CN108699474A - The lubricant compositions of amine and molybdenum based on neutralization - Google Patents
The lubricant compositions of amine and molybdenum based on neutralization Download PDFInfo
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- CN108699474A CN108699474A CN201780012826.1A CN201780012826A CN108699474A CN 108699474 A CN108699474 A CN 108699474A CN 201780012826 A CN201780012826 A CN 201780012826A CN 108699474 A CN108699474 A CN 108699474A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
-
- 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
- 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
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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
-
- 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
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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
- 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
- C10N2030/36—Seal compatibility, e.g. with rubber
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to lubricant compositions to reduce the purposes of the friction between two surfaces, at least one of two surfaces surface is carbon coated, and the composition includes:At least one base oil;At least one molybdenum compound;At least one amine salt neutralized completely or partially, amine meet lower formula (I):R-N(X)-Y(I).
Description
[Technical field]
The present invention relates to lubricant compositions field, more particularly to for speed changer or engine and especially motor-driven
The field of the lubricant compositions of vehicle motor.
[Background technology]
The first purpose of lubricant compositions is friction phenomenon and the abrasion for the mechanical part for reducing the movement that is in contact with each other.Profit
The special purpose of one of lubricant composition is that these limited in vehicle motor, especially motor vehicle engine rub now
As.In addition, the use of carbon coating is growing in engine, especially motor vehicle engine.It is therefore advantageous that can carry
Go out to allow to reduce for no matter the lubricant combination of the friction phenomenon of steel/steel, carbon coating/carbon coating or steel/carbon coating contact
Object.
In general, in order to limit friction phenomenon, friction improver can be integrated into lubricant compositions.Especially
Know addition fatty amine as friction improver.However, these amine can to the sealing element of sealing element, especially mechanical part, and
Significantly fluorinated polymer sealing element has adverse effect.These amine can effectively result under the acceleration of the mechanical performance of sealing element
Drop.
It it is known that and reduce friction phenomenon using organic molybdenum, more particularly for the contact between two steel surfaces
Friction phenomenon.It is known, however, to those skilled in the art that organic molybdenum, especially includes aminodithioformic acid
The use of the organic molybdenum of root can cause the abrasion of mechanical part to aggravate.And be also observed, contained in having in lubricant
It the degradable carbon coating of machine molybdenum compound and is even detached from itself and surface, and observes that this degradation can be in lubricant
Organic molybdenum content increase and aggravate.
It is advantageous, therefore, to provide lubricant compositions, reduce and are especially the rubbing in the presence of surface that carbon coats
While wiping phenomenon, especially there is to other engine components and to sealing element the influence of appropriateness.
Additionally, one of the target of lubricant compositions is to improve engine yield and therefore permit saving fuel.
[Invention content]
Therefore it is an object of the present invention to provide reduction friction phenomenon is allowed, especially on the surface with carbon coating
In the presence of friction phenomenon lubricant compositions, there is limited influence on the degradation of sealing element, sealing element especially sends out
Motivation sealing element, specifically for the sealing element of the sealing element of vehicle motor, such as motor vehicle engine.
The further object of the present invention is to provide the composition, allow reduce for no matter steel/steel, carbon coating/carbon
Coating or the friction phenomenon of steel/carbon coating contact.
The further object of the present invention is to provide the composition for also allowing to reduce fuel consumption.
By reading the following explanation of the present invention, other purposes will be apparent.
The shortcomings that cope with these purposes and known lubricants composition, the present invention propose a kind of lubricant compositions,
It includes:
At least one base oil;
At least one organic molybdenum;
At least one amine salt neutralized completely or partially, amine meet lower formula (I):
R-N(X)-Y(I)
Wherein:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 2 to 24 carbon atoms, preferably 4 to
24 carbon atoms, and more preferable 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
X is hydrogen atom;Linear chain or branched chain, fully saturated or fractional saturation alkyl has 1 to 24 carbon atom,
It is preferred that 1 to 10 carbon atom, especially 1 to 8 carbon atom;Benzyl;Or formula-R1-[NH-R2]n-NH2Group;
Y is hydrogen atom;Linear chain or branched chain, fully saturated or fractional saturation alkyl has 1 to 24 carbon atom,
It is preferred that 1 to 10 carbon atom, especially 1 to 8 carbon atom;Benzyl;Or formula-R1-[NH-R2]n-NH2Group;
N is 0 to 3 integer, preferably 0 to 2, preferably 0 or 1;
R1And R2It is identical or different, it is the alkyl of linear chain or branched chain, there are 2 to 4 carbon atoms, preferably 2 to 3 carbon originals
Son, preferably CH2CH2Or CH2CH2CH2;
At least one X or Y are hydrogen atom or-R1-[NH-R2]n-NH2;
X, at least one Y or R be linear chain or branched chain, fully saturated or fractional saturation alkyl, have 4 to 24 carbon
Atom, preferably 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
The acid of neutralizing amine is selected from the monoacid of formula (II):
R'COOH(II)
Wherein R ' is the linear chain or branched chain with 2 to 24 carbon atoms, fully saturated or fractional saturation alkyl.
Inventor also unexpectedly demonstrates the amine salt neutralized completely or partially and organic molybdenum of the present invention
Combination allow to make for no matter the friction phenomenon of steel/steel, carbon coating/carbon coating or steel/carbon coating contact is restricted, and
And there is minimum or limited influence on sealing element degradation.In addition, inventor has also been demonstrated that, it is of the invention partially or completely
The amine salt of neutralization has the compatibility of the better seal part compared with corresponding unneutralized amine, especially and engine sealing
And the especially compatibility of the sealing element of motor vehicle engine.In this application, sealing element be engine design in institute
The sealing element of use, is generally polymer seal, is especially elastomeric seal, preferred fluorinated elastomeric seal.
Particularly, with unneutralized amine on the contrary, the lubricant combination for including at least one amine salt partially or completely neutralized of the present invention
Object allows to limit engine sealing, the especially abrasion of motor vehicle engine sealing element.
It is intended to be neutralized and the amine used in the present compositions is preferably the amine for meeting following formula (Ia):
R-N(X)-R1-[NHR2]n-NH2(Ia)
Wherein R, X, R1,R2There is definitions given above with n, and
At least one X or R be linear chain or branched chain, fully saturated or fractional saturation alkyl, has 4 to 24 carbon originals
Son, preferably 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms.
Preferably, in the formula (I) of the present invention or the compound of (Ia):
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 14 to 24 carbon atoms, especially
16 to 24 carbon atoms, such as 18 to 24 carbon atoms;And
X is hydrogen atom;The alkyl of linear chain or branched chain with 2 to 8 carbon atoms;Benzyl;Or formula-R1-[NH-R2]n-NH2
Group.
