybdenum compound.
The example of organic molybdenum comprises the xanthogenic acid molybdenum, sulfo-xanthogenic acid molybdenum, pure molybdenum, carboxylic acid molybdenum (the derivative of polyhydroxy fatty ester for example, for example MOLYVAN  855), molybdenum dialkyldithiocarbamacompositions, dialkyl dithio phosphonous acid molybdenum and molybdenum dialkyl-dithiophosphate.
Molybdenum compound for example can be for monokaryon, two nuclears, trinuclear or tetranucleate.
Two nuclear molybdenum compounds can be used formula M o 2O xS 4-xL 2Represent that wherein L is a part, for example dialkyl dithiocarbamate and dialkyl dithiophosphate, x is 0～4 integer.The example of (or dimerization) molybdenum dialkyldithiocarbamacompositions of two nuclears is to be represented by following general formula:
Figure A0215756600121
R wherein 1～R 4Representative has the straight chain of 1～24 carbon atom, side chain or aromatic hydrocarbyl alone; X 1～X 4Represention oxygen atom or sulphur atom alone.Four alkyl R 1～R 4Can be same to each other or different to each other.
What another that uses in lubricating oil composition of the present invention organized organic molybdenum is three nuclear (or trimerization) molybdenum compounds, especially by formula Mo 3S kL nQ zRepresented those with and composition thereof, wherein L is the independent part of selecting, and its organic group has the carbon atom of enough numbers, thereby can make compound dissolution in oil, n is 1～4, k is 4～7, and Q is selected from neutral electron compound, for example water given, amine, alcohol, phosphuret-(t)ed hydrogen and ether, the scope of z is 0～5 and comprises non-stoichiometric value.In all part organic groups, should have at least 21 carbon atoms altogether, for example be at least 25, be at least 30 or be at least 35 carbon atoms.
Part can be selected from following group :-X-R 1, And composition thereof, X wherein, X 1, X 2Be selected from oxygen and sulphur, R with Y 1, R 2Be selected from hydrogen and organic group with R, they can be identical or different.Preferred organic group is alkyl, for example alkyl (carbon atom that for example wherein is connected part remainder office be one-level or secondary), aryl, the aryl of replacement and ether group.More preferably each part has identical alkyl.
The term that here uses " alkyl " refers to carbon atom and directly is connected the substituting group of part remainder office and mainly is feature with alkyl.This substituting group comprises:
1, hydrocarbon substituent, Zhi Zu (for example alkyl or alkenyl) just, alicyclic (for example cycloalkyl or cycloalkenyl group) substituting group, aromatics-, the aromatic kernel of aliphatic series-and alicyclic ring-group replacement, and cyclic substituents, wherein ring is (that is to say that any two substituting groups of pointing out can form an alicyclic group together) of finishing by another part of part.
2, the hydrocarbon substituent of Qu Daiing just contains those of non-hydrocarbyl group, and they can not change the dominant characteristics of alkyl in the substituting group.Skilled in the art will recognize which is the group (for example, halogen, especially chlorine and fluorine, amino, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group, sulphur oxygen base (sulfoxy) etc.) that is fit to.
Thereby importantly the organic group in the part will have the carbon atom of enough numbers that compound can be dissolved in the oil.For example, the carbonatoms in each group is preferably 1～30 usually 1～100, more preferably 4～20.Preferred part comprises dialkyl dithiophosphate, alkyl xanthate, carboxylate salt, dialkyl dithiocarbamate (" dtc ") and its mixture.Dialkyl dithiocarbamate most preferably.Those skilled in the art will appreciate that wanting to form compound of the present invention just needs to select to have the part of appropriate charge with balance core electric charge (this is discussed below).
Has formula M o 3S kL nQ zCompound have the positively charged ion core, this core is surrounded by anion ligand, wherein the positively charged ion core be by such as With
Figure A0215756600132
Structure represented, it has+net charge of 4 valencys.By selecting appropriate negatively charged ion and cation compound so that three nuclear molybdenum Mo 3S kClass (wherein k is 4～7) is electric neutrality.Preferred four single anion ligands, for example dithiocar-bamate.Under the situation that is not subjected to any theory constraint, it is believed that two or more three cores can or interconnect by the constraint of one or more ligand, and these ligands can be multiple tooth, promptly have a plurality of the connection with one or more core.It is believed that oxygen and/or selenium in core can replace with sulphur.
