CN101511986A - Grease composition including at least two different molybdenum compounds for constant velocity joints - Google Patents

Grease composition including at least two different molybdenum compounds for constant velocity joints Download PDF

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Publication number
CN101511986A
CN101511986A CNA2006800560134A CN200680056013A CN101511986A CN 101511986 A CN101511986 A CN 101511986A CN A2006800560134 A CNA2006800560134 A CN A2006800560134A CN 200680056013 A CN200680056013 A CN 200680056013A CN 101511986 A CN101511986 A CN 101511986A
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grease composition
molybdenum
compound
composition
grease
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Inventor
E·吉生
F·雷赫尔
L·芒塔达
S·罗森克兰茨
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GKN Driveline International GmbH
GKN Driveline North America Inc
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GKN Driveline International GmbH
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/12—Metal carbonyls
    • 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
    • C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
    • C10M113/08—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/106—Carboxylix acids; Neutral salts thereof used as thickening agents
    • 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
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C10M2219/0445—Sulfonic acids, Derivatives thereof, e.g. neutral salts used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Abstract

In order to provide for a grease composition reducing or preventing noise, vibration and harshness (NVH) in the driveline, a grease composition for use in constant velocity joints is suggested, comprising a) a base oil composition; b) at least one tri-nuclear molybdenum compound of the formula Mo3SkLnQ2, wherein L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dis- persible in the oil, n is from 1 to 4, k varies from 4 though 7, Q is selected from the group of neutral electron donating compounds such as amines, al- cohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non- stoichiometric values. c) at least one further molybdenum containing compound; and d) at least one simple and/or complex soap thickener.

Description

The grease composition that is used for constant velocity cardan joint that comprises at least two kinds of different molybdenum compounds
The present invention relates to lubricating grease, it is mainly used in the constant velocity cardan joint (universal joint) that uses, especially ball joint or tripod joint on the transmission line of Motor vehicles.
Motion at constant velocity cardan joint (CVJ) inner assembly becomes complicated because of the combination of rolling, sliding and spinning.When this joint bore moment of torsion, these assemblies were loaded together, and this not only causes the wearing and tearing on the surface in contact of assembly, and caused rolling contact fatigue and the outstanding frictional force between these surfaces.These wearing and tearing can cause the destruction of joint and this frictional force to cause noise, vibration and roughness (NVH) in transmission line.The NVH axial force that produces among (plunging) type CVJ of pitching by being determined at is usually come " measurement ".Ideally, the grease that is used for constant velocity cardan joint not only needs to reduce wear, and has low frictional coefficient with power of reducing friction and minimizing or prevent NVH.
Constant velocity cardan joint also has the seal bootr of elastomer material, and it has bellows form usually, and an end is connected in the outside of CVJ and the interconnected or output shaft that the other end is connected in CVJ.This cover is retained in grease in the joint and prevents dirt and water is entered.
Not only this grease must reduce wear and rub and prevent rolling contact fatigue initial too early in CVJ, also and compatible with the elastomer material that constitutes this cover.Also have the degraded of cover material in addition, this degraded can cause the early failure of this cover, the destruction that makes grease escape and finally cause CVJ.The material that is used for two kinds of main types of CVJ cover is chloroprene rubber (CR) and thermoplastic elastomer (TPE), especially ether-ester segmented copolymer thermoplastic elastomer (TPC-ET).
Typical C VJ grease has base oil, and the latter is the blend that naphthenic (saturated rings) and paraffinic hydrocarbons belong to (saturated chain of straight chain and branching) mineral oil.Synthetic oil also can add.Well-knownly be that this base oil all has a big influence (swelling or contraction) for the change of the cover of being made by CR and TPC-ET is bad.Mineral oil commonly used and synthetic base oil be extracting elasticizer and other oil-soluble protective material from cover material.Paraffinic mineral oils and poly-alpha olefins (PAO) synthetic base oil seldom is diffused into especially in the cover of being made by elastomeric material and causes contraction, but naphthenic mineral oil and synthetic ester is diffused in the cover material and as softening agent and can cause swelling on the other hand.Softening agent or plasticizer composition exchange this naphthenic mineral oil can reduce characteristic significantly, especially at low temperatures, and can cause that this cover is destroyed by cold cracking, finally causes the destruction of CVJ.If significant swelling or softening takes place, then Zhao top-speed capability can reduce, and this is owing to poor stability under speed and/or over-drastic radial swelling.