Preferably, in the formula (I) of the present invention or the compound of (Ia):
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 14 to 24 carbon atoms, especially
16 to 24 carbon atoms, such as 18 to 24 carbon atoms;And
X is hydrogen atom or formula-R1-[NH-R2]n-NH2Group.
Preferably, in the compound of the formula (I) of the present invention:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 14 to 24 carbon atoms, especially
16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
Y is-R1-[NH-R2]n-NH2;
N=0;
R1It is CH2CH2CH2;And
X is CH2CH2CH2NH2Or H.
Preferably, in the compound of the formula (Ia) of the present invention:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 14 to 24 carbon atoms, especially
16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
N=0;
R1It is CH2CH2CH2;And
X is CH2CH2CH2NH2Or H.
In particularly preferred mode, amine is selected from following amine:
RNHCH2CH2CH2CNH2, wherein R represent with 16 to 18 carbon atoms linear chain or branched chain, it is fully saturated or
The alkyl of fractional saturation;Or
N(R)(CH2CH2CH2NH2)(CH2CH2CH2NH2), wherein R represents the linear chain or branched chain with 16 to 18 carbon atoms
, fully saturated or fractional saturation alkyl.
In the present invention, formula is preferably selected from for neutralizing the acid of amine of formula defined above (I) or (Ia) in a salt form
(II) acid, wherein R ' is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 7 to 24 carbon atoms, excellent
Select 10 to 24 carbon atoms, such as 14 to 20 carbon atoms, especially 16 to 20 carbon atoms.
In particularly preferred mode, it is oleic acid to allow the acid that the amine of formula (I) or (Ia) neutralize.
The amine used in the composition of the present invention is neutralized completely or partially.Preferably, in amine the molal quantity of nitrogen-atoms with
Molar ratio between the molal quantity of the acid functional group of formula (II) is between 9:1 and 1:Between 1, it is preferably between 5:1 and 1:Between 1.
By organic molybdenum according to the present invention, be intended to indicate it is any dissolve in oil, be especially soluble in base oil
In organic molybdenum.
The organic molybdenum of the present invention can be selected from organic molybdenum complex compound, such as can be via molybdenum oxide or ammonium molybdate and fat
Fat, glyceride, aliphatic acid or aliphatic acid derivative (ester, amine, amide ...) the reaction carboxylate, ester, the molybdenum amide that obtain.
Preferably, organic molybdenum is selected from the molybdenum complex of not sulfur-bearing and phosphorus, has acid amide type ligand, mainly passes through molybdenum
Source (such as molybdenum trioxide) and amine derivative with there is such as 4 to 28 carbon atoms, the aliphatic acid of preferably 8 to 18 carbon atoms
It is prepared by the reaction of (such as contained in the aliphatic acid in vegetable oil or animal oil).
The synthesis of such compound is described in such as patent US4889647, EP0546357, US5412130, EP1770153
In.
In a preferred embodiment of the present invention, organic molybdenum is obtained organic selected from the reaction via following substance
Molybdenum complex:
(i) monoglyceride, two glyceride or triglycerin ester type fat or aliphatic acid;
(ii) the amine source of formula (A):
Wherein:
-X1It is oxygen atom or nitrogen-atoms;
-X2It is oxygen atom or nitrogen-atoms;
Work as X1Or X2When being oxygen atom, n and m are 1;
Work as X1Or X2When being nitrogen-atoms, n and m are 2;
And (iii) molybdenum source, it is selected from molybdenum trioxide or molybdate, preferably ammonium molybdate, the total weight relative to complex compound
Meter presents in an amount at least sufficient to and provides 0.1% to 30% molybdenum.
In one embodiment of the invention, relative to the total weight of complex compound, organic molybdenum complex compound may include from 2% to
The molybdenum of 8.5% weight.
In a preferred embodiment of the present invention, organic molybdenum complex compound is (single by the compound of at least one formula (III) or (IV)
Solely or as a mixture) constitute:
Wherein:
X1It is oxygen atom or nitrogen-atoms;
X2It is oxygen atom or nitrogen-atoms;
Work as X1N is 1 when being oxygen atom, and works as X2M is 1 when being oxygen atom;
Work as X1N is 2 when being nitrogen-atoms, and works as X2M is 2 when being nitrogen-atoms;
R1It is linear chain or branched chain, saturated or unsaturated alkyl, there are 3 to 30 carbon atoms, preferably 3 to 20 carbon
Atom, advantageously 7 to 17 carbon atoms;
Wherein:
X1It is oxygen atom or nitrogen-atoms;
X2It is oxygen atom or nitrogen-atoms;
Work as X1N is 1 when being oxygen atom, and works as X2M is 1 when being oxygen atom;
Work as X1N is 2 when being nitrogen-atoms, and works as X2M is 2 when being nitrogen-atoms;
R1It is linear chain or branched chain, saturated or unsaturated alkyl, there are 3 to 30 carbon atoms, preferably 3 to 20 carbon
Atom, advantageously 7 to 17 carbon atoms;
R2It is linear chain or branched chain, saturated or unsaturated alkyl, there are 3 to 30 carbon atoms, preferably 3 to 20 carbon
Atom, advantageously 7 to 17 carbon atoms.
In one embodiment of the invention, organic molybdenum complex compound is prepared by following reaction:
(i) monoglyceride, two glyceride or triglycerin ester type fat or aliphatic acid;
(ii) diethanol amine or 2- (2- aminoethyls) ethylaminoethanol;And
(iii) molybdenum source, is selected from molybdenum trioxide or molybdate, preferred ammonium molybdate, relative to the total weight of complex compound,
Amount is enough to provide 0.1% to 20.0% molybdenum.
In a preferred embodiment of the present invention, organic molybdenum complex compound is by least one formula (III-a) or the chemical combination of (III-b)
Object individually or is as a mixture constituted:
Wherein:
R1It is linear chain or branched chain, saturated or unsaturated alkyl, there are 3 to 30 carbon atoms, preferably 3 to 20 carbon
Atom, advantageously 7 to 17 carbon atoms,
Wherein R1It is linear chain or branched chain, saturated or unsaturated alkyl, there are 3 to 30 carbon atoms, preferably 3 to 20
A carbon atom, advantageously 7 to 17 carbon atoms.
The example of molybdenum complex as not sulfur-bearing according to the present invention can be mentioned that and be sold by Vanderbilt
Molyvan
In another embodiment, organic molybdenum can be selected from molybdenum dithiophosphate or molybdenum dithiocarbamate.
In a preferred embodiment of the present invention, organic molybdenum is selected from molybdenum dithiocarbamate.