Oil-soluble three nuclear molybdenum compounds can be by making molybdenum source, for example (NH in suitable liquid/solvent 4) 2Mo 3S 13N (H 2O), wherein n is 0～2 and comprises non-stoichiometric value, and with suitable ligand sources, for example thiuram disulfide reacts and prepares.Other oil-soluble three nuclear molybdenum compounds can be at suitable molybdenum source, for example (NH 4) 2Mo 3S 13N (H 2O), ligand sources, thiuram disulfide for example, dialkyl dithiocarbamate or dialkyl dithiophosphate and sulphur extraction agent, cyanide ion for example, the phosphuret-(t)ed hydrogen of sulfite ion or replacement, solvent in reaction form.Perhaps, three nuclear molybdenum-sulfur halide salt, for example [M '] 2[Mo 3S 7A 6] can with ligand sources, for example dialkyl dithiocarbamate or dialkyl dithiophosphate react in suitable liquid/solvent to form oil-soluble trinuclear molybdenum compound, wherein M ' is a gegenion, A is a halogen, for example Cl, Br or I.The liquid/solvent that is fit to can be, for example water-based or organically.
Thereby selected part must have the carbon atom of enough numbers makes compound may be dissolved in the lubricating oil composition.
The three nuclear molybdenum compounds that are used for the present composition can be formula M o 3S 7((alkyl) 2Dtc) 4Those of representative, wherein alkyl has about 8～18 carbon atoms, and alkyl is preferably " cocounut oil " alkyl chain, and this chain is by the C that is generally derived from Oleum Cocois 8～C 18Alkyl, be mainly C 10, C 12And C 14The mixture that different even carbon atom chains are formed in the alkyl.
The example of other molybdenum compound comprises the composition that contains moly-sulfide, it is to prepare by following mode: (i) acid molybdenum compound and basic nitrogen compound are reacted the complex compound that forms molybdenum in the presence of polar accelerant, wherein basic nitrogen compound is selected from succinimide, carboxylic acid amide, the alkyl monoamine, phosphamide, thio-phosphamide, Mannich alkali, dispersant viscosity index improvers or its mixture and (ii) thereby the reaction of the compound of molybdenum complex and sulfur-bearing is formed the composition of sulfur-bearing and molybdenum.
In one embodiment of the invention, molybdenum compound is preferably two nuclears or trinuclear, more preferably trinuclear.
In another embodiment of the present invention, regardless of the nuclearity (nuclearity) of molybdenum compound, it promptly only contains sulphur as non-metallic element in the nuclear, for example Mo all by complete cure 2S 4, Mo 3S 4And Mo 3S 7
In another embodiment of the present invention, molybdenum compound is preferably the dithiocar-bamate compound, for example two nuclear or trinuclear molybdenum dithiocarbamates; Special compounds effective is by formula M o 3S 7((alkyl) 2Dtc) 4The molybdenum dialkyldithiocarbamacompositions compound of expression.
Also can use the colloid low friction compound in the present invention, graphite for example, borate and molybdenumdisulphide, they exist by dispersion in oil compositions.
Lubricating oil composition can contain the mixture of low friction compound and molybdenum compound, and for example for being attracted to the polar compound on the metallic surface, no matter it is organic or organometallic to described low friction compound.
In another embodiment, low friction compound is a molybdenum compound.
The amount of low friction compound will be enough to improve the efficient of the fuel combustion of lubricated engine.Its content is generally 0.01～5.0, is preferably 0.05～1.5, and 0.1 or 0.15～0.5 quality % more preferably is in the quality of lubricating oil composition.
At low friction compound is under the situation of molybdenum compound, and lubricating oil composition preferably contains 5～5000, more preferably 10～1000, and especially be 50～750, the molybdenum of 75～500ppm (is unit with the quality) for example is in the quality of oil compositions.The content of molybdenum is measured according to ASTM D5185.
Detergent compositions
Washing agent also can be present in the lubricating oil composition of the present invention.
Washing agent is a kind of piston deposit in the engine that reduces, for example the additive of high temperature greasy filth and lacquer deposit thing formation; It has in the acid and performance and be the solid of fine dispersion in suspensoid.It is based on metal " soap ", just is considered to the organic acid metal-salt of tensio-active agent here.
Washing agent comprises a polar head, and promptly organic acid metal-salt and long is used for oil-soluble hydrophobic tail.Therefore, organic acid generally has one or more functional group, for example OH or COOH or SO 3H; And hydrocarbyl substituent.