In order to solve this problems referred to above, US 6,656,890 B1 have proposed special base oil binding substances, it comprises one or more poly-alpha olefinss of 10-35wt%, the synthetic organic ester of one or more of 3-15wt%, one or more naphthenic oil of 20-30wt%, the remainder of this binding substances is one or more paraffin oils and in addition, lithium soap-thickened agent and do not have the friction modifiers of sulphur, this properties-correcting agent can be the organic-molybdenum mixture, molybdenum dithiophosphate and zinc dialkyl dithiophosphate, and other additive such as corrosion inhibitor, antioxidant, extreme pressure additive and tackiness agent (tackinessagents).Yet according to US 6,656, frictional coefficient and abrasion resistance properties that the grease composition of 890 B1 is measured in SRV (Schwingungen, Reibung, the abbreviation of the German speech of Verschlei β) test need be improved.
Therefore, the purpose of this invention is to provide grease composition, it is mainly used in constant velocity cardan joint, has good consistency between said composition and the cover made by thermoplastic elastic body, and low wearing and tearing and low friction are arranged when using in CVJ.
This purpose of the present invention can realize that said composition comprises by the grease composition that is used for constant velocity cardan joint
A) base oil composition;
B) have at least a three of following formula and examine molybdenum compounds, preferred content is the 0.25wt%-5wt% of grease composition total amount, more preferably 0.3wt%-3wt%:
Mo 3S kL nQ z， (I)
Wherein L is the independent ligand of selecting with organic group, this organic group has the carbon atom of sufficient amount and can be scattered in the oil so that this compound dissolves in maybe, n is 1-4, k is 4-7, Q is selected from the neutral sub-compound of power supply such as amine, alcohol, phosphine and ether, and z is 0-5 and comprises non-stoichiometric value
C) at least a other the compound that contains molybdenum and
D) at least a simple and/or complex soap thickener.
In whole ligands of this three nuclear molybdenum compound, the quantity of carbon atom of existence in the middle of the organic group is at least 21 carbon atoms, preferably at least 25, and more preferably at least 30 and most preferably at least 35.Can be used for three among the present invention nuclear molybdenum compound and be disclosed in US 6,172, among 013 B1, its disclosure is introduced among the present invention as a reference.The present inventor finds, examines molybdenum compounds according at least a three of claim 1 and will significantly reduce frictional coefficient and wearing and tearing with other existence that contains the compound of molybdenum, when being used for CVJ.
As base oil composition according to the present invention, be disclosed in US 6,656, the base oil composition among 890 B1 is preferred the use, the disclosure of this patent is hereby incorporated by reference.Yet, the base oil composition of any other type, the blend of mineral oil especially, the blend of synthetic oil, or the blend of the mixture of mineral oil and synthetic oil can use.This base oil composition should preferably have under 40 ℃ about 32 and about 250mm 2Kinematic viscosity between the/s and under 100 ℃, having about 5 and about 25mm 2Kinematic viscosity between the/s.Preferably, this mineral oil is selected from least a naphthenic oil and/or at least a paraffin oils.The synthetic oil that can be used among the present invention is selected from least a poly-alpha olefins (PAO) and/or at least a synthetic organic ester.The organic synthesis ester preferably has the dicarboxylic acid derivatives based on the subbase group of fatty alcohol.Preferably, this fatty alcohol has the uncle's genus straight or branched carbochain that contains 2-20 carbon atom.Preferably, this organic synthesis ester is selected from sebacic acid-two (2-(ethyl hexyl) esters) (" dioctyl sebacate " (DOS)), hexanodioic acid-two-(2-(ethyl hexyl) ester) (" Octyl adipate " (DOA)), and/or nonane diacid-two (2-(ethyl hexyl) esters) (" dioctyl azelate " (DOZ)).
If poly-alpha olefins is present in this base oil composition, preferably this poly-alpha olefins is chosen in the viscosity that has about 40 centistokes of about 2-under 100 ℃.For the selected naphthenic oil of base oil composition preferably has at about 20-about 180mm under 40 ℃ 2Viscosity between the/s, and if paraffinic hydrocarbons belongs to oil and is present in this base oil composition, preferably this paraffinic hydrocarbons belongs to oil have about 400mm at about 25-under 40 ℃ 2Viscosity between the/s.
