CN108026469A - For preventing or reducing the lubricating composition early fired in engine - Google Patents
For preventing or reducing the lubricating composition early fired in engine Download PDFInfo
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- CN108026469A CN108026469A CN201680054791.3A CN201680054791A CN108026469A CN 108026469 A CN108026469 A CN 108026469A CN 201680054791 A CN201680054791 A CN 201680054791A CN 108026469 A CN108026469 A CN 108026469A
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- molybdenum
- carbon atoms
- lubricating composition
- sulphur
- compound
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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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/024—Well-defined aliphatic compounds unsaturated
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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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
- 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
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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
- 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
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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
- 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
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- 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
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- 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
- C10N2030/02—Pour-point; Viscosity index
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- 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
- C10N2040/255—Gasoline engines
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
It is used to prevent the present invention relates to the lubricating composition including at least one base oil and at least one organic molybdenum or reduces engine, the purposes early fired in preferred vehicle engine, wherein the organic molybdenum is selected from phosphordithiic acid molybdenum compound or the molybdenum complex without sulphur.
Description
It is used to prevent the present invention relates to lubricating composition or reduces the purposes early fired in engine.More specifically, this hair
It is bright to be related to the lubricating composition comprising at least one base oil and at least one organic molybdenum for preventing or reducing to start
The purposes early fired in machine (preferred vehicle engine, especially motor car engine).
The invention further relates to application the lubricating composition come prevent or reduce engine (preferred vehicle engine, especially
Motor car engine) in the method early fired.
It is used to prevent in lubricating composition the invention further relates to organic molybdenum or reduces engine (preferred vehicle is started
Machine, especially automobile engine) in the purposes early fired.
Technical background
Under ideal conditions, the production of the spark sent when the mixture (especially fuel and air) of fuel by spark plug
When giving birth to and being ignited in the combustion chamber of cylinder interior, the normal combustion in flashing igniter motor.This normal combustion
Be generally characterized as flame front by combustion chamber by order it is controlled in a manner of extend.
But in some cases, before being lighted by the spark of spark plug, air/fuel mixture can pass through a little
Combustion source is prematurely lighted, and causes the phenomenon referred to as early fired.
It is preferred that early combustion is reduced or even eliminated, because early combustion typically results in the obvious liter there are temperature and pressure in combustion chamber
Height, and can thus cause the significant negative effect of efficiency and overall performance to engine.In addition, early combustion can cause to starting
The notable infringement of cylinder, piston, spark plug and valve in machine, and in some cases, can even result in engine failure or
Even engine damage.
Recently, low speed early combustion (LSPI) regards as puffer (or reduced size by (specifically, automaker)
Engine) potential problems.LSPI usually occurs under low speed and high load capacity, and can cause to piston and/or cylinder
Serious infringement.
Accordingly, it is desirable to it can prevent or reduce the lubricant of the early risk for firing (including LSPI) with one kind.
Have been described for reducing calcium content or increase zinc dithiophosphate or aminodithioformic acid in lubricant
Scheme (Takeuchi et al., " Investigation of Engine Oil Effect on Abnormal of molybdenum content
Combustion in Turbocharged Direct Injection-Spark Ignition Engines,"SAE
Int.J.Fuels Lubr.5(3):1017-1024,2012；Hirano et al., " Investigation of Engine Oil
Effect Abnormal Combustion in Turbocharged Direct Injection-Spark Ignition
Engines (part 2), " SAE Technical Paper 2013-01-2569,2013).But these schemes are still insufficient
Early fire and be difficult to carry out to substantially reduce, especially in the country of high alkalinity level in requiring fuel.In addition, these schemes companion
Consistency problem with lubricant stable or with after-treatment system.
WO2015023559 is disclosed by being added in lubricating composition for the additive of late ignition to reduce morning
The method of combustion, wherein the additive is selected from the organic compound for including at least one aromatic ring.But these lightweights (light)
Organic compound can cause the volatile excessively increase of lubricant.
Therefore, the lubricating composition it is an object of the present invention to provide compound and comprising these compounds, to overcome
All or part of aforementioned drawback.
It is a further object to provide a kind of early combustion being used to prevent or reduce in engine and its formula to hold
The lubricating composition easily implemented.
Make us it is a further object to provide a kind of for maintenance when preventing or reducing the early excessively heated axle in engine
The lubricating composition of satisfied or improved lubricating property.
It is a further object of the present invention to provide a kind of for preventing or reducing the lubricating method early fired in engine.
The content of the invention
Therefore, the present invention relates to used comprising the lubricating composition of at least one base oil and at least one organic molybdenum
The purposes early fired in prevention or reduction engine, wherein the organic molybdenum is selected from：
Phosphordithiic acid molybdenum compound (Mo-DTP), or
Molybdenum complex without sulphur.
Surprisingly, it has been discovered by the applicants that at least one organic-molybdenum selected from Mo-DTP and the molybdenum complex without sulphur
Presence of the compound in lubricating composition prevents or reduces hair when the lubricating composition is applied within the engine
Early combustion in motivation.
Therefore, the present invention can prepare such lubricating composition：The lubricating composition is within the engine in use, carry
Good early combustion prevention is provided at the same time for good stability or reduces performance.
Advantageously, lubricating composition according to the present invention is within the engine in application, with good early combustion prevention or subtract
Few performance, without (especially requiring them and other technical solutions to reduce calcium or content of magnesium or causing lubricating composition
Volatile excessively increased technical solution) combine to prevent or reduce early combustion.
Advantageously, when lubricating composition according to the present invention is applied within the engine with prevention or reduce early fire it is good
Performance, and it is prepared and easily implements.
In one embodiment according to the present invention, organic molybdenum is the molybdenum complex of no sulphur, it, which is selected from, has
The organic molybdenum complex compound of amide ligands, and 4 to 28 carbon originals (are preferably comprised by the derivative and aliphatic acid of molybdenum source and amino
Son, more preferably 8 to 18 carbon atoms) reaction and prepare.