The organic acid example comprises sulfonic acid, phenols and its sulfurized derivative and carboxylic acid.
Therefore, the detergent compositions that contains one or more organic acid metal-salt can have, for example the mixture of metal sulfonate and metal phenates.
Have now found that the detergent compositions that contains aromatic carboxylic acid's metal-salt can make performance be improved.
Preferred detergent compositions comprises the aromatic carboxylic acid's metal-salt greater than 50 moles of %, in the mole number of metal salts of organic acids in detergent compositions.The ratio of preferred aromatic carboxylic acid's metal-salt is at least 60 or be at least 70 moles of %, and more preferably at least 80 or be at least 90 moles of %, in the mole number of metal salts of organic acids in the detergent compositions.
In the most preferred embodiment, detergent compositions contains aromatic carboxylic acid's metal-salt of 100 moles of %, in the mole number of metal salts of organic acids in the detergent compositions; That is to say that detergent compositions only comprises that the aromatic carboxylic acid is as organic acid.
The aromatics part can contain heteroatoms among the aromatic carboxylic acid, for example nitrogen and oxygen.Preferred this part only contains carbon atom; More preferably this part contains six or more carbon atom, and for example this part is preferably benzene.
The aromatic carboxylic acid can be contained one or more aromatics part, for example one or more phenyl ring, or condensed or connect through alkylidene bridge.
Carboxylic moiety can directly or indirectly partly link to each other with aromatics.Optimization acid's group directly links to each other with carbon atom on aromatics part, for example the carbon atom on phenyl ring.
More preferably aromatics part also contains second functional group, for example hydroxyl or sulfonation group, they can be directly and the indirect and aromatics carbon atom on partly be connected.
Preferred aromatic carboxylic acid's example is Whitfield's ointment and its sulfurized derivative, for example Whitfield's ointment and its derivative of alkyl replacement.
Make the Whitfield's ointment sulfurized method of for example alkyl replacement similar with the method that is used for phenols, they are well-known to those skilled in the art.
Whitfield's ointment generally can for example prepare by the Kolbe-Schmitt method by the carboxylation of phenates, in the case, it normally in thinner to obtain with the form of the mixture of carboxylic acidifying phenol not.
Substituting group in the oil soluble Whitfield's ointment is preferably alkyl substituent.In the Whitfield's ointment that alkyl replaces, alkyl contains 5～100, and is preferred 9～30, especially is 14～20 carbon atoms.When having an above alkyl, the mean number of carbon atom is preferably at least 9 to guarantee suitable oil soluble in all alkyl.
Detergent compositions is except containing the aromatic carboxylic acid, sulfonic acid for example, and phenols and its sulfurized derivative also can contain the organic acid metal-salt outward.This organic acid is disclosed among the WO97/46643, here it is introduced as the reference data.
Each component in detergent compositions or metallo-detergent can be neutral or overbasic, and this qualification is understandable for a person skilled in the art.
Washing agent of the present invention can be salt or the salt of organic acid more than one type, for example the hybrid complex washing agent of one type of organic acid.Preferably they are the salt of one type of organic acid.
The hybrid complex washing agent is a kind of like this washing agent: the basic material in this washing agent is stable by the organic acid more than a type.The organic acid that it will be appreciated by those skilled in the art that single type can contain same type organic acid mixture.For example, sulfonic acid can contain the mixture of different molecular weight sulfonic acid.This organic acid composition is considered to one type.Therefore, the mixture of the high alkali cleaning agent that the complex compound washing agent can be different with two or more is distinguished mutually, and the example of this mixture is the mixture of overbased calcium salicylate washing agent and high alkalinity phenol calcium washing agent.
The example of high alkaline complex washing agent has been described in the prior art.For example described neutralization among the international application published 97-46643/4/5/6 and 7, made mixture be high alkalinity afterwards and produce hybrid complex by more than one the acidic organic compound and the mixture of alkaline metal cpds.The example of hybrid complex washing agent comprises phenol calcium-calcium salicylate-calcium sulphonate washing agent, phenol calcium-calcium sulphonate washing agent and phenol calcium-calcium salicylate washing agent.
EP-A-0750659 discloses a kind of Whitfield's ointment phenol calcium complex, and it is after the phenol calcium carboxylateization, and the mixture sulfuration of calcium salicylate and phenol calcium and high alkalinityization (overbasing) are produced.This complex compound can be described as " phenalates ".