In a preferred embodiment of the invention, other compound that contains molybdenum is selected from molybdenum dithiocarbamate and/or molybdenum dithiophosphate.At least a molybdenum dithiophosphate (MoDTP) and/or molybdenum dithiocarbamate (MoDTC) preferably are present in according in the grease composition of the present invention with the amount between the about 3wt% of about 0.3wt%-, under each situation with respect to the total amount of grease composition.Yet same any compound that other contains molybdenum is as amount of component b) be present in according in the grease composition of the present invention, wherein organic molybdenum is preferred.Can contain one or more MoDTC and/or MoDTP and their mixture especially according to grease composition of the present invention.MoDTP according to the present invention has following general formula:
Figure A200680056013D00061
Wherein X or Y represent S or O and R 1-R 4In each can be identical or different and separately expression have primary (straight chain) or secondary (side chain) alkyl between 6 and 30 carbon atoms.
MoDTC according to the present invention has following general formula:
[(R 5)(R 6)N-CS-S] 2-Mo 2O mS n (III)
R wherein 5And R 6Expression independently of one another has 1-24, the alkyl of preferred 3-18 carbon atom; M is that 0-3 and n are 4-1, and precondition is m+n=4.
Two kinds of interpolations that contain the compound of molybdenum significantly reduce frictional coefficient and CVJ wearing and tearing in use, and a kind of in two kinds is three-molecule molybdenum compound (TNMoS) of sulfur-bearing, and other compound that contains molybdenum at least a among MoDTP and/or the MoDTC preferably.Especially, this frictional coefficient has reduced at least about 25%, and only contains the grease composition of at least a TNMoS and compares.
Preferably, at least a simple and/or complex soap thickener according to desired grease composition is selected from lithium soap and/or calcium soap.
On meaning of the present invention, lithium soap or calcium soap are the reaction product of at least a lipid acid and lithium hydroxide or calcium hydroxide.Preferably, this thickening material can be from stearic acid, 12-oxystearic acid, hydrogenated castor oil or the simple lithium or the calcium soap that form from other similar lipid acid or their mixture or this type of sour methyl ester.Additionally, can use lithium and/or the calcium compound soap that forms from the mixture of for example longer chain fatty acid and coordination agent (for example borate of one or more dicarboxylic acid).The use of complex lithium and/or calcium soap allows grease composition according to the present invention to operate under up to about 180 ℃ temperature, and for simple lithium and/or calcium soap, this grease composition will only be operated under about 120 ℃ at the most temperature.Yet whole above-mentioned mixtures of thickening agents also can be used.
In other embodiments of the present invention, this grease composition further comprises at least a zinc compound additive, more preferably, and total with respect to this grease composition, content between the about 3wt% of about 0.1wt%-, the preferred zinc compound additive between the about 2wt% of about 0.3wt%-.Most preferred, this zinc compound additive is selected from least a zinc dithiophosphate (ZnDTP).Preferably, zinc dithiophosphate is selected from the zinc dialkyl dithiophosphate with following formula:
(R 7O)(R 8O)SP-S-Zn-S-PS(OR 9)(OR 10) (IV)
R wherein 7-R 10In each can be identical or different and separately expression have 1-24, preferred 3-20, the most preferably uncle of 3-5 carbon atom or secondary alkyl.Especially, if substituent R 7, R 8, R 9And R 10Expression respectively has the binding substances of primary and secondary alkyl of 3-8 carbon atom, then can expect the effect of excellence.
By at least a zinc compound additive being added to according in the grease composition of the present invention, the wearing and tearing in CVJ further significantly reduce.
According to another embodiment of the present invention, this grease composition further comprises the additive packing batching, and the latter is selected from antioxidant, corrosion inhibitor, anti-wear agent, friction modifiers, and/or anti-extreme pressure agent (extreme-pressure additive, i.e. EP additive).
This extreme-pressure additive preferably has about 25mm under 40 ℃ 2The no metal of the viscosity of/s, sulfurized fatty acid methyl ester agent preferably exist with the amount with respect to the about 3wt% of about 0.1-of the total amount of this grease composition.About 10% (by weight) of the preferably about 8-of the total sulfur of extreme-pressure additive and active sulfur content are about 1% (by weight).This extreme-pressure additive for the card of CVJ sting prevent for demonstrate excellent effect.If this sulphur content surpasses the upper limit of above definition, then rolling contact fatigue of its promotion contacting metal assembly and wearing and tearing is initial.