In another embodiment of the method in accordance with the present invention, organic molybdenum is the molybdenum complex of no sulphur, it is included at least
It is a kind of to be selected from following compounds：
The compound of-formula (A)
Wherein：
·X1Represent oxygen atom or nitrogen-atoms；
·X2Represent oxygen atom or nitrogen-atoms；
Work as X1Represent that n represents 1 during oxygen atom, and work as X2Represent that m represents 1 during oxygen atom；
Work as X1Represent that n represents 2 during nitrogen-atoms, and work as X2Represent that m represents 2 during nitrogen-atoms；
·R1Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised；
The compound of-formula (B)
Wherein：
·X1Represent oxygen atom or nitrogen-atoms；
·X2Represent oxygen atom or nitrogen-atoms；
Work as X1Represent that n represents 1 during oxygen atom, and work as X2Represent that m represents 1 during oxygen atom；
Work as X1Represent that n represents 2 during nitrogen-atoms, and work as X2Represent that m represents 2 during nitrogen-atoms；
·R1Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised；
·R2Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised.
The mixture of the compound of-at least one formula (A) and the compound of at least one formula (B).
In another embodiment of the present invention, organic molybdenum is the molybdenum complex of no sulphur, it includes at least one
The compound of formula (A1)：
Wherein, R1Represent straight or branched, saturation or undersaturated alkyl group, it is excellent it includes 3 to 30 carbon atoms
3 to 20 carbon atoms are selected, advantageously comprise 7 to 17 carbon atoms.
In another embodiment of the present invention, organic molybdenum is the molybdenum complex of no sulphur, it includes formula (A1)
Compound, wherein R1Represent the alkyl group for including 11 carbon atoms.
In another embodiment of the present invention, organic molybdenum is the molybdenum complex of no sulphur, it includes at least one
The compound of formula (A2)：
Wherein R1Represent straight or branched, saturation or undersaturated alkyl group, it is excellent it includes 3 to 30 carbon atoms
3 to 20 carbon atoms are selected, advantageously comprise 7 to 17 carbon atoms.
In another embodiment of the present invention, organic molybdenum is Mo-DTP compounds, it includes：
Relative to the gross weight of Mo-DTP compounds, 1 to 40%, preferably 2 to 30%, more preferably 3 to 28%, it is still more excellent
Select 4 to 15%, advantageously 5 to 12wt.-% molybdenum；
Relative to the gross weight of Mo-DTP compounds, 1 to 40%, preferably 2 to 30%, more preferably 3 to 28%, even more
Preferentially 4 to 15wt.-% sulphur；
Relative to the gross weight of Mo-DTP compounds, 1 to 10%, preferably 2 to 8%, more preferably 3 to 6wt.-% phosphorus.
In another embodiment of the present invention, Mo-DTP compounds are selected from dimerization Mo-DTP compounds or trimerization Mo-DTP
Compound.
In another embodiment of the present invention, Mo-DTP compounds are the dimerization Mo-DTP compounds of formula (C)：
Wherein：
R3, R4, R9 and R10 be it is identical or different, its independently represent selected from alkyl, alkenyl, aryl, cycloalkyl or
The hydrocarbyl group of cycloalkenyl groups,
R5, R6, R7 and R8 are identical or different, it independently represents oxygen atom or sulphur atom.
In another embodiment of the present invention, Mo-DTP compounds are the dimerization Mo-DTP compounds of formula (C1)：
Wherein R3, R4, R9 and R10 is identical or different that it is independently represented selected from alkyl, alkenyl, aryl, cycloalkyl
Or the hydrocarbyl group of cycloalkenyl groups, preferably comprise 4 to 12 carbon atoms, advantageously comprise the alkyl group of 6 to 10 carbon atoms.
In another embodiment of the present invention, compound Mo-DTP is the dimerization Mo-DTP compounds of formula (C1), wherein
R3, R4, R9 and R10 are identical, it represents C8- alkyl groups, preferably ethylhexyl group.
In another embodiment of the present invention, pressed relative to the gross weight of the lubricating composition, organic molybdenum
The content range of weight meter is 0.05 to 3%, preferably 0.1 to 2%, be advantageously 0.1 to 1%.
In another embodiment of the present invention, the lubricating composition is further included selected from following other additions
Agent：Add except Mo-DTP compounds with the friction improver of the molybdenum complex without sulphur, detergent, anti-doping (anti-doping)
Add agent and antiwear additive, EP agent, viscosity index improver, dispersant, antioxidant, pour point improver, defoamer,
Thickener and its mixture.
In another embodiment of the present invention, the lubricating composition is used to prevent or reduce vehicle (preferably motor vehicle)
Early combustion in engine.
In another embodiment of the present invention, the lubricating composition is used to prevent or reduce engine (preferred vehicle
Engine, preferably motor vehicle engine) in low speed early combustion (LSPI).
The invention further relates to the method early fired in prevention or reduction engine, wherein making the described method includes at least one
The step of mechanical part of engine is contacted with lubricating composition as defined above.
The invention further relates to organic molybdenum in the lubricating composition comprising at least one base oil be used for prevent or
The purposes early fired in engine is reduced, wherein the organic molybdenum is selected from：
Phosphordithiic acid molybdenum compound (Mo-DTP), or
Molybdenum complex without sulphur.
Detailed description of the invention
Percentage given below corresponds to the percentage of active ingredient by weight.
Lubricating composition used according to the invention includes at least one organic molybdenum, it is selected from：
Phosphordithiic acid molybdenum compound (Mo-DTP), or
Molybdenum complex without sulphur.
Molybdenum complex without sulphur
In an embodiment of the invention, the organic molybdenum may be selected from the carboxylic of the molybdenum complex such as molybdenum of no sulphur
Hydrochlorate, ester, molybdenum acid amides, it can be spread out by the molybdate of molybdenum oxide or ammonium and aliphatic material, glyceride, aliphatic acid or aliphatic acid
The reaction of biological (ester, amine, acid amides ...) and obtain.
In a preferred embodiment of the invention, organic molybdenum is selected from the complexing of the molybdenum without sulphur with amide ligands
Thing, it is mainly prepared by molybdenum source (it can be such as molybdenum) and the reaction of amine derivative and aliphatic acid, and the aliphatic acid is excellent
Choosing include 4 to 28 carbon atoms, more preferably 8 to 18 carbon atoms, as example, fat included in vegetable oil or animal oil
Acid.