Molybdenum dithiocarbamate compound (Mo-DTC compounds) is the metal core with one or more ligand bindings
The heart is formed by complex compound, which is alkyl aminodithioformic acid root.These compounds are those skilled in the art crowd institutes
Known.
In one embodiment of the invention, relative to the total weight of Mo-DTC compounds, Mo-DTC compounds may include from
1% to 40% weight, preferably 2% to 30% weight, more preferable 3% to 28% weight, the advantageously molybdenum of 4% to 15% weight.
In another embodiment of the present invention, relative to the total weight of Mo-DTC compounds, Mo-DTC compounds may include
From 1% to 40% weight, preferably 2% to 30% weight, more preferable 3% to 28% weight, advantageously 4% to 15% weight
Sulphur.
In another embodiment of the present invention, Mo-DTC compounds can be selected from the Mo-DTC with the core containing 2 molybdenum atoms
Compound (also referred to as dimerization Mo-DTC) and the Mo-DTC compounds with the core containing 3 molybdenum atoms (are also referred to as trimerization Mo-
DTC)。
In another embodiment of the present invention, trimerization Mo-DTC accord with Formula Mo3SkLn, wherein:
K is at least 4, preferably 4 to 10, advantageously 4 to 7 integer;
N is 1 to 4 integer;And
L is alkyl aminodithioformic acid root, which there is 1 to 100 carbon atom, preferably 1 to 40 carbon atom to have
3 to 20 carbon atoms in sharp ground.
As the example of trimerization Mo-DTC compounds according to the present invention, it can be mentioned that and be for example described in document WO 98/
Compound and preparation method thereof in 26030 and US 2003/022954.
In a preferred embodiment of the present invention, Mo-DTC compounds are dimerization Mo-DTC compounds.
As the example of dimerization Mo-DTC compounds, can be mentioned that for example be described in document EP 0757093,
Compound and preparation method thereof in EP150719851, EP 0743354 or EP 1013749.
Dimerization Mo-DTC compounds correspond generally to the compound of formula (V):
Wherein:
R3,R4,R5,R6It is identical or different, it is each independently alkyl selected from the following:Alkyl, alkenyl, aryl, naphthenic base
Or cycloalkenyl group;
X3,X4,X5And X6It is identical or different, respectively stand alone as oxygen atom or sulphur atom.
About the present invention meaning in alkyl, indicate with 1 to 24 carbon atom linear chain or branched chain, saturation or
Undersaturated alkyl.
In one embodiment of the invention, alkyl is selected from methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
Isotridecyl, myristyl, cetyl, stearyl, eicosyl, docosyl, tetracosyl, melissyl,
2- ethylhexyls, 2- butyl octyls, 2- butyl decyl, 2- hexyls octyl, 2- hexyls decyl, 2- octyl-decyls, 2- hexyls 12
Alkyl, 2- octyldodecyls, 2- decyls myristyl, 2- dodecyls cetyl, 2- cetostearyls, 2- ten
Tetraalkyl octadecyl, myristyl, palmityl and stearyl.
About the alkenyl in the meaning of the present invention, indicates comprising at least one double bond and there are 2 to 24 carbon atoms
Linear chain or branched chain alkyl.Alkenyl can be selected from vinyl, allyl, acrylic, cyclobutenyl, isobutenyl, pentenyl, isoamyl
Alkenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, dodecenyl succinic, tetradecene base and oil
Alkenyl.
About the aryl in the meaning of the present invention, polycyclic aromatic hydrocarbon or aromatic group are indicated, replaced by alkyl or not
Replaced by alkyl.Aryl can have 6 to 24 carbon atoms.
In one embodiment, aryl can be selected from phenyl, toluyl groups, xylyl, cumenyl, mesitylene base, benzyl
Base, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propyl phenyl, butyl phenyl, amylbenzene
Base, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl, dodecylphenyl, benzene
Base phenyl, benzyl phenyl, phenyl-styrene, p- cumyl phenyl and naphthalene.
In the meaning of the present invention, naphthenic base and cycloalkenyl group may be selected from but not limited to cyclopenta, cyclohexyl, suberyl, methyl
Cyclopenta, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl group, cycloheptenyl, methyl cyclopentene base, methyl cyclohexane
Alkenyl.Naphthenic base and cycloalkenyl group can have 3 to 24 carbon atoms.
In a preferred embodiment of the present invention, R3,R4,R5And R6It is identical or different, it respectively stands alone as with 4 to 18 carbon
The alkyl of atom or alkenyl with 2 to 24 carbon atoms.
In one embodiment of the invention, X3,X4,X5And X6Can be identical, and sulphur atom can be represented.
In another embodiment of the present invention, X3,X4,X5And X6Can be identical, and oxygen atom can be represented.
In another embodiment of the present invention, X3And X4Sulphur atom, and X can be represented5And X6Oxygen atom can be represented.
In another embodiment of the present invention, X3And X4Oxygen atom, and X can be represented5And X6Sulphur atom can be represented.
In another embodiment of the present invention, the ratio of the number of the sulphur atom of Mo-DTC compounds and the number of oxygen atom
It (S/O) can be from (1:3) (3 are changed to:1).
In another embodiment of the present invention, the Mo-DTC compounds of formula (V) can be selected from symmetrical Mo-DTC compounds, asymmetry
Mo-DTC compounds, and combinations thereof.
About symmetrical Mo-DTC compounds according to the present invention, the Mo-DTC compounds of formula (V), wherein R are indicated3,R4,
R5And R6Group is identical.
About asymmetry Mo-DTC compounds according to the present invention, the Mo-DTC compounds of formula (V), wherein group are indicated
R3And R4It is identical, group R5And R6It is identical, and group R3And R4Different from group R5And R6。
In a preferred embodiment of the present invention, Mo-DTC compounds are at least one symmetrical Mo-DTC compounds and at least one
The mixture of kind asymmetry Mo-DTC compounds.
In one embodiment of the invention, R3And R4It is identical, and the alkyl with 5 to 15 carbon atoms is represented, and R5With
R6It is identical, but unlike that R3And R4, and represent the alkyl with 5 to 15 carbon atoms.
In a preferred embodiment of the present invention, R3And R4It is identical, and represent the alkyl with 6 to 10 carbon atoms, R5With
R6Represent the alkyl with 10 to 15 carbon atoms.
In another preferred embodiment of the present invention, R3And R4It is identical, the alkyl with 10 to 15 carbon atoms is represented, and
And R5And R6It is the alkyl with 6 to 10 carbon atoms.
In another preferred embodiment of the present invention, R3,R4,R5And R6It is identical, and alkyl is represented, there are 5 to 15 carbon
Atom, preferably 8 to 13 carbon atoms.