As antioxidant, grease composition of the present invention can comprise amine, preferred aromatic amine, more preferably phenyl-a-naphthylamine or pentanoic or their derivative.Antioxidant is used for preventing that the grease composition change relevant with oxidation is bad.Can contain with respect to the antioxidant of about 0.1-about 2% (by weight) of grease composition total amount suppressing the oxidative degradation of base oil according to grease composition of the present invention, and the life-span that prolongs grease composition, therefore prolong the life-span of CVJ.
Typically, the final operation before the assembling of CVJ be washing removing the machining chip, and therefore need this grease to absorb the characteristic that the surplus water of any trace and anti-sealing cause corrosion and influence CVJ unfriendly, therefore need to add corrosion inhibitor.As corrosion inhibitor, can comprise the metal-salt that is selected from oxidized petroleum waves according to grease composition of the present invention, the metal-salt of mahogany acid (especially obtained) by the aromatic hydrocarbon component sulphonation that will in the fraction of lubricating oil, exist, and/or the metal-salt of alkyl aromatic sulfonic acid is (as dinonylnaphthalene sulfonic acid salt, alkyl benzene sulphonate (ABS), or peralkaline alkyl benzene sulphonate (ABS)) at least a metal-salt.The example of metal-salt comprises sodium salt, sylvite, and calcium salt, magnesium salts, zinc salt and quaternary ammonium salt, this calcium salt is most preferred.The calcium salt of oxidized petroleum waves is also guaranteed excellent effect.
Antiwear agents according to the present invention avoids physical absorption by interpolation film-forming properties compound protection surface or chemical reaction prevents metal and metallic contact.The ZnDTP compound also can be used as antiwear agents.As corrosion inhibitor according to the present invention, preferably use the sulfonic acid calcium salt, preferred content is about 3% (by weight) of about 0.5-with respect to the grease composition total amount.
Traditional friction modifiers such as fatty acid amide and amine phosphates be used for for many years grease and other lubricant (referring to, for example, Klamann, Dieter-" Lubricants ", Verlag Chemie GmbH 1983, chapter 9.6 are as a reference).Their effect is that lubricant is stablized but not necessarily reduction friction in very big operational condition scope.
In another preferred embodiment of the present invention, grease composition comprises, under each situation with respect to the total amount of grease composition, the base oil composition of the about 98wt% of about 55wt%-, at least a three nuclear molybdenum compounds of the about 5wt% of about 0.1wt%-, at least a other molybdenum compound of the about 2wt% of about 0.3wt%-and at least a soap thickening material of the about 25wt% of about 1wt%-.
In other preferred embodiment of the present invention, the three nuclear molybdenum compounds that in composition, exist, molybdenum dithiophosphate, molybdenum dithiocarbamate, and/or the amount of zinc dithiophosphate is the about 2wt% of about 0.3wt%-with respect to the grease composition total amount.Most preferably, the three nuclear weight percentage of being added of molybdenum compounds for the grease composition total amount are substantially equal to the weight percentage of the molybdenum dithiophosphate, molybdenum dithiocarbamate or the zinc dithiophosphate that are added, preferably under each situation with respect to grease composition total amount 0.4wt%, about 0.5wt%, about 0.6wt% and/or about 0.7wt%.
In addition, grease composition according to the present invention has by what SRV test recorded and is no more than 0.08 the coefficient of sliding friction, and typically is lower than 0.07.
Implement optimal mode of the present invention
In order to measure by according to the frictional coefficient that grease composition of the present invention brought and the reduction effect of wearing and tearing, use Optimol Instruments SRV tester to carry out the SRV test.Preparation is from Optimol Instruments Pruftechnik GmbH, Westendstrasse 125, and the flat disk lower sample that the 100Cr6 standard bearing steel that Munich (use solvent suitably clean) obtains is made also contacts with the grease composition that will investigate.This SRV test is industrial standards test and especially relevant for the test of CVJ with grease.This test is upper strata ball sample to-and-fro movement on aforesaid flat disk lower sample under load of the diameter 10mm that makes from the 100Cr6 bearing steel.In the test of imitation tripod joint, the applied load of 200N applies 60 minutes (comprising trial trip) with the frequency of 40Hz under 80 ℃.Stroke is respectively 1.5mm and 3.0mm.The frictional coefficient that is obtained is recorded on computers.For each grease, the value of being reported is the mean value (two rounds of 1.5mm stroke and two rounds of 3.0mm stroke) of four data of ending of testing in four rounds.Use profilometer and digital planimeter to measure wearing and tearing.By using this profilometer, can obtain the pattern of cross section in the centre of wearing surface.The area of this cross section (S) is measured by using digital planimeter.Abrasion loss is estimated by V=SI, and wherein V is that the volume and the I of wearing and tearing are strokes.From Wr=V/L[μ m 3/ m] obtain wear rate (Wr), wherein L is total sliding distance in test.For this trial trip, it is to begin with the applied load of 50N under above defined terms and carried out 1 minute.Then, this applied load was through 30 seconds increase 50N to 200N.