The complex compound washing agent is preferably Whitfield's ointment alkali washing agent.For example phenol calcium-calcium salicylate-calcium sulphonate washing agent and " phenalates ".
Have in single washing agent under the organic acid situation more than a type, the organic acid of any one type and alternative ratio do not have strict restriction, as long as detergent compositions comprises aromatic carboxylic acid's metal-salt of determining ratio.
For avoiding suspecting that detergent compositions also can comprise ashless washing agent, promptly contains nonmetallic washing agent.
Preferred detergent compositions comprises at least a overbased metal washing agent.
Preferred high alkalinity metal washing agent comprises one or more aromatic carboxylic acid's metal-salt, preferably one or more salicylic metal-salt.
1 family's metal and 2 family's metals are preferably as the metal in the washing agent; More preferably calcium and magnesium, especially preferred calcium.
Have now found that and contain at least a calcium salicylate base washing agent, the detergent compositions of preferred at least a overbased calcium salicylate base washing agent is effective especially in the present invention.
Therefore, the applicant thinks only contains calcium salicylate base washing agent, and no matter it is neutrality or high alkalinity, detergent compositions be very favourable.
The preferred amount of detergent compositions in oil compositions is every kg of oil composition at least 5, preferably be at least 10, for example at least 20 or at least 30, more preferably at least 50,75 mmole tensio-active agents (mmol/kg) at the most most preferably are in the content of tensio-active agent.In this embodiment, the consumption of detergent compositions is 10～15mmol/kg in the oil compositions, in the content of tensio-active agent.
The method that is used to measure surfactant content and aromatic carboxylic acid's metal-salt content is well-known for a person skilled in the art.For example, those skilled in the art can from the information of raw material (for example organic acid) consumption of producing washing agent and final oil compositions the content information calculations of washing agent go out content in final lubricating oil composition.But also operational analysis method (for example, potentiometric titration and chromatography) is measured the content of tensio-active agent and aromatic carboxylic acid's metal-salt.
The method that it will be appreciated by those skilled in the art that metal salts of organic acids (also the being called as tensio-active agent) content of determining to comprise aromatic carboxylic acid's metal-salt content at most also is proximate method, and diverse ways will always not provide identical result; But they are enough accurate for enforcement of the present invention.
Dispersant additives
The oil-insoluble substance that dispersant additives obtains oxidation in the use remains in the fluidic suspensoid, thereby has prevented flocculation and sedimentation or the precipitation of mud on metal parts.So-called ashless dispersant is an organism, compares with metallic (becoming ash with like this) washing agent, and this organism do not form ashes basically when burning.The no metal dispersion of borated also is considered to ashless dispersant here.Suitable dispersion agent comprises, for example, the carboxylic acid derivative that long chain hydrocarbon replaces, wherein alkyl has less than 15000, as less than 5000 number-average molecular weight; The example of this derivative is the derivative of the succsinic acid that high-molecular-weight hydrocarbons replaces.The carboxylic acid that this alkyl replaces can with such as nitrogenous compound, react advantageously with the reaction of polyalkylene polyamine, or with alcohol.Particularly preferred dispersion agent is the reaction product of polyalkyleneamines and alkenyl succinic anhydrides.At US-A-3202678,3154560,3172892,3024195,3024237,3219666,3216936 and the embodiment of the specification sheets of BE-A-662875 in the dispersion agent of the above-mentioned type is disclosed.
Alternately or additionally, dispersion force can be provided by the macromolecular compound that improved viscosity index performance and dispersion force can be provided, this kind compound is known as multifunctional viscosity index improver.The difference of this kind polymkeric substance and conventional viscosity index improving agent is that except improving viscosity index, they also can provide serviceability, as dispersion force and/or resistance to oxidation.
Dispersant olefin copolymers and dispersion agent polymethacrylate are the examples of multifunctional viscosity index improver.Multifunctional viscosity index improver is by making various functional moieties, for example, amine, pure and mild acid amides, chemistry is connected on the polymkeric substance and preparation, this polymkeric substance preferably has at least 15000, the number-average molecular weight in 20000～600000 scopes for example, it is determined by gel permeation chromatography or light scattering method.Used polymkeric substance can be those materials relevant with viscosity modifier of above describing.Therefore, can add amine molecule giving dispersion force and/or resistance to oxidation characteristic, yet also can add the phenol molecule to improve antioxidant properties.Therefore, its specific examples is and reactive monomer, and for example grafting behind the maleic anhydride is afterwards with the multipolymer of for example alcohol or amine deutero-ethylene-propylene.