Advantageously, Mo-DTC compounds are selected from the compound of formula (V),
Wherein:
-X3And X4It is oxygen atom;
-X5And X6It is sulphur atom;
-R3It is the alkyl with 8 carbon atoms or the alkyl with 13 carbon atoms;
-R4It is the alkyl with 8 carbon atoms or the alkyl with 13 carbon atoms;
-R5It is the alkyl with 8 carbon atoms or the alkyl with 13 carbon atoms;
-R6It is the alkyl with 8 carbon atoms or the alkyl with 13 carbon atoms.
Therefore advantageously, Mo-DTC compounds are selected from the compound of formula (V-a):
Wherein group R3,R4,R5And R6Such as it is defined for formula (V).
More advantageously, Mo-DTC compounds are the mixtures of following compound:
The Mo-DTC compounds of formula (V-a), wherein R3,R4,R5And R6Represent the alkyl with 8 carbon atoms;
The Mo-DTC compounds of formula (V-a), wherein R3,R4,R5And R6Represent the alkyl with 13 carbon atoms;And
The Mo-DTC compounds of formula (V-a), wherein R3,R4Represent the alkyl with 13 carbon atoms, and R5And R6It represents
Alkyl with 8 carbon atoms;And/or
The Mo-DTC compounds of formula (V-a), wherein R3,R4Represent the alkyl with 8 carbon atoms, and R5And R6Represent tool
There is the alkyl of 13 carbon atoms.
As the example of Mo-DTC compounds, can be mentioned that by R.T VanderbiltThe product of sale
Molyvan Molyvan Or MolyvanOr the product Sakura-lube sold by AdekaSakura-lube Sakura-lube Or Sakura-lube
Preferably, relative to the total weight of composition, lubricant compositions of the invention include 0.05% to 5% weight
Amount, the amine salt of preferably 0.1% to 2% weight partially or completely neutralized.
Preferably, relative to the total weight of composition, lubricant compositions of the invention include 0.01% to 3% weight
The organic molybdenum of amount, preferably 0.05% to 3% weight, such as 0.1% to 2% weight.
In general, the lubricant compositions of the present invention may include any kind of mineral known to technical staff, conjunction
At or natural, animality or vegetal lubricant base oil.
The base oil used in lubricant compositions of the present invention can be the I to V in the classification belonged to defined in API classification
Or mixtures thereof the mineral of class or the oil (or equivalent in its ATIEL classification) (Table A) of synthesis source.
Table A
The mineral base oil of the present invention includes all types of base oils obtained in the following manner:Vacuum and normal pressure steam
Crude oil is evaporated, then carries out refining operation, such as solvent extraction, depitching, solvent dewaxing, hydrotreating, hydrocracking plus hydrogen are different
Structure and hydrofinishing.
The mixture of synthetic oil and mineral oil also can be used.
In general, about the different lubricating base oils to prepare lubricating composition of the present invention use there is no limit,
In addition to they must have the performance suitable for engine or transmission for vehicles, especially viscosity, viscosity index (VI), sulfur content,
Oxidation resistent susceptibility.
The base oil of lubricant compositions of the present invention is further selected from synthetic oil, certain esters of such as carboxylic acid and alcohol;And choosing
From poly alpha olefin.Poly alpha olefin as base oil is obtained from the monomer for example with 4 to 32 carbon atoms, such as obtained from pungent
Alkene or decene, and have 1.5 to 15mm at 100 DEG C according to standard ASTM D4452.s-1Viscosity.According to standard ASTM
D5296, their average molecular weight are typically in the range of between 250 and 3 000.
Preferably, base oil of the invention be selected from aromatic content between 0% and 45%, be preferably between 0% with
The above base oil between 30%.The aromatic content of oil is measured according to UV Burdett methods.It is being not intended to be taken office
In the case of what theoretical constraint, the aromaticity of base oil is that the work of the polymer changed according to temperature is allowed to be optimal
Characteristic.Optimization at relatively high temperatures is allowed to the selection of the oil with low aromaticity content.
Advantageously, relative to the total weight of composition, lubricant compositions of the invention include at least 50% weight
Base oil.
More advantageously, relative to the total weight of composition, lubricant compositions of the invention include at least 60% weight,
The even at least base oil of 70% weight.
Particularly advantageously, relative to the total weight of composition, lubricant compositions of the invention include 60% to
The base oil of 99.5% weight, the preferably base oil of 70% to 99.5% weight.
Can be used numerous additives for the present invention the lubricant compositions.
The preferable additives of lubricant compositions for being used in the present invention be selected from detergent, antiwear additive, with
The different friction improver of organic molybdenum, EP agent, dispersant, pour-point depressant, antifoaming agent, thickener and its
Mixture.
Preferably, lubricant compositions of the present invention include at least one antiwear additive, at least one EP agent
Or mixtures thereof.
Antiwear additive and EP agent protect friction surface by forming the protective film of absorption on the surface.
There are various antiwear additives.Preferably, for lubricating composition of the present invention, antiwear additive choosing
From phosphorus-sulfide additive, such as metal alkylthiophosphates, especially alkylthio trbasic zinc phosphate, and more specifically dioxane
Base zinc dithiophosphate or ZnDTP.Preferred compound has formula Zn ((SP (S) (OR1)(OR2))2, wherein R2And R3It is identical or
Difference is each independently alkyl, the preferably alkyl with 1 to 18 carbon atom.
Amine phosphate is also the antiwear additive that can be used in lubricant compositions of the present invention.However, being added by these
Add the phosphorus that agent is contributed that can play toxic action to the catalysis system of motor vehicles, because these additives generate ash content.It can pass through
Not phosphorous additive (such as polysulfide, especially olefine sulfide) partly makes these influences instead of amine phosphate
Reach minimum.
Advantageously, relative to the total weight of lubricant compositions, lubricating composition of the present invention may include 0.01% to 6%
Weight, preferably 0.05% to 4% weight, the antiwear additive and EP agent of more preferable 0.1% to 2% weight.
Advantageously, lubricant compositions of the present invention may include at least one additional friction different from organic molybdenum
Improve additive.Additional friction improves the compound and ashless point of compound that additive can be selected from providing metallic element.It is carrying
Among the compound of metallic element, transition metal complex, such as Mo, Sb, Sn, Fe, Cu, Zn can be mentioned that, ligand can be with
It is the hydrocarbon compound comprising oxygen atom, nitrogen-atoms, sulphur atom or phosphorus atoms.Improvement additive is wiped for ashless centimorgan generally to derive from
Organic matter, and can be selected from the monoesters, fat epoxide, boric acid fat epoxide of aliphatic acid and polyalcohol;Or aliphatic acid is sweet
Grease.According to the present invention, fatty compound includes at least one alkyl with 10 to 24 carbon atoms.