In addition, measure according to following method by the axial force that the tripod joint of pitching produces at each splice angle:
Axial cyclic force produces test
This test is used under high moment of torsion and lower velocity the axial-periodic force measurement that produced by the drive shaft assembly or the constant velocity cardan joint that pitches, is similar to startup (take off) the vibration condition in vehicle.Drive shaft assembly with the joint that pitches is assembled in and can applies on rotation, moment of torsion and the hinged test-bed constant velocity cardan joint.This test-bed is equipped with the joint cooling system.Load cell is installed on the test-bed and is used to measure along the axial power of the rotation of this joint.
Before test, the trial trip program is used as follows:
-grease distributes: guarantee the moment of torsion of+100Nm and+speed of 200rpm under consistent lubricating condition, under the angle between the 0-20 degree, scan 5 minutes with sinusoidal manner per minute 4 cycle lifies.
The axial force value of-complete stabilityization under the following conditions:
-heat up: for the moment of torsion of+300Nm and+joint that has complete trial trip under the speed of 200rpm already guarantees stable temperature and lubricating condition, under the angle between the 0-20 degree with sinusoidal manner per minute 4 cycle lifies scanning 15 minutes
-lubricating grease trial trip: for the joint that has complete trial trip under the condition is below already tried lubricating grease out:
Figure A200680056013D00111
Other condition:
Joint angle: 2.5,5,7.5,10,12.5,15,17.5 and 20 degree
The moment of torsion that applies+/-the 600Nm moment of torsion ,+/-200rpm speed
The bearing load ability of CVJ grease is the key property of definition anti-adhesive wear of this grease and scuffing.For grease, it is defined as by according to Energy Institute, London, measured fusion (welding) load (newton) of 4 ball EP test of the IP-239 standard that UK publishes.
Following material is used for the grease composition investigated:
Base oil composition
Employed base oil composition has under 40 ℃ about 32 and about 250mm 2Kinematic viscosity between the/s and Under 40 ℃Have about 5 and about 25mm 2Kinematic viscosity between the/s.Two kinds of base oil blends are used for the present invention.Base oil blends A is one or more naphthenic oil of the about 60wt% of about 10-, and the mixture of one or more poly-alpha olefinss (PAO) of one or more paraffin oils of the about 80wt% of about 30-and the about 40wt% of about 5-is with respect to the total amount of this oil mixt.Oil blend A does not contain the organic synthesis ester, and contains the DOS of the about 10wt% of 2-that has an appointment with respect to total gauging blend B of oil mixt.
This naphthenic oil is selected at has the about 180mm of about 20-under 40 ℃ 2The viscosity of/s, paraffin oils are selected at has the about 400mm of about 25-under 40 ℃ 2The viscosity of/s and PAO are selected at has the about 40mm of about 6-under 100 ℃ 2The viscosity of/s.
Three molecule molybdenum compounds (TNMoS)
Be used for three molecule molybdenum compounds according to grease composition of the present invention and be with trade name C9455B from lnfineum International Ltd. three of the sulfur-bearing that UK obtains-nuclear molybdenum compound.Its organization definition is at US 6,172, among 013 B1.
Other of comparative example contains the compound of molybdenum
By Asahi Denka Co.Ltd., the molybdenum dithiophosphate (MoDTP) that Japan sells has chemical formula phosphorodithioic acid 2-ethylhexyl molybdenum, dilutes with mineral oil with trade name Sakuralube 300 (S-300) in use.In addition, use the solid-state molybdenum dithiocarbamate according to general formula III (MoDTC) with trade name Sakuralube 600 (S-600) sale, by Asahi Denka Co.Limited, Japan produces.