EP-A-24146 and EP-A-0854904 disclose the example of dispersion agent and dispersant viscosity index improvers, here it are introduced as reference.
The heavy duty diesel engine lubricating oil composition is compared the dispersion agent that needing to be tending towards high level with for example carrying engine oil composition, because more oil-insoluble substance, for example carbon deposit can be formed in the heavy duty diesel engine.Therefore, the consumption of the dispersant additives in the heavy duty diesel engine lubricating oil composition (no matter being the form of dispersant additives and/or the form of multifunctional viscosity index improver additive), in nitrogen, be preferably at least 0.06, more preferably be at least 0.09, especially be at least 0.12 quality %, based on the quality of lubricating oil composition.Generally can not surpass 0.2 quality % by dispersion agent deutero-nitrogen content.
In each case, lubricating oil composition all has the phosphorus content less than 0.09 quality %, in the quality of lubricating oil composition.And lubricating oil composition does not contain the dispersant viscosity index improvers additive, the content of nitrogen preferably is at least 0.045 in lubricating oil composition, more preferably 0.5, for example be at least 0.055, advantageously be at least 0.06, especially be at least 0.065, for example be at least 0.08, at least 0.1 quality % for example is in the quality of oil compositions.Nitrogen content is preferably at the most 0.3, and 0.25 or at the most 0.2 quality % at the most for example is in the quality of oil compositions.The content of nitrogen can be measured according to ASTM D4629.The amount of preferred nitrogen is by dispersant additives, and for example polyisobutenyl succinimide is derived.Have in lubricating oil composition under the situation of dispersant viscosity index improvers additive, nitrogen content can be lower than 0.045 quality %, for example, and from 0.001～0.04 quality %, in the quality of oil compositions.In an embodiment preferred, no matter whether oil compositions contains the dispersant viscosity index improvers additive, and its nitrogen content is at least 0.045 quality %.Contain at oil compositions under the situation of dispersant viscosity index improvers additive, the amount of additive is preferably 0.01～5, is preferably 0.05～3, especially is 0.1～2 quality %, in the quality of oil compositions.
Be total to additive
Other additive also can be present in the lubricating oil composition of the present invention.
Be suitable for additive altogether of the present invention and comprise viscosity index improver, inhibiter, other oxidation retarder or oxidation inhibitor, rust oxidation or rust-preventive agent, anti-wear agent, pour point reducer, emulsion splitter and defoamer.
Viscosity index improver (or viscosity improving agent) can be given lubricating oil high-temp and cold operation and can make lubricating oil at high temperature keep the stability of shearing, and also has acceptable viscosity or flowability at low temperatures.The compound that is suitable as the viscosity improving agent is generally the high-molecular weight hydrocarbon polymer, comprises polyester, for example polymethacrylate; Poly-(ethene-copolymerization-propylene) polymkeric substance and the variant (so-called olefin copolymer) that is closely related with it; Hydrogenant gathers (vinylbenzene-copolymerization-divinyl or vinylbenzene-copolymerization-isoprene) polymkeric substance and variant; Poly-(vinylbenzene-copolymerization-maleic anhydride) polymkeric substance of esterification.The polymkeric substance of oil soluble viscosity modified has at least 15000～1000000 usually, preferred 20000～600000 number-average molecular weight, and it is by gel permeation chromatography or light scattering determining.At " Chemistry﹠amp; Technology of Lubricants ' the 5th chapter is edited by R.M.Mortier and S.T.Orzulik, first version,, Blackie Academic ﹠amp in 1992; Content disclosed in the Professional here is introduced into.
Inhibiter can reduce the aging of the metal parts that contacts with lubricating oil composition.Thiadiazoles (thiadiazoles), for example at US-A-2719125, those disclosed in 2719126 and 3087932 all are the examples that are used for the inhibiter of lubricating oil.
Oxidation retarder or oxidation inhibitor can reduce mineral oil rotten tendency takes place in time limit of service, and obviously this going bad for example can produce varnish shape settling and make greasy filth and the viscosity increase on metallic surface.The oxidation retarder that is fit to comprises sulfurized induced by alkyl hydroxybenzene and its basic metal or alkaline earth salt; Hindered phenol; Diphenylamine; Phenyl naphthyl amines and phosphorus sulfurized (phosphosulfurized) or sulfurized hydrocarbon.