Advantageously, relative to the total weight of lubricant compositions, lubricant compositions of the present invention may include from 0.01%
To 2% weight or from 0.01% to 5% weight, preferably change from 0.1% to 1.5% weight or from the friction of 0.1% to 2% weight
Into additive.
Advantageously, lubricant compositions of the invention may include at least one antioxidant.
Antioxidant generally allows the delay degradation of the lubricant compositions in use.This degradation can be explained especially
To form deposit, the viscosity of lubricant compositions is construed to there are sludge or increased.
Antioxidant especially serves as free radical inhibitors or hydrogen peroxide decomposition agent.It is anti-oxidant what is frequently used
Among additive, the antioxidant of phenols type, the antioxidant of amine type can be mentioned that, phosphorus-vulcanization is anti-oxidant to be added
Add agent.Some producible ash contents of such as phosphorus-vulcanization antioxidant in these antioxidants.The anti-oxidant addition of phenols
Agent without ash content or can be in neutrality or the form of alkaline metal salt.Antioxidant particularly can be selected from steric hindrance
Phenol, the ester of sterically hindered phenol and sterically hindered phenol comprising thioether bridge, diphenylamine, by least one C1-C12It is alkyl-substituted
Diphenylamine, N, N'Dialkyl group-aryl-diamines and its mixture.
Preferably, according to the present invention, sterically hindered phenol is selected from the compound comprising phenolic groups, wherein carrying alcohol functional group
Carbon at least one adjacent carbons by least one C1-C10Alkyl, preferably C1-C6Alkyl, preferably C4Alkyl replaces, preferably by uncle
Butyl replaces.
Amino-compound is another kind of workable antioxidant, optionally with phenols antioxidant group
It closes.The example of amino-compound is aromatic amine, such as formula NR3R4R5Aromatic amine, wherein R3It is optionally substituted aliphatic group
Group or aromatic group, R4It is optionally substituted aromatic group, R5It is hydrogen atom, alkyl, aryl or formula R6S(O)zR7Base
Group, wherein R6It is alkylidene or alkenylene, R7It is alkyl, alkenyl or aryl, and z is 0,1 or 2.
The alkyl phenol of vulcanization or its alkali metal salt or alkali salt also are used as antioxidant.
Another kind of antioxidant is copper compound antioxidant, such as D2EHDTPA copper or phosphordithiic acid
The salt of copper, copper and carboxylic acid;Dithiocar-bamate, sulfonate, phenates and the acetylacetonate of copper.I and II also can be used
The salt of valence mantoquita, succinic acid or acid anhydrides.
Lubricant compositions of the present invention can contain any kind of antioxidant well known by persons skilled in the art.
Advantageously, lubricant compositions include at least one without ash content antioxidant.
Additionally advantageously, relative to the total weight of composition, lubricant compositions of the present invention include 0.5% to 2% weight
At least one antioxidant.
The lubricant compositions of the present invention also may include at least one detergent additive
It is heavy on metal part surface that detergent additive generally allows to reduce by dissolving secondary oxidation and combustion product
The formation of product object.
The detergent additive that can be used in the lubricant compositions of the present invention is generally known to the skilled in the art.
Detergent additive can be anionic compound, and it includes lipophilicity hydrocarbon long-chain and hydrophilic heads.The cation to be associated can be with
It is the metal cation of alkali metal or alkaline earth.
Detergent additive be preferably selected from the carboxylate of alkali or alkaline earth metal, sulfonate, salicylate, naphthenate and
Phenates.Alkali and alkaline earth metal ions are preferably calcium, magnesium, sodium or barium.
These metal salts generally comprise the metal of stoichiometric amount or the gold of excessive (that is, more than amount of stoichiometric amount)
Belong to.Then they are high alkali cleaning additives;Assign detergent additive high alkaline nature excessive metal then be usually oil not
The form of soluble metal salts, such as carbonate, hydroxide, oxalates, acetate, glutamate, preferably carbonate.
Advantageously, relative to the total weight of lubricant compositions, lubricant compositions of the invention may include 2% to
The detergent additive of 4% weight.
Additionally advantageously, lubricating composition of the present invention can further include at least one pour-point depressant additive.
By slowing down the formation of alkane crystal, pour-point depressant generally improves lubricant compositions of the present invention in low temperature
Under performance.
As the example of pour point depressant additives, alkyl polymethacrylates, polyacrylate, poly- aryl acyl can be mentioned that
Amine, poly- alkyl phenol, poly- alkylnaphthalene, alkylated polystyrene.
Advantageously, lubricating composition of the invention also may include at least one dispersant.
Dispersant can be selected from Mannich base, succinimide and its derivative.
Additionally advantageously, relative to the total weight of lubricant compositions, lubricant compositions of the present invention may include from 0.2%
Weight to 10% weight dispersant.
Lubricant compositions of the present invention also may include at least one additional polymer for improving viscosity index (VI).As improvement
The example of the additional polymer of viscosity index (VI), can be mentioned that polymer esters;Styrene, the hydrogenation of butadiene and isoprene or not
The homopolymer or copolymer of hydrogenation;Polymethacrylates (PMA).
The invention further relates to lubricant compositions lubricating mechanical components of the present invention (especially to be sent out in speed changer and/or vehicle
Motivation, preferably in motor vehicle engine) purposes.
The composition of the present invention is especially for reducing in especially vehicle motor and preferred motor vehicle engine
(especially between two steel surfaces, table is coated between two carbon coating surfaces or in steel surface and carbon between two surfaces
Between face) friction.
In particularly advantageous way, the present invention relates to lubricant compositions lubricating mechanical components of the present invention (especially to exist
Speed changer and/or vehicle motor, preferably in motor vehicle engine) purposes, wherein at least one of component component is
Carbon coated.Preferably, one of component is carbon coated, and (multiple) other components are steel or carbon.
In particularly advantageous way, the present composition is used for, and especially in vehicle motor, preferably motor vehicles are sent out
The friction between two surfaces is reduced in motivation, at least at least one of two surfaces surface is carbon coated, preferably
Ground, a surface in two surfaces is carbon coated, and another surface is steel surface or two surfaces are through carbon
Coating.
In the present invention, about"Carbon coating"Or"Carbon coating", indicate any coating for including carbon.About carbon coating,
It especially indicates diamond coatings, and more particularly nano diamond coating.These coatings especially can be at least one layer of pure
The form for the nanocrystal diamond that degree is 70% to 99%.Preferably, carbon coating is selected from Nano diamond in the form of the following
Coating:At least one layer of nanocrystal diamond, purity are 70% to 99%, preferably 70% to 97%, advantageously 75%, and its
Thickness is 0.1 μm to 3 μm, and preferably 0.5 μm to 2 μm, advantageously thickness is 1.5 μm.