The synthesis of this kind of compound, in such as US 4.889.547, EP 0546357, US 5.412.130 and EP
Described in 1770153.
In a preferred embodiment of the invention, molybdenum complex of the organic molybdenum selected from no sulphur, it passes through following anti-
It should obtain：
(i) single-, two- or Three-glycerol ester-type aliphatic material or aliphatic acid,
(ii) the amino source of formula (D)：
Wherein：
-X1Represent oxygen atom or nitrogen-atoms,
-X2Represent oxygen atom or nitrogen-atoms,
- work as X1Or X2When representing oxygen atom, n and m represent 1,
- work as X1Or X2When representing nitrogen-atoms, n and m represent 2,
(iii) and molybdenum source, it is selected from molybdenum trioxide or molybdate, preferably ammonium molybdate, and the amount of the molybdenum source is enough to provide base
In the molybdenum of the gross weight 0.1 to 30% of complex compound.
In an embodiment of the invention, the molybdenum complex of no sulphur can include the weight based on complex compound
2 to 8.5% molybdenum.
In a preferred embodiment of the invention, the molybdenum complex of no sulphur is selected from following compounds including at least one：
The compound of-formula (A)
Wherein：
·X1Represent oxygen atom or nitrogen-atoms；
·X2Represent oxygen atom or nitrogen-atoms；
Work as X1Represent that n represents 1 during oxygen atom, and work as X2Represent that m represents 1 during oxygen atom；
Work as X1Represent that n represents 2 during nitrogen-atoms, and work as X2Represent that m represents 2 during nitrogen-atoms；
·R1Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised；
The compound of-formula (B)：
Wherein：
·X1Represent oxygen atom or nitrogen-atoms；
·X2Represent oxygen atom or nitrogen-atoms；
Work as X1Represent that n represents 1 during oxygen atom, and work as X2Represent that m represents 1 during oxygen atom；
Work as X1Represent that n represents 2 during nitrogen-atoms, and work as X2Represent that m represents 2 during nitrogen-atoms；
·R1Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised；
·R2Represent straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3
To 20 carbon atoms, 7 to 17 carbon atoms are advantageously comprised.
The mixture of the compound of-at least one formula (A) and the compound of at least one formula (B).
In an embodiment of the invention, the molybdenum complex of the no sulphur is by prepared by following reacted：
(i) it is single-, double-or Three-glycerol ester-type aliphatic material or aliphatic acid,
(ii) diethanol amine or 2- (2- aminoethyls) ethylaminoethanol,
(iii) and molybdenum source, it is selected from molybdenum trioxide or molybdate, preferably ammonium molybdate, and the amount of the molybdenum source is enough to provide base
In the molybdenum of the weight 0.1 to 20.0% of complex compound.
In a preferred embodiment of the invention, the molybdenum complex of no sulphur includes the compound or formula of at least one formula (A1)
(A2) compound, either individually or as mixture：
Wherein, R1Represent straight or branched, saturation or undersaturated alkyl group, it is excellent it includes 3 to 30 carbon atoms
3 to 20 carbon atoms are selected, advantageously comprise 7 to 17 carbon atoms,
Wherein, R1Represent straight or branched, saturation or undersaturated alkyl group, it is excellent it includes 3 to 30 carbon atoms
3 to 20 carbon atoms are selected, advantageously comprise 7 to 17 carbon atoms.
Advantageously, the organic molybdenum is the molybdenum complex of no sulphur, it includes the compound of formula (A1), wherein R1Table
Show the alkyl group for including 11 carbon atoms.
The example of the molybdenum complex of no sulphur includes Molyvan 855, commercially available by R.T Vanderbilt Company.
Phosphordithiic acid molybdenum compound (Mo-DTP)
Molybdenum dithiophosphate (Mo-DTP) compound be by the metal ring with one or more ligand bindings into network
Compound, wherein the ligand is alkyl dithiophosphoric acid foundation group.
In one embodiment, can be included for the Mo-DTP compounds in lubricating composition according to the present invention opposite
In Mo-DTP compounds gross weight by weight 1 to 40%, preferably 2 to 30%, more preferably 3 to 28%, even more preferably 4 to
15%, it is advantageously 5 to 12% molybdenum.
In one embodiment, can be included for the Mo-DTP compounds in lubricating composition according to the present invention opposite
In Mo-DTP compounds gross weight by weight 1 to 40%, preferably 2 to 30%, more preferably 3 to 28%, even more preferably 4 to
15% sulphur.
In one embodiment, can be included for the Mo-DTP compounds in lubricating composition according to the present invention opposite
In the phosphorus of the gross weight by weight 1 to 10%, preferably 2 to 8%, more preferably 3 to 6% of Mo-DTP compounds.
Its structure, which is may be selected from, for the Mo-DTP compounds in lubricating composition according to the present invention includes two molybdenum atoms
Compound (also referred to as dimerization Mo-DTP) and its structure compound (being also referred to as trimerization Mo-DTP) for including three molybdenum atoms.
Trimerization Mo-DTP compounds have following formula Mo3SkLn, wherein：
Integer of-k the expressions at least equal to 4, preferably 4 to 10,4 to 7 are advantageously,
- n represents the integer that scope is 1 to 4, and
- L represents alkyl dithiophosphoric acid foundation group, it includes 1 to 100 carbon atom,
It is preferred that 1 to 40 carbon atom, advantageously comprises 3 to 20 carbon atoms.
The example of Mo-DTP- tripolymer compounds according to the present invention includes such as WO98/26030 and US2003/022954
Described in compound and its preparation method.
Advantageously, the Mo-DTP compounds used in the present case are dimerization Mo-DTP compounds.
The example of dimerization Mo-DTP compounds includes the compound described in EP0757093 or EP0743354.
Dimerization Mo-DTP generally corresponds to the compound of formula (C)：
Wherein：
R3, R4, R9 and R10 can be same or different, it is independently represented selected from alkyl, alkenyl, aryl, ring
The hydrocarbyl group of alkyl or cycloalkenyl groups,
R5, R6, R7 and R8 can be same or different, it independently represents oxygen atom or sulphur atom.