Other can be used for oxidation retarder or antioxidant packages oil scraper dissolubility copper compound in the lubricating oil composition.The form of the oil-soluble copper compounds that copper is can be any suitable is mixed in the oil.It is oil-soluble in oil or in the mixed additive under normal blended condition that so-called oil soluble refers to compound.Copper can for example be the form of dialkyl sulfo-or phosphorodithioic acid copper.Perhaps copper can be with synthetic or natural carboxylic acid, for example C 8～C 18Lipid acid, unsaturated acid or branched carboxylic acids, the form of mantoquita add.Also can use oil-soluble dithiocarbamic acid copper in addition, sulfonic acid copper, phenol copper and Acetyl Acetone acid copper.The example of useful especially copper compound is an alkalescence, neutrality or tart copper Cu IAnd/or Cu IISalt, they are by alkenyl succinic or acid anhydrides deutero-.
The general usage quantity of copper oxidation inhibitor is the copper of about 5～500ppm weight in final lubricating oil composition.
Spendable rust-preventive agent is selected from nonionic polyoxyalkylene polyols and its ester, polyoxyalkylene phenol and anionic alkylsulphonic acid.
Anti-wear agent can reduce the wearing and tearing of metal parts as its name.Dialkyl zinc dithiophosphate (ZDDPs) is widely used as anti-wear agent.The example that is used in the ZDDPs in the oil-based composition is by general formula Zn[SP (S) (OR 1) (OR 2)] 2Represented those, wherein R 1And R 2Contain 1～18, preferred 2～12 carbon atoms.
Sulfur-bearing or the compound that contains molybdenum also are the examples of anti-wear agent.The compound that also has ashless phosphorous and sulfur-bearing that other is suitable.
Pour point reducer perhaps is called the lubricating oil improving agent that flows and can makes fluid flow or can topple over the minimum temperature that and reduce.This additive is well-known.Foamy control can be passed through polysiloxane type defoamer, and for example silicone oil or polydimethylsiloxane provide.
Can use a spot of emulsion splitter.Preferred emulsion splitter is disclosed among the EP-A-0330522.It is that the reaction of the adducts that obtains by alkylene oxide and diepoxides and polyol reaction obtains.
More above-mentioned additives can provide multiple effect; Therefore, for example a kind of additive can play a part dispersion agent and oxidation retarder.This result is well-known, does not here need it is described further.
The preferred anti-wear agent that exists in lubricating oil composition of the present invention for example is the metal-salt of dialkyl phosphorodithioic acid, for example dialkyl zinc dithiophosphate.
When lubricating oil composition contained one or more above-mentioned additive that comprises washing agent, every kind of additive generally was mixed in the crude oil, and its consumption is wanted to make additive that its required function is provided.When they were used in the lubricating oil, its effective level was:
Additive Quality %a.i. *(wide) Quality %a.i. *(preferably)
Viscosity modifier ????0.01-6 ????0.01-4
Inhibiter ????0.01-5 ????0.01-1.5
Oxidation retarder ????0.01-5 ????0.01-1.5
Low friction compound ????0.01-5 ????0.01-1.5
Dispersion agent ????0.1-20 ????0.1-8
Dispersant viscosity modifiers ????0.01-5 ????0.05-5
Washing agent ????0.01-6 ????0.01-3
Anti-wear agent ????0.01-6 ????0.01-4
Pour point reducer ????0.01-5 ????0.01-1.5
Rust-preventive agent ????0.001-0.5 ????0.01-0.2
Defoamer ????0.001-0.3 ????0.001-0.15
Emulsion splitter ????0.001-0.5 ????0.01-0.2
*Quality % activeconstituents is based on final lubricating oil composition
Additive can any mode easily be added in the crude oil.Therefore, every kind of additive is by it is dispersed or dissolved in the oil with required concentration level and directly be added in the oil.This mixing can be carried out under room temperature or high temperature.