These carbon coatings are further selected from the coating of DLC types (diamond-like-carbon).Any kind of DLC coatings can be used.
In general, DLC returns a set of substantially carbon containing amorphous materials family together.Among these families, using hydrogenation
DLC, especially a-C:H;With unhydrogenated DLC, especially a-C or ta-C.
DLC has the performance for mixing carbon content and hydrogen content with its sp3 and changing.Some DLC variants can be doped with gold
Belong to element, such as iron, chromium or tungsten.
Compared to diamond coatings, DLC coatings generally have lower mechanical endurance and heat resistance, because they are without fixed
Shape material.On the other hand, they are generally less coarse, and more particularly can they be deposited on most of substrates at low temperature
On.Preferably, DLC is hydrogenation DLC, the especially a-C containing 10% to 40% hydrogen:H.
Advantageously, the use of lubricant compositions of the present invention is prevented from aggravating and even be reduced especially in vehicle startup
Machine, preferably between the abrasion between two in motor vehicles surface, especially two steel surfaces, two carbon coating surface it
Between or steel surface and carbon coating surface between abrasion.
The invention further relates to lubricant compositions of the present invention reducing the fuel consumption of vehicle (especially motor vehicles)
Purposes.
Advantageously, inventor has also been shown that, the amine salt partially or completely neutralized of the invention have with it is corresponding not in
With amine compare it is more preferably simultaneous with sealing element (sealing element of special engine sealing and especially motor vehicle engine)
Capacitive.In the present invention, sealing element is the sealing element that uses in engine design, and generally polymer seal, especially
Elastomeric seal, the elastomeric seal of preferred fluorinated.Compared with unneutralized amine, the present composition especially allows to limit
The abrasion of engine sealing (especially in motor vehicle engine) processed.
Therefore, it additionally reduces the invention further relates to the present composition and is contained in vehicle motor (preferably motor vehicles)
In sealing element deterioration purposes.
The invention further relates to (be especially in speed changer and/or vehicle motor, special motor vehicle for lubricating mechanical components
In engine) method comprising the placement of at least one component to be contacted at least with lubricant compositions of the present invention
One step.Preferably, at least one of each component component is carbon coated, other (multiple) components be steel part or
The component of carbon coating.
The invention further relates to the frictions between two surfaces for reducing vehicle motor (especially motor vehicles)
Method comprising at least one to contact the placement of at least one of each surface surface with lubricant compositions of the present invention
Step.Each surface is for example defined above.Particularly, this method is related between reducing by two steel surfaces, the table of two carbon coating
Friction between face or between steel surface and the surface of carbon coating.Preferably, the present invention relates to (special to reduce vehicle motor
Not motor vehicle engine) two surfaces between friction method, at least one of each surface surface is applied through carbon
Cover, this method include at least one of each surface surface is placed contact with lubricant compositions of the present invention it is at least one
Step.Preferably, a surface in each surface is carbon coated, and another is steel, or two surfaces it is equal
It is carbon coated.
Advantageously, can not be aggravated using the method for the present invention and even reduce especially vehicle motor and preferably it is motor-driven
Between two surfaces in vehicle motor, between especially two steel surfaces, two carbon coating surface between or steel surface
Abrasion between the surface of carbon coating.
Advantageously, it can not aggravate and even reduce the abrasion between two surfaces, the surface using the method for the present invention
In at least one surface be carbon coated.
The invention further relates to the methods of the fuel consumption for reducing vehicle (preferably motor vehicles) comprising to by vehicle
The mechanical part of engine places at least one step contacted with lubricant compositions (all as defined above).
The engine of the present invention can be two-stroke internal combustion engine or four-stroke ic engine.Engine can be to be intended to
By the petrol engine or diesel engine of conventional gasoline or diesel driven.In the present invention, about"Conventional gasoline"Or it closes
In"Conventional diesel oil", indicate to be started by the fuel driven that is obtained after refining the oil (such as crude oil) of mineral origin
Machine.Engine, which can also be, to be improved to by being driven containing oil fuel (such as alcohol-based fuel or biodiesel) from recyclable materials
Dynamic petrol engine or diesel engine.
The vehicle of the present invention can be light vehicle, such as car and motorcycle.The vehicle can also be heavy vehicle, apply
Work machinery, ship.
The speed changer of the present invention can be such as motor vehicles etc light vehicle in the speed changer that uses, especially tooth
Roller box.
The present invention speed changer can also be the speed changer used in heavy vehicle, construction machinery, especially gear-box or
Axis.
The speed changer of the present invention can also be the speed changer used in industrial machine, especially for for wind turbine
Gear or gear-box.
Other themes of the present invention are that the amine salt (all as defined above) that neutralizes completely or partially is organic at least one
Purposes of the combination of molybdenum compound in the lubricant compositions comprising at least one base oil, to reduce engine (especially
Vehicle motor and especially motor vehicle engine) between two surfaces, particularly between two steel surfaces, steel surface with
Friction between the surface of carbon coating or between the surface of two carbon coating.
The further subject matter of the present invention is the amine salt (all as defined above) neutralized completely or partially and at least one
Purposes of the combination of organic molybdenum in the lubricant compositions comprising at least one base oil, to reduce engine
Friction in (special vehicle motor and especially motor vehicles) between two surfaces, at least one of described surface surface
It is carbon coated.Preferably, a surface in the surface is carbon surface, and the other is steel surface or two tables
Face is carbon surface.
Using use above, it can not also aggravate and even reduce especially in vehicle motor and preferred motor vehicles hair
Abrasion between two steel surfaces in motivation, between the surface of steel surface and carbon coating or between the surface of two carbon coating.
Using use above, it can not also aggravate and even reduce by two surfaces (especially in vehicle motor, preferably
In motor vehicle engine) between abrasion, at least one of described surface surface is carbon coated.Preferably, institute
It is carbon coated to state in surface surface, and another surface is steel surface or two surfaces are carbon coated.
Aforementioned difference purposes also allows to reduce the sealing element being contained in vehicle motor (preferably motor vehicles)
Deterioration.
[Specific implementation mode]
The present invention is described below by way of non-limiting example.
Example 1:The present invention lubricant compositions, compare lubricant compositions preparation and these compositions with it is motor-driven
The compatibility evaluation of the sealing element used in vehicle motor.
Lubricant compositions (referring to 1) are prepared according to the following table 1 (provide and form with weight (g)).