In one embodiment, R3, R4, R9 and R10 can be same or different that it independently represents to include 4
To 18 carbon atoms alkyl group or include the alkenyl groups of 2 to 24 carbon atoms.
In one embodiment, R5, R6, R7 and R8 can be identical and can represent sulphur atom.
In another embodiment, R5, R6, R7 and R8 can be identical and can represent oxygen atom.
In another embodiment, R5 and R6 can represent sulphur atom, and R7 and R8 can represent oxygen atom.
In another embodiment, R5 and R6 can represent oxygen atom, and R7 and R8 can represent sulphur atom.
In a preferred embodiment of the invention, compound Mo-DTP is selected from the compound of formula (C), wherein：
- R5 and R6 represents oxygen atom,
- R7 and R8 represents sulphur atom,
- R3 represents the alkyl group comprising 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms,
- R4 represents the alkyl group comprising 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms,
- R9 represents the alkyl group comprising 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms,
- R10 represents the alkyl group comprising 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms.
Advantageously, Mo-DTP compounds are selected from the compound of formula (C), wherein：
- R5 and R6 represents oxygen atom,
- R7 and R8 represents sulphur atom,
- R3 represents ethylhexyl group,
- R4 represents ethylhexyl group,
- R9 represents ethylhexyl group,
- R10 represents ethylhexyl group.
Advantageously, compound Mo-DTP is selected from the compound of formula (C1)：
Wherein, R3, R4, R9 and R10 are as limited formula (C).
Advantageously, compound Mo-DTP is selected from the compound of formula (C1), and wherein R3, R4, R9 and R10 is identical or different
, it independently represents the hydrocarbyl group selected from alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl group, preferably comprises 4 to 12 carbon originals
The alkyl group of son, preferably 6 to 10 carbon atoms.
Even more desirably, compound Mo-DTP is selected from the compound of formula (C1), wherein R3, R4, R9 and R10 represents C8-
Alkyl group, preferably ethylhexyl group.
As the example of Mo-DTP compounds, the company commercially available Molyvan of R.T Vanderbilt Company are can be mentioned that
L products or the Sakuralube 300 or Sakuralube 310G products of company Adeka sale.
In an embodiment of the invention, relative to the gross weight of the lubricating composition, organic molybdenum
Content scope by weight is 0.05 to 3%, preferably 0.1 to 2%, is advantageously 0.1 to 1%.
Lubricating composition used according to the invention is also comprising at least one base oil.
In general, lubricating composition used according to the invention can include any types well known by persons skilled in the art
Mineral lubricant base oil, synthesis or natural lubricating base oil, animal or plant lubricating base oil.
Base oil for lubricating composition according to the present invention can be the oil or synthesis source of mineral origin
Oil --- limited classification of being classified according to API, it belongs to I groups to V groups (or classifying according to ATIEL, its equivalent) (table
A) --- or its mixture.
Table A
Mineral base oil according to the present invention includes all types of base oils obtained by following manner：Normal pressure and true
Sky distills the crude oil, then carry out refining operation for example solvent extraction, desalination, solvent dewaxing, hydrotreating, be hydrocracked, be hydrogenated with it is different
Structure and hydrofinishing.
The mixture of artificial oil and mineral oil can also be used.
For the typically no limit of use of the different lubrication base-materials for producing lubricating composition used according to the invention
System, is suitable for property in engine or suitable for system of vehicle transmission except they must have, especially viscosity, viscosity index (VI),
Sulfur content, the property of resistance to oxidation.
The base oil of lubricating composition used according to the invention also selected from artificial oil (such as some carboxylic acids and alcohol
Ester) and selected from polyalphaolefin.Polyalphaolefin as base oil is for example obtained by the monomer comprising 4 to 32 carbon atoms, such as
Obtained by octene or decene, according to ASTM D445, it is in 100 DEG C of viscosity in 1.5 and 15mm2.s-1Between.According to ASTM
D5296, their average molecular weight is usually between 250 and 3 000.
Preferably, it is upper between 0 and 45%, preferably between 0 and 30% to be selected from arene content with base oil of the invention
State base oil.According to the arene content of Byrd spy (Burdett) UV methods measurement oil.
Advantageously, lubricating composition used according to the invention include relative to the composition gross weight by weight
At least 50% base oil.
More advantageously, lubricating composition used according to the invention include relative to the composition gross weight by weight
Meter at least 60%, or even by weight at least 70% base oil.
Particularly advantageously, lubricating composition used according to the invention is included and pressed relative to the gross weight of the composition
The base oil of the base oil of weight meter 60 to 99.5%, preferably by weight 70 to 99.5%.
Many additives can be used for lubricating composition used according to the invention.
Preferable additives for lubricating composition used according to the invention are selected from except Mo-DTP compounds and without sulphur
The friction improver of molybdenum complex, detergent, antiwear additive, EP agent, viscosity index improver, dispersant, anti-
Oxidant, pour point improver, defoamer, thickener and its mixture.
Preferably, lubricating composition used according to the invention includes at least one antiwear additive and at least one extreme pressure
Additive or its mixture.
Antiwear additive and EP agent protect these surfaces by forming protective film of the absorption on friction surface.
There are substantial amounts of antiwear additive.In the preferred embodiment for lubricating composition according to the present invention, wherein institute
State antiwear additive be selected from phosphorous-sulphur additive, such as metal alkylthiophosphates, especially alkylthio trbasic zinc phosphate, more
Specifically zinc dialkyl dithiophosphate or ZnDTP.Preferable compound has formula Zn ((SP (S) (OR11)(OR12))2,
Wherein R11And R12Can be same or different, it independently represents alkyl group, preferably comprises 1 to 18 carbon atom
Alkyl group.
Phosphamide is also the antiwear additive available for lubricating composition according to the present invention.But by these additives
The phosphorus of offer may act as the poisonous substance of the catalysis system of automobile, because these additives are grey propellant (ash generator).This
A little effects can by with no phosphorus additive such as such as polysulfide (the especially alkene of sulfur-bearing) partly substitute phosphamide and by
Minimize.