When using multiple additives, wish to be made into one or more mixed additive that contains additive (additive package) (being also referred to as compositions of additives or enriched material), but this not necessarily, and therefore several additives except concentration improving agent, multifunctional concentration improving agent and pour point reducer can be added to simultaneously and form lubricating oil composition in the crude oil.The dissolving of mixed additive in lubricating oil can promote by thinner or solvent and by the mixing with mild heat, but this not necessarily.When mixed additive combined with the crude oil of predetermined amount, mixed additive was configured to make the amount of contained additive to provide desired concn in final prescription usually.Nitrogen content in this multifunctional additive for lubricating oils is generally 0.5～1.5, is preferably 0.7～1.0 quality %, in the quality of multifunctional additive for lubricating oils.Therefore, one or more washing agent can (for example join in a spot of crude oil or other the compatible solvent with other desired additives, carrier oil or thinning oil), thereby form the mixed additive that contains activeconstituents, based on the mixed additive meter, the content of activeconstituents for example is 2.5～90 quality %, be preferably 5～75 quality %, most preferably be 8～60 quality %, wherein additive and residuum are proper proportion, and residuum is a thinner.Usually the mixed additive that contains 5～40 quality % in the final prescription, residuum are thinner.
Additive level in final lubricating oil composition depends on the type of oil compositions usually, and for example, the heavy duty diesel engine lubricating oil composition has 2～20, be preferably 5～18, more preferably 7～16, the additive of 8～14 quality % for example is in the quality of oil compositions.
Therefore the method for oil compositions produced according to the present invention comprises the compound of lubricant viscosity is oily and one or more qualification or contains one or more mixed additive that limits compound and mixes.
Should be appreciated that after joining additive in the oil compositions, between any two or more additives, comprise between any two or more washing agent, can interact.Interaction occurs in the mixing process, perhaps under any condition subsequently that composition is exposed, is included in and uses said composition under its Working environment.Join in the composition of the present invention when other helps additive, or add fashionablely with oil ingredient, also can interact.This interaction comprises the interaction that changes the additive chemistry formation, therefore composition of the present invention comprises such as the interactional composition of generation between any additives, and such as interactional composition does not take place between the blended component in oil.
In this manual:
When using term " to comprise " herein or when " containing ", refer to the feature, things, step or the component that offer some clarification on, do not exist or add one or more feature, things, step, component or its generic but do not get rid of.
Term used herein " oil soluble " or " oily dispersibility " are not meant that additive is soluble, soluble (dissolvable), miscible or can be suspended in the oil with any ratio.But they refer to really, and for example, additive is the degree of solvable or stable dispersion in oil, are enough to the environment that adopts this oil compositions is applied its effect.And, can influence solubility of additive or dispersiveness such as the extra adding of those other additives of above describing.
" in a large number " refers to 50 quality % above composition.
" on a small quantity " refers to 50 quality % less than composition, and with regard to described additive and with regard to regard to the total mass % of all additives of existing in the composition, it is based on, and activeconstituents in the additive calculates.
" TBN " is the total basicnumber (Total Base Number) that records with ASTM D2896.
Unless otherwise indicated, it is the quality % of base that all per-cents are with the activeconstituents, does not promptly consider carrier oil or thinning oil.
Abbreviation SAE represents Society of automotive engineers, and this association classifies to lubricating oil with viscosity grade.
The present invention describes by following embodiment, but is not limited thereto.
Embodiment
Lubricating oil composition mixes so that every kind of composition is SAE 5W30 lubricating oil composition by known method.Every kind of lubricating oil composition comprises the detergent compositions that contains salicylate detergents; The dialkyl zinc dithiophosphate; Dispersion agent with boration.Therefore, every kind of oil compositions can compare each other, because except embodiment 1 and 2, they contain identical additive, embodiment 1 and 2 also contains low friction compound: embodiment 1 and contains XU 61518.10 as low friction compound, its content is 0.3 quality %, and embodiment 2 contains three nuclear molybdenum dithiocarbamates as low friction compound, and its content is the molybdenum of 450ppm.
Do the fuel combustion efficiency test of lubricating oil composition (Comparative examples A, embodiment 1 and embodiment 2) on the whole drive system device, described drive train arrangement comprises that Volvo FH-12 rises heavy duty diesel engine and comprises wheel casing and the variator of axle.
This device is extensive use of based on electronic motor management system, and it links together the Transaxle CAN (Contro1led Area Network) of variator and a certain angle as full drive train arrangement.This device is disclosed in " the Neues F﹠amp of Peter Ahrweiler and Gerd Rentel; E-Zentrum Fur Antriebsstrang-Schmierung " in, ATZAutomobiletechnische Zeitschrift, 100 (1998), 3, the 202～209 pages.One of major advantage of full drive train arrangement is the formation that can reduce heavy-duty diesel oil fuel combustion efficiency measuring error.If want to measure accurately the efficient of fuel combustion, the removal of source of error is absolutely necessary, and these source of errors are relevant with the test of fleet, for example officer's difference, the difference of tire pressure, the difference of driving the cycle is with aerodynamic different.Can use full drive train arrangement now.Historical data shows that the fuel combustion efficiency of measuring at 95% fiducial interval place is genuine and believable greater than 0.29%.