Base oil 1:Group III base oil (the mm of the kinematic viscosity at 40 DEG C measured according to standard ASTM D445=202/
s);
Base oil 2:Group III base oil (the mm of the kinematic viscosity at 40 DEG C measured according to standard ASTM D445=252/
s);
Viscosity index improver:Hydrogenated styrene/isoprene copolymer;
Additive packet:Phosphordithiic acid zinc-type antiwear agents, diphenyl amine type antioxidant, calcium salicylate Orvus Gardinol
(by Infineum sale);
Pour-point depressant:Polymethacrylates (the Lubrizol sold by Lubrizol);
Amine 1:Aliphatic diamine (the Duomeen sold by Akzo Nobel of neutralization);
Amine 2:Unneutralized aliphatic diamine (the Duomeen sold by Akzo Nobel);
Friction improver:Molybdenum dithiocarbamate (the Sakuralube sold by Adeka)。
Table 1
The lubricant compositions and comparative composition of the present invention are prepared according to the following table 2 (provide and form with weight (g)).
Table 2
The simultaneous of prepared lubricant compositions and RE1 type elastomeric seals is evaluated according to standard CEC-L-39-T96
Capacitive, and obtained result is provided in table 3.
Table 3
The results show that with the lubricant compositions (comparison combination that includes unneutralized amine and the combination of organic molybdenum
Object 1) it compares, including the lubricant compositions of the present invention (composition 1) of the combination of the amine and organic molybdenum that neutralize have more
The good compatibility with sealing element used in engine (especially fluorinated elastomer sealing element).
Example 2:The lubricant compositions of the present invention, the preparation for comparing lubricant compositions and their reductions are about DLC/
The evaluation of the performance of the friction of steel contact
Lubricant compositions (referring to 2) are prepared according to the following table 4 (provide and form with weight (g)).
Base oil:Group III base oil is (according to kinematic viscosity=19mm at 40 DEG C of standard ASTM D445 measurements2/
s);
Viscosity index improver:Hydrogenated styrene/isoprene copolymer;
Additive packet:Dispersant, calcium phenoxide Orvus Gardinol, calcium carboxylates Orvus Gardinol and sulfoacid calcium Orvus Gardinol;
Pour-point depressant:Polymethacrylates (the Viscoplex1- sold by Evonik);
Amine 1:Aliphatic diamine (the Duomeen sold by Akzo Nobel of neutralization);
Amine 2:Unneutralized aliphatic diamine (the Duomeen sold by Akzo Nobel);
Amine 3:Fatty triamine (the Armolube sold by Akzo Nobel of neutralization);
Amine 4:The unneutralized fat triamine (Triameen sold by Akzo Nobel);
Friction improver:Molybdenum dithiocarbamate (the Sakuralube sold by Adeka)。
Table 4
The lubricant compositions and comparative composition of the present invention are prepared according to the following table 5 (provide and form with weight (g)).
Table 5
The frictional behaviour of lubricant compositions is evaluated using the first experiment.
Using linear friction meter, DLC pearls/steel plane evaluate friction coefficient under the following conditions:
The type of steel:100c6;
The type of DLC coatings on pearl:a:CH hydrogenates DLC, contains the hydrogen between 31 and 33%, and have 55:
45 molar ratio (sp2Carbon/sp3Carbon);
The thickness of DLC layer:1.5μ;
Temperature:110℃;
The normal duty of -5N;
- 10mm stroke distances.
Second of experiment is also performed to evaluate the frictional behaviour of lubricant compositions, which allows to follow representing NEDC
The operating point upper table sign engine friction of the point scanned during ring (new Europe driving pattern).
Test engine is the H4BT engines of RENAULT, corresponds to 3- cylinder multiple spot indirect injection gasoline engines,
Meet 5 standards of EURO.
The non-dots combustion Thermal Motor is driven by generator with required speed.Fluid (coolant and lubricant) is temperature control
, because not burnt using such experiment.The driving heating power hair that generator is provided is measured at each operating point
The torque of motivation.Mark is allowed to show best frictional behaviour using the comparison between the driving torque of the engine of different lubricants
Those of lubricant.
Test operation point is as follows:
Engine speed (rpm):4000-3500-3000-2500-2000-1500-1000-750
The lubricant temperature adjusted at manifold:40℃–60℃–90℃–110℃
The water temperature adjusted at engine export:40℃–60℃–90℃–100℃
When the experiment is completed, the value obtained is lower, and the reduction frictional behaviour for the lubricant tested is better.
The characteristic of the prepared lubricant compositions of evaluation, and it is given in Table 6 result.
Table 6
The results show that the lubricant compositions of the present invention (composition 2 of the combination of amine and organic molybdenum comprising neutralization
Reduce frictional behaviour (especially DLC/ steel contact on) with 3) showing, at least with include unneutralized amine and organic-molybdenum chemical combination
The lubricant compositions (comparative composition 3 and 4) of the combination of object are quite and even more preferable than the latter.
Claims (16)
1. lubricant compositions are to reduce the purposes of the friction between two surfaces, at least one of two surfaces surface
Carbon coated, the composition includes:
At least one base oil;
At least one molybdenum compound;
At least one amine salt neutralized completely or partially, amine meet lower formula (I):
R-N(X)-Y (I)
Wherein:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, has 2 to 24 carbon atoms, preferably 4 to 24
Carbon atom, more preferable 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
X is hydrogen atom;Linear chain or branched chain, fully saturated or fractional saturation alkyl, have 1 to 24 carbon atom, preferably 1
To 10 carbon atoms, especially 1 to 8 carbon atom;Benzyl or formula-R1-[NH-R2]n-NH2Group;
Y is hydrogen atom;Linear chain or branched chain, fully saturated or fractional saturation alkyl, have 1 to 24 carbon atom, preferably 1
To 10 carbon atoms, especially 1 to 8 carbon atom;Benzyl;Or formula-R1-[NH-R2]n-NH2Group;
N is 0 to 3 integer, preferably 0 to 2, preferably 0 or 1;
R1And R2It is identical or different, it is the alkyl of linear chain or branched chain, has 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms excellent
It is selected as CH2CH2Or CH2CH2CH2;
At least one X or Y are hydrogen atom or-R1-[NH-R2]n-NH2;
X, at least one Y or R be linear chain or branched chain, fully saturated or fractional saturation alkyl, have 4 to 24 carbon originals
Son, preferably 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms;
The acid of neutralizing amine is selected from the monoacid of formula (II):
R'COOH (II)
Wherein R ' is the linear chain or branched chain with 2 to 24 carbon atoms, fully saturated or fractional saturation alkyl.
2. purposes according to claim 1, wherein amine meet following formula (Ia):
R-N(X)-R1-[NHR2]n-NH2 (Ia)
Wherein R, X, R1,R2There is the definition provided in claim 1 with n,
At least one X or R be linear chain or branched chain, fully saturated or fractional saturation alkyl, has 4 to 24 carbon atoms,
It is preferred that 14 to 24 carbon atoms, especially 16 to 24 carbon atoms, such as 18 to 24 carbon atoms.