Advantageously, lubricating composition according to the present invention can be included relative to the lubricating composition gross weight by weight
The antiwear additive and extreme pressure of meter 0.01 to 6%, preferably by weight 0.05 to 4%, more preferably by weight 0.1 to 2% add
Add agent.
Advantageously, lubricating composition according to the present invention can include it is at least one it is other, except Mo-DTP compounds and
Friction beyond the molybdenum complex of no sulphur improves additive.The other friction improves additive and may be selected from providing metallic element
Compound and ashless (ash-free) compound.In the compound that metallic element is provided, transition metal complex can be mentioned that
Such as Mo, Sb, Sn, Fe, Cu and Zn, its ligand can be the hydrocarbon compound for including oxygen, nitrogen, sulphur or phosphorus.Ashless friction improves addition
Agent is typically organic origin, it may be selected from the monoesters of aliphatic acid and polyalcohol, alkoxylated amines, alkoxylated fats amine, fat
Fat race epoxides, borate aliphatic epoxide, fatty amine or fatty glyceride.According to the present invention, aliphatic compound
Thing includes at least one hydrocarbyl group containing 10 to 24 carbon atoms.
Advantageously, lubricating composition according to the present invention can be comprising the gross weight relative to the lubricating composition by weight
Meter 0.01 to 2% or by weight 0.01 to 5%, preferably by weight 0.1 to 1.5% or by weight 0.1 to 2% it is wear-resistant
Additive and EP agent.
Advantageously, lubricating composition according to the present invention can include at least one antioxidant.
Degraded of the antioxidant commonly used to the lubricating composition in delay use.The degraded can significantly cause to deposit
The increase of the viscosity of the formation of thing, the presence of sludge or lubricating composition.
Antioxidant is especially used as the disrupting agent (destroyer) of free radical inhibitors or hydroperoxides.Logical
In the antioxidant often used, phenolic antioxidant, amine type antioxidant, the anti-oxidant addition of phosphorus sulphur can be mentioned that
Agent.Some in these antioxidants, such as phosphorus sulphur antioxidant, can be grey propellants.Phenols is anti-oxidant to be added
Agent is added to be ashless or can be neutral or alkaline metal salt form.Antioxidant can be especially selected from steric hindrance
Phenol, steric hindrance phenolic ester and sterically hindered phenol comprising thioether bridge, diphenylamine, by least one C1-C12Alkyl group substitutes
Diphenylamine and N, N'- dialkyl group-aryl-diamines and its mixture.
Preferably, according to the present invention, sterically hindered phenol is selected from the compound for including phenolic group group, wherein the carbon with carbinol-functional
At least one ortho position carbon by least one C1-C10Alkyl group, preferably C1-C6Alkyl group, preferably C4Alkyl group substitutes,
It is preferred that substituted by tertiary butyl groups.
Amino-compound is the another kind of antioxidant being optionally used in combination with phenols antioxidant.Amine
The example of compound is aromatic amine, such as formula NR13R14R15Aromatic amine, wherein R13Represent the aliphatic group or virtue optionally substituted
Race's group, R14Represent the aromatic group optionally substituted, R15Represent hydrogen atom, alkyl group, aromatic yl group or formula R16S(O)zR17
Group, wherein R16Represent alkylidene group or alkenylene group, R17Represent alkyl group, alkenyl group or aromatic yl group simultaneously
And z represents 0,1 or 2.
Sulphurized alkyl phenols or its alkali metal salt and alkali salt also are used as antioxidant.
Another kind of antioxidant is copper compound, such as D2EHDTPA copper or phosphordithiic acid copper, copper and carboxylic acid
Salt, aminodithioformic acid copper, sulfonic acid copper, phenol copper, acetylacetone copper.Copper I and II salt can also be used, amber acid or anhydride
Salt.
Lubricating composition according to the present invention can include all types of anti-oxidant additions well known by persons skilled in the art
Agent.
Advantageously, lubricating composition includes at least one ashless antioxidant.
Equally advantageous, lubricating composition according to the present invention include relative to the composition gross weight by weight
0.5 to 2% at least one antioxidant.
Lubricating composition according to the present invention can also include at least one cleaning additive.
Cleaning additive can usually be deposited by dissolving secondary oxidative and combustion product on metal part surface
The formation of thing is reduced.
Generally it is known to the skilled in the art available for the cleaning additive in lubricating composition according to the present invention.
Cleaning additive can be the anionic compound for including long lipophilicity hydrocarbon chain and hydrophilic head.With reference to cation can be alkali
The metal cation of metal or alkaline-earth metal.
Cleaning additive be preferably selected from the alkali or alkaline earth metal salt of carboxylic acid, sulfonate, salicylate, naphthenate and
Phenates.Alkali and alkaline earth metal ions are preferably calcium, magnesium, sodium or barium.
These metal salts usually include gold with the amount of stoichiometry or with excessive (therefore with amount more than stoichiometry)
Belong to.Then, it is related to overbasic cleaning additive；Bring the excessive metal of high alkalinity feature then usual for cleaning additive
For the form of the metal salt insoluble in oil, such as carbonate, hydroxide, oxalates, acetate, glutamate, preferably carbonic acid
Salt.
Advantageously, lubricating composition according to the present invention can be comprising the gross weight relative to the lubricating composition by weight
The cleaning additive of meter 2 to 4%.
Equally advantageous, lubricating composition according to the present invention can also include at least one pour point depressant additives.
By slowing down the formation of paraffin crystal, pour point depressant additives generally improve lubricating composition according to the present invention
Cryogenic property (cold behavior).
As the example of pour point depressant additives, polyalkyl methacrylate, polyacrylate, poly- aryl acyl can be mentioned that
Amine, poly- alkyl phenol, poly- alkylnaphthalene and alkylated polystyrene.
Advantageously, lubricating composition according to the present invention can also include at least one dispersant.
Dispersant may be selected from Mannich base, succinimide and its derivative.
Equally advantageous, lubricating composition according to the present invention can be included and pressed relative to the gross weight of the lubricating composition
The dispersant of weight meter 0.2% to 10%.