The measurement of fuel combustion efficiency is cited as improving measuring of size with per-cent, and it can be compared with the lubricating oil composition that has with the same binder component of Comparative examples A, but it will be mixed into SAE 15W40 level.
Table 1 has been summed up resulting result, by the table in as can be seen, use low friction compound can improve motor spirit incendiary efficient in the heavy duty diesel engine lubricating oil composition, this improvement approximately is 2 times of the oil compositions (relatively Comparative examples A and embodiment 1 or 2) that the do not contain low friction compound effect that can reach.Table 1 also provides some performance of oil compositions.
Table 1:
Comparative examples A Embodiment 1 Embodiment 2
SAE J300 classification ??5W30 ??5W30 ??5W30
Phosphorus, % quality (ASTM D5185) ??0.12 ??0.13 ??0.12
Sulphur, % quality (ASTM D5185) ??0.33 ??0.34 ??0.41
Nitrogen, quality % ??0.10 ??0.10 ??0.11
Base-material mixes @100 ℃ of Nian Du, mm 2s -1 ??8.83 ??8.80 ??8.89
The improvement of fuel combustion efficiency, % 1 ??0.69 2 ??1.50 ??1.35
The improved per-cent of the fuel combustion efficiency of 1-for the lubricating oil composition that is mixed into SAE 15W40 level; The mean value of twice measurement of 2-.

Claims (10)

1, a kind of purposes of one or more compound in the heavy duty diesel engine lubricating oil composition of effective content, coefficient has improved the efficient of heavy duty diesel engine fuel combustion thereby this compound can be reduced friction under mixed lubrication or condition of boundary lubrication.
2, a kind of heavy duty diesel engine lubricating oil composition comprises a large amount of lubricant viscosity oil and is added with therein:
(A) under the condition of mixed lubrication or boundary lubrication, can reduce one or more compound of the significant quantity of frictional coefficient;
(B) contain the detergent compositions of aromatic carboxylic acid's metal-salt on a small quantity; With
(C) paucidisperse agent addition agent; As long as lubricating oil composition has the nitrogen content of at least 0.06 quality %, in the quality of composition.
3, according to the oil compositions of claim 2, wherein oil compositions will satisfy API CG-4 performance specification and/or ACEA E2-96 performance specification at least.
4, according to the oil compositions of claim 2 or 3, it is the form of SAE 5W-X or SAE OW-X lubricating oil composition, and wherein X is any one in 20,30,40 and 50.
5, according to the oil compositions of one of claim 2～4, wherein the base-material of composition mixing viscosity is at least 8.2mm in the time of 100 ℃ 2s -1
6, according to the oil compositions of one of claim 2～5, wherein at least a compound has polar head group and oil loving hydrocarbyl chain.
7, according to the oil compositions of one of claim 2～5, wherein at least a compound is a molybdenum compound.
8, a kind of heavy duty diesel engine additive concentrate compositions, it comprises a kind of thinner and one or more additive, described additive comprises:
(A) one or more can be at the compound of mixed lubrication or condition of boundary lubrication decline low-friction coefficient;
(B) contain the detergent compositions of aromatic carboxylic acid's metal-salt; With
(C) dispersant additives; When lubricating oil composition contains the additive of 2～20 quality %, the heavy duty diesel engine lubricating oil composition that each shared ratio will can provide claim 2 to limit.
9, combining of the lubricating oil composition that limited of a kind of heavy duty diesel engine in the continental rise vehicle and one of claim 2～7, wherein the engine that uses in the continental rise vehicle has at least 6.5 liters total flow rate and the discharge capacity of each cylinder is at least 1.0 liters/cylinder.
10, the method for the medium and heavy diesel motor of a kind of lubricated continental rise vehicle, the engine that uses in the continental rise vehicle has at least 6.5 liters total flow rate and the discharge capacity of each cylinder is at least 1.0 liters/cylinder, and this method comprises to engine supplies with the lubricating oil composition that one of claim 2～7 is limited.
CN02157566A 2001-12-21 2002-12-20 Lubricating oil composition for heavy diesel engine Pending CN1427069A (en)

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