3. purposes according to claim 1 or 2, wherein:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, have 14 to 24 carbon atoms, especially 16 to
24 carbon atoms, such as 18 to 24 carbon atoms;
X is hydrogen atom;The alkyl of linear chain or branched chain with 2 to 8 carbon atoms;Benzyl or formula-R1-[NH-R2]n-NH2Base
Group.
4. purposes according to any one of claim 1 to 3, wherein:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, have 14 to 24 carbon atoms, especially 16 to
24 carbon atoms, such as 18 to 24 carbon atoms;
X is hydrogen atom or formula-R1-[NH-R2]n-NH2Group.
5. purposes according to any one of claim 1 to 4, wherein:
R is linear chain or branched chain, fully saturated or fractional saturation alkyl, have 14 to 24 carbon atoms, especially 16 to
24 carbon atoms, such as 18 to 24 carbon atoms;
Y is-R1-[NH-R2]n-NH2;
N=0;
R1It is CH2CH2CH2;And
X is CH2CH2CH2NH2Or H.
6. purposes according to any one of claim 1 to 5, wherein in the composition, mole of the nitrogen-atoms in amine
Molar ratio between number and the molal quantity of the acid of formula (II) is between 9:1 and 1:Between 1, it is preferably between 5:1 and 1:Between 1.
7. purposes according to any one of claim 1 to 6, wherein R ' are linear chain or branched chains, fully saturated or part
The alkyl of saturation has 7 to 24 carbon atoms, preferably 10 to 24 carbon atoms, such as 14 to 20 carbon atoms, especially 16
To 20 carbon atoms.
8. purposes according to any one of claim 1 to 7, wherein the organic molybdenum is aminodithioformic acid
Molybdenum compound.
9. purposes according to any one of claim 1 to 8, wherein amine are selected from following amine:
RNHCH2CH2CH2CNH2, wherein R is the linear chain or branched chain with 16 to 18 carbon atoms, fully saturated or fractional saturation
Alkyl;Or
N(R)(CH2CH2CH2NH2)(CH2CH2CH2NH2), wherein R is the linear chain or branched chain with 16 to 18 carbon atoms, complete
The alkyl of full saturation or fractional saturation.
10. purposes according to any one of claim 1 to 9, wherein the total weight relative to the composition, described
Composition includes from 0.05% to 5% weight, the preferably amine of the neutralization of 0.1% to 2% weight.
11. purposes according to any one of claim 1 to 10, wherein the total weight relative to the composition, institute
It includes the organic-molybdenum from 0.01% to 3% weight, preferably 0.05% to 3% weight, such as 0.1% to 2% weight to state composition
Compound.
12. purposes according to any one of claim 1 to 11, wherein the composition further includes at least one resist
Additive is worn, the compound of the compound of phosphatization, the compound of vulcanization or phosphorus-vulcanization is preferably selected from, is preferably selected from two sulphur
For trbasic zinc phosphate.
13. purposes according to any one of claim 1 to 12, to reduce vehicle motor, preferably in motor vehicles
Friction.
14. purposes according to any one of claim 1 to 13, to reduce vehicle motor, preferably in motor vehicles
Friction between steel surface and the surface of carbon coating.
15. purposes according to any one of claim 1 to 13, to reduce vehicle motor, preferably in motor vehicles
Friction between the surface of two carbon coating.
16. the purposes according to any one of claim 1 to 15, preferably motor-driven additionally to reduce vehicle motor
The deterioration of sealing element accommodated in vehicle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1651804A FR3048433B1 (en) | 2016-03-03 | 2016-03-03 | LUBRICATING COMPOSITION BASED ON NEUTRALIZED AMINES AND MOLYBDENE |
| FR1651804 | 2016-03-03 | ||
| PCT/EP2017/055006 WO2017149119A1 (en) | 2016-03-03 | 2017-03-03 | Lubricant composition based on neutralized amines and molybdenum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108699474A true CN108699474A (en) | 2018-10-23 |
| CN108699474B CN108699474B (en) | 2021-05-11 |
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| CN201780012826.1A Active CN108699474B (en) | 2016-03-03 | 2017-03-03 | Lubricant composition based on neutralized amine and molybdenum |
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| Country | Link |
|---|---|
| EP (1) | EP3423551A1 (en) |
| JP (1) | JP6889175B2 (en) |
| KR (1) | KR102329180B1 (en) |
| CN (1) | CN108699474B (en) |
| BR (1) | BR112018016701A2 (en) |
| FR (1) | FR3048433B1 (en) |
| WO (1) | WO2017149119A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521817A (en) * | 2022-10-18 | 2022-12-27 | 中国石油化工股份有限公司 | Lubricating oil antiwear additive, preparation method and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017123614A1 (en) * | 2017-10-11 | 2019-04-11 | Volkswagen Aktiengesellschaft | Lubricant composition, use for lubrication of a gearbox as well as gearbox |
| SG11202008101XA (en) * | 2018-03-02 | 2020-09-29 | Chevron Oronite Tech Bv | Lubricating oil composition providing wear protection at low viscosity |
| WO2020007945A1 (en) * | 2018-07-05 | 2020-01-09 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| KR102113797B1 (en) * | 2018-12-10 | 2020-05-25 | 박용우 | Combination Composition for Cleaning and Lubricating |
| EP3907268A1 (en) * | 2020-05-04 | 2021-11-10 | Total Marketing Services | Lubricating composition for reducing wear and tear on dlc parts used in internal combustion engines |
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- 2017-03-03 KR KR1020187024969A patent/KR102329180B1/en active IP Right Grant
- 2017-03-03 EP EP17708269.0A patent/EP3423551A1/en not_active Withdrawn
- 2017-03-03 CN CN201780012826.1A patent/CN108699474B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115521817A (en) * | 2022-10-18 | 2022-12-27 | 中国石油化工股份有限公司 | Lubricating oil antiwear additive, preparation method and application thereof |
| CN115521817B (en) * | 2022-10-18 | 2023-06-02 | 中国石油化工股份有限公司 | Lubricating oil antiwear additive and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3423551A1 (en) | 2019-01-09 |
| JP2019507230A (en) | 2019-03-14 |
| FR3048433B1 (en) | 2020-03-13 |
| KR102329180B1 (en) | 2021-11-19 |
| BR112018016701A2 (en) | 2018-12-26 |
| WO2017149119A1 (en) | 2017-09-08 |
| FR3048433A1 (en) | 2017-09-08 |
| CN108699474B (en) | 2021-05-11 |
| JP6889175B2 (en) | 2021-06-18 |
| KR20180122337A (en) | 2018-11-12 |
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