The lubricating composition of the present invention can also include the additive of at least one improvement viscosity index (VI).Improve viscosity index (VI)
The example of additive includes polymer esters；Styrene, the hydrogenation of butadiene and isoprene or non-hydrogenated homopolymer or copolymer,
Especially polyacrylate, polymethacrylates (PMA) or olefin copolymer, especially ethylene/propene copolymer.
Lubricating composition according to the present invention can be various forms.Lubricating composition according to the present invention can be specifically
Anhydrous composition.
Preferably, which is not lotion.
Lubricating composition defined above is used to prevent or reduce the early combustion in engine.
According to the present invention, engine more specifically refers to vehicle motor, such as：
- motor car engine, including petrol engine and diesel engine, and including combustion gas and petrol engine
(dual-fuel gas/petrol engine) and combustion gas and diesel engine (dual-fuel gas/diesel engine)；
The engine of-heavy goods vehicles, more specifically, with the engine of the heavy goods vehicles of combustion gas operation.
According to the present invention, engine also refers to 4 Stroke Engines, more specifically, 4 Stroke Engine peculiar to vessel, preferably with combustion
4 Stroke Engine peculiar to vessel of fate row.
In a preferred embodiment of the invention, lubricating composition is used for preventing or reducing vehicle motor, preferably motor-driven
Early combustion in car engine.
According to the present invention, early combustion includes producing the low-frequency vibration phenomenon of rumbling sound effective value.According to the present invention, early combustion is more specific
Ground refers to low speed early combustion (LSPI).
In a preferred embodiment of the invention, lubricating composition is used to prevent or reduces engine (preferred vehicle is started
Machine, preferably motor car engine) in low speed early combustion (LSPI).
The invention further relates to the method early fired in prevention or reduction engine, wherein making the described method includes at least one
The step of mechanical part of engine is contacted with lubricating composition as defined above.
For all features described in use above and preferably it is equally applicable to this method.
The invention further relates to organic molybdenum in the lubricating composition comprising at least one base oil be used for prevent or
The purposes early fired in engine is reduced, wherein the organic molybdenum is selected from：
Phosphordithiic acid molybdenum compound (Mo-DTP), or
Molybdenum complex without sulphur.
The feature and preferable set for being related to above-mentioned organic molybdenum and lubricating composition are equally applicable to the purposes.
The various aspects of the present invention are illustrated by following examples：
Embodiment 1：The preparation of lubricating composition according to the present invention
Classification and amount according to being presented in table 1 mix the various components of lubricating composition Cl1 and Cl2 according to the present invention.
Table 1
Embodiment 2：Compare the preparation of lubricating composition
Classification and amount mixing according to being shown in table 2 compare the various components of lubricating composition CC1.
Table 2
Embodiment 3：Lubricating composition Cl1 and Cl2 according to the present invention and the early combustion reduction for comparing lubricating composition CC1
The assessment of performance
The assessment is performed by assessing influence of every kind of lubricating composition to low speed early combustion (LSPI).
For this, increased by lighting turbine including total displacement for the GM Ecotech model sparks of 4 cylinder of array of 2.0L
Hydraulic motor quantifies LSPI phenomenons.
In the engine speed and 4x10 of 2000rpm5(4.105) Pascal's effective average pressure (EAP) start it is airborne
Under lotus, after the heating cycle of 20 minutes, test program consists of：In heavy load (with the speed of 2000rpm, 23x105
(23.105) Pascal EAP) lower 2 steps (sequence), in low load (with the speed of 1250rpm, 13x105
(13.105) Pascal EAP) lower 2 steps, and 2 steps under the heavy load equal to first 2.Each step includes
The 25000 motor cycles (motor cycle), to ensure the good statistics of studied phenomenon representativeness.
Each cylinder is equipped with sensor to measure the pressure during engine is run in combustion chamber.High frequency recording instrument is remembered
Pressure signal is recorded, this allows to carry out rigorous analysis to burning.If realize one of following 2 standards, then it is assumed that burning is LSPI
Event：
- maximum pressure in cycle is more than the average value of the maximum pressure on considered Overall Steps+measures in step
4.7 times of standard deviation of maximum pressure；
Crank shaft angle of the 2% of-fuel mixture quality when period demand burns be less than fuel mixture quality 2%
Average crank shaft angle when burning in the Overall Steps considered is fired plus the 2% of the quality of combustible mixture in all frequencies
4.7 times of the average deviation of crank shaft angle during burning.
For giving lubricating composition, the summation of LSPI events is calculated in all 6 steps of program.For every kind of institute
The lubricating composition of test, the test are repeated 4 times.
By comparing the par to the LSPI events of four Engine Block Tests and considering to four Engine Block Tests
The standard deviation of calculating compares influence of the lubricating composition to LSPI.
On lubricating composition Cl1 and Cl2 according to the present invention and the result for comparing lubricating composition CC1 in table 3
Provide；The quantity of LSPI events is lower, and the performance that lubricating composition prevention or reduction are early fired is better.
Table 3
| CI1 | CI2 | CC1 | |
| The quantity of LSPI events | 193 | 229 | 324 |
The results show that compared with the lubricating composition comprising molybdenum dithiocarbamate organic-molybdenum (Mo-DTC) compound,
Lubricating composition according to the present invention comprising Mo-DTP (composition Cl1) and the molybdenum complex (composition Cl2) without sulphur respectively
Show that improved LSPI reduces performance.
Claims (11)
1. lubricating composition prevention or reduction vehicle startup including at least one base oil and at least one organic molybdenum
The purposes early fired in machine, molybdenum complex of the organic molybdenum selected from no sulphur.
2. purposes according to claim 1, wherein the organic molybdenum is the molybdenum complex of no sulphur, the no sulphur
Molybdenum complex is selected from the organic complex of molybdenum and amide-type ligand, and prepared by the reaction through molybdenum source, amine derivative and aliphatic acid,
Wherein described aliphatic acid preferably has 4 to 28 carbon atoms, more preferably 8 to 18 carbon atoms.
3. purposes according to claim 1 or 2, wherein the organic molybdenum be the molybdenum complex of no sulphur and including
Selected from following at least one compounds：
The compound of-formula (A)：
Wherein：
●X1It is oxygen atom or nitrogen-atoms；
●X2It is oxygen atom or nitrogen-atoms；
● work as X1When being oxygen atom, n is 1, and works as X2When being oxygen atom, m is 1；
● work as X1When being nitrogen-atoms, n is 2, and works as X2When being nitrogen-atoms, m is 2；
●R1It is straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3 to 20
Carbon atom, advantageously comprises 7 to 17 carbon atoms；
The compound of-formula (B)
Wherein：
●X1It is oxygen atom or nitrogen-atoms；
●X2It is oxygen atom or nitrogen-atoms；
● work as X1When being oxygen atom, n is 1, and works as X2When being oxygen atom, m is 1；
● work as X1When being nitrogen-atoms, n is 2, and works as X2When being nitrogen-atoms, m is 2；
●R1It is straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3 to 20
Carbon atom, advantageously comprises 7 to 17 carbon atoms；
●R2It is straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3 to 20
Carbon atom, advantageously comprises 7 to 17 carbon atoms.
The mixture of the compound of-at least one formula (A) and the compound of at least one formula (B).
4. purposes according to any one of claim 1 to 3, wherein the organic molybdenum is the molybdenum complex of no sulphur
And include the compound of at least one formula (A1)：
Wherein R1It is straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3 to 20
A carbon atom, advantageously comprises 7 to 17 carbon atoms.
5. the purposes according to preceding claims, wherein the organic molybdenum be the molybdenum complex of no sulphur and including
The compound of formula (A1), wherein R1It is the alkyl group for including 11 carbon atoms.
6. purposes according to any one of claim 1 to 3, wherein the organic molybdenum is the molybdenum complex of no sulphur
And include the compound of at least one formula (A2)
Wherein R1 is straight or branched, saturation or undersaturated alkyl group, it includes 3 to 30 carbon atoms, preferably 3 to 20
A carbon atom, advantageously comprises 7 to 17 carbon atoms.
7. purposes according to any one of the preceding claims, wherein relative to the gross weight of the lubricating composition, it is described
The weight content scope of organic molybdenum is 0.05% to 3%, preferably 0.1% to 2%, advantageously scope be 0.1% to
1%.
8. purposes according to any one of the preceding claims, wherein the lubricating composition further comprises other add
Add agent, the other additive is selected from the friction improver in addition to the molybdenum complex of no sulphur, detergent, wear-resistant addition
Agent, EP agent, viscosity index improver, dispersant, antioxidant, pour-point depressant, defoamer, thickener and its mixing
Thing.
9. purposes according to any one of the preceding claims, it prevents or reduces vehicle motor, and preferably motor vehicle is sent out
Early combustion in motivation.
10. purposes according to any one of the preceding claims, it prevents or reduction engine, preferred vehicle engine,
Low speed early combustion (LSPI) advantageously in motor car engine.
11. the organic molybdenum of the molybdenum complex selected from no sulphur prevents in the lubricating composition including at least one base oil
Or the purposes early fired in reduction engine.
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| FR1557585 | 2015-08-06 | ||
| FR1557585A FR3039836B1 (en) | 2015-08-06 | 2015-08-06 | LUBRICATING COMPOSITIONS FOR PREVENTING OR REDUCING PRE-IGNITION IN AN ENGINE |
| PCT/EP2016/068720 WO2017021522A1 (en) | 2015-08-06 | 2016-08-05 | Lubricating compositions for preventing or reducing pre-ignition in an engine |
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| CN201680049760.9A Pending CN107949628A (en) | 2015-08-06 | 2016-08-05 | For preventing or reducing the lubricating composition early fired in engine |
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| US (2) | US20180230395A1 (en) |
| EP (2) | EP3331973A1 (en) |
| CN (2) | CN108026469A (en) |
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| CN113004335A (en) * | 2021-03-17 | 2021-06-22 | 辽宁大学 | Sulfur-phosphorus-free lubricating oil additive molybdate and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3461877B1 (en) * | 2017-09-27 | 2019-09-11 | Infineum International Limited | Improvements in and relating to lubricating compositions08877119.1 |
| JP6963521B2 (en) * | 2018-02-27 | 2021-11-10 | 株式会社パイロットコーポレーション | Oil-based ink composition for writing instruments and writing instruments using it |
| FR3092337B1 (en) | 2019-02-04 | 2021-04-23 | Total Marketing Services | Lubricating composition to prevent pre-ignition |
| FR3092335B1 (en) | 2019-02-04 | 2021-04-30 | Total Marketing Services | Lubricating composition to prevent pre-ignition |
| FR3093110B1 (en) | 2019-02-25 | 2021-05-21 | Total Marketing Services | Lubricating composition for preventing or reducing pre-ignition in an engine |
| FR3095209B1 (en) * | 2019-04-18 | 2021-10-22 | Total Marketing Services | PROCESS FOR REDUCING AND / OR CONTROL OF ABNORMAL GAS COMBUSTION IN A MARINE ENGINE OR A CONTROLLED IGNITION ENGINE |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889647A (en) * | 1985-11-14 | 1989-12-26 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| US5137647A (en) * | 1991-12-09 | 1992-08-11 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| WO2015042341A1 (en) * | 2013-09-19 | 2015-03-26 | The Lubrizol Corporation | Lubricant compositions for direct injection engines |
| WO2015091466A1 (en) * | 2013-12-17 | 2015-06-25 | Total Marketing Services | Lubricant composition made from fatty triamines |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07197068A (en) | 1993-12-30 | 1995-08-01 | Tonen Corp | Lubricating oil composition |
| US5412130A (en) | 1994-06-08 | 1995-05-02 | R. T. Vanderbilt Company, Inc. | Method for preparation of organic molybdenum compounds |
| JPH0931483A (en) | 1995-07-20 | 1997-02-04 | Tonen Corp | Lubricant composition |
| KR100516268B1 (en) | 1996-12-13 | 2005-09-20 | 엑손 리써치 앤드 엔지니어링 컴파니 | Lubricating oil compositions containing organic molybdenum complexes |
| US6074993A (en) * | 1999-10-25 | 2000-06-13 | Infineuma Usa L.P. | Lubricating oil composition containing two molybdenum additives |
| KR100812577B1 (en) | 2000-12-15 | 2008-03-13 | 니혼 유피카 가부시키가이샤 | O/w aqueous thermosetting resin dispersion, frp precision filter medium made with the aqueous dispersion, and process for producing the same |
| US6723685B2 (en) * | 2002-04-05 | 2004-04-20 | Infineum International Ltd. | Lubricating oil composition |
| CN101090958B (en) * | 2004-11-24 | 2011-12-21 | 新日本石油株式会社 | Lubricating oil composition |
| GB2423524A (en) * | 2005-02-28 | 2006-08-30 | Infineum Int Ltd | Crankcase lubricating oil |
| US7205423B1 (en) | 2005-09-23 | 2007-04-17 | R.T. Vanderbilt Company, Inc. | Process for the preparation of organo-molybdenum compounds |
| JP4597223B2 (en) * | 2008-06-09 | 2010-12-15 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
| JP5731170B2 (en) * | 2010-11-19 | 2015-06-10 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for sliding part provided with aluminum material and lubricating method |
| WO2015023559A1 (en) | 2013-08-12 | 2015-02-19 | Shell Oil Company | Methods for modifying auto-ignition properties of a base oil or lubricant composition |
| JP6300686B2 (en) * | 2014-01-31 | 2018-03-28 | Ｅｍｇルブリカンツ合同会社 | Lubricating oil composition |
| US10519394B2 (en) * | 2014-05-09 | 2019-12-31 | Exxonmobil Research And Engineering Company | Method for preventing or reducing low speed pre-ignition while maintaining or improving cleanliness |
| US20150322369A1 (en) * | 2014-05-09 | 2015-11-12 | Exxonmobil Research And Engineering Company | Method for preventing or reducing low speed pre-ignition |
| US20150322368A1 (en) * | 2014-05-09 | 2015-11-12 | Exxonmobil Research And Engineering Company | Method for preventing or reducing low speed pre-ignition |
| US20150322367A1 (en) * | 2014-05-09 | 2015-11-12 | Exxonmobil Research And Engineering Company | Method for preventing or reducing low speed pre-ignition |
| US9944877B2 (en) * | 2014-09-17 | 2018-04-17 | Exxonmobil Research And Engineering Company | Composition and method for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
| JP6572900B2 (en) * | 2014-09-19 | 2019-09-11 | 出光興産株式会社 | Lubricating oil composition and method for producing the lubricating oil composition |
| JP6197124B2 (en) * | 2015-03-24 | 2017-09-13 | 出光興産株式会社 | Lubricating oil composition for gasoline engine and method for producing the same |
| EP3320065A1 (en) * | 2015-07-07 | 2018-05-16 | ExxonMobil Research and Engineering Company | Composition and method for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
| US10421922B2 (en) * | 2015-07-16 | 2019-09-24 | Afton Chemical Corporation | Lubricants with magnesium and their use for improving low speed pre-ignition |
| US10280383B2 (en) * | 2015-07-16 | 2019-05-07 | Afton Chemical Corporation | Lubricants with molybdenum and their use for improving low speed pre-ignition |
-
2015
- 2015-08-06 FR FR1557585A patent/FR3039836B1/en not_active Expired - Fee Related
- 2015-10-12 FR FR1559665A patent/FR3039837B1/en not_active Expired - Fee Related
-
2016
- 2016-08-05 US US15/750,262 patent/US20180230395A1/en not_active Abandoned
- 2016-08-05 CN CN201680054791.3A patent/CN108026469A/en active Pending
- 2016-08-05 EP EP16756615.7A patent/EP3331973A1/en not_active Withdrawn
- 2016-08-05 WO PCT/EP2016/068721 patent/WO2017021523A1/en active Application Filing
- 2016-08-05 CN CN201680049760.9A patent/CN107949628A/en active Pending
- 2016-08-05 EP EP16750764.9A patent/EP3331972A1/en not_active Withdrawn
- 2016-08-05 US US15/750,254 patent/US20180223215A1/en not_active Abandoned
- 2016-08-05 WO PCT/EP2016/068720 patent/WO2017021522A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889647A (en) * | 1985-11-14 | 1989-12-26 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| US5137647A (en) * | 1991-12-09 | 1992-08-11 | R. T. Vanderbilt Company, Inc. | Organic molybdenum complexes |
| WO2015042341A1 (en) * | 2013-09-19 | 2015-03-26 | The Lubrizol Corporation | Lubricant compositions for direct injection engines |
| WO2015091466A1 (en) * | 2013-12-17 | 2015-06-25 | Total Marketing Services | Lubricant composition made from fatty triamines |
Non-Patent Citations (3)
| Title |
|---|
| KOSUKE FUJIMOTO ET AL.: "Engine Oil Development for Preventing Pre-Ignition in Turbocharged Gasoline Engine", 《SAE INTERNATIONAL JOURNAL OF FUELS AND LUBRICANTS》 * |
| 姚俊兵: "几种油溶型非硫磷摩擦改进剂的性能", 《石油商技》 * |
| 胡建强: "《有机钼润滑添加剂的抗氧协同行为及作用机理》", 31 March 2007, 中国矿业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004335A (en) * | 2021-03-17 | 2021-06-22 | 辽宁大学 | Sulfur-phosphorus-free lubricating oil additive molybdate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR3039836A1 (en) | 2017-02-10 |
| EP3331973A1 (en) | 2018-06-13 |
| WO2017021523A1 (en) | 2017-02-09 |
| FR3039837B1 (en) | 2017-09-15 |
| US20180223215A1 (en) | 2018-08-09 |
| EP3331972A1 (en) | 2018-06-13 |
| FR3039837A1 (en) | 2017-02-10 |
| CN107949628A (en) | 2018-04-20 |
| WO2017021522A1 (en) | 2017-02-09 |
| US20180230395A1 (en) | 2018-08-16 |
| FR3039836B1 (en) | 2017-09-15 |
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