Zinc compound additive
As zinc compound additive, use with trade name Paranox-15 by lnfineumInternational Ltd., the ZnDTP that UK sells, it is the zinc dialkyl dithiophosphate with primary and secondary alkyl, preferably dilutes with mineral oil.
Thickening material
As lithium soap (Li soap), use Brugarolas S.A., what Spain supplied reacts the reaction product that obtains by lipid acid and lithium hydroxide.In addition, use calcium compound soap (calcium compound soap), it is the reaction product of calcium hydroxide and two kinds of carboxylic-acids, wherein a kind of short carbon chain length of the 2-5 of having carbon atom and another kind of long carbon chain lengths with 16-20 carbon atom, and wherein the ratio of short chain and long-chain is between 1:2 and 1:5.
Additive
As antioxidant agent (oxidation inhibitor), use diphenylamine with butyl and/or octyl group, by Ciba Specialty Chemicals, Switzerland supplies with trade name L-57 (Irganox157).As extreme pressure additive (EP additive 1), use sulfurized organic compound (fatty acid methyl ester), it with trade name Anglamol 33 by The Lubrizol Corporation, OH, U.S.A. (EP additive 1) sold, or with trade name DeoAdd MD10 by DOG DeutscheOeIfabrik Gesellschaft fur chemische Erzeugnisse mbH und Co, Hamburg, Germany sells (" EP additive " in an embodiment).Another example of EP additive is the grease that contains the calcium sulphonate thickening material, and by Brugarolas S.A., Spain produces, trade name Ca-S Grease (Ca-S grease).
As corrosion inhibitor, use the calcium salt of dinonylnaphthalene sulfonic acid salt, for example by KingIndustries, Norwalk, CT, U.S.A. distributes, trade name NaSuI 729 (Ca-sulfonate).
At first, according to the advantage of grease composition of the present invention is by with the frictional coefficient and the abradability of this grease composition and do not contain the TNMoS compound and do not contain the grease composition that other contains the compound of molybdenum, or the grease composition that only contains the TNMoS compound is to recently investigating.Produce seven different grease compositions, as listed in following table:
Table 1
Grease composition [wt%] Embodiment A 1 Embodiment A 2 Embodiment A 3 Embodiment A 4 Embodiment A 5 Embodiment A 6 Embodiment A 7
TNMoS 0.5 1.5 1.0 2.0 2.0
ZnDTP 0.5 1.0 0.5 1.0 1.0
MoDTP 0.5 1.0 1.0 0.5 1.0
MoDTC 0.5 0.5
Antioxidant 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Oil blend A 81.75 80.75 81.75 80.75 80.75 81.75 82.75
The calcium compound soap 16 16 16 16 16 16 16
The result of the frictional coefficient of embodiment A 1 to A7 and the SRV observed value of abradability can derive from Fig. 1.Embodiment A 7 neither contains the TNMoS compound and does not also contain the compound that other contains molybdenum, and embodiment A 3 does not contain any other compound that contains molybdenum.Opposite with them, embodiment A 6 contains other compound that contains molybdenum, but does not contain the TNMoS compound.Therefore, according to of the present invention only be embodiment A 1, A2, A4 and A5.From Fig. 1 (a), can clearly derive, when be not grease composition according to the present invention when comparing, in grease composition according to the present invention, significantly reduce frictional coefficient, this frictional coefficient is lower than 0.08.In addition, this grease composition A1, A2, the abradability of A4 and A5 (referring to Fig. 1 (b)) can't be measured, or is lower than and is not according to grease composition of the present invention.
In the test of additional series, preparation is according to 8 kinds of grease compositions of the present invention, and they contain any in the TNMoS compound of different concns or other compound that contains molybdenum (MoDTP and MoDTC).This grease composition is listed in the table 2.
Table 2
Grease composition [wt%] Embodiment B 1 Embodiment B 2 Embodiment B 3 Embodiment B 4 Embodiment B 5 Embodiment B 6 Embodiment B 7 Embodiment B 8
TNMoS 0.5 15 0.1 0.3 1.0 0.5 0.5 0.5
ZnDTP 0.5 0.5 0.5 0.5 1.0 0.5 0.5
MoDTP 0.5 1.0 0.5 0.5 0.5 0.5 1.0 0.5
MoDTC 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.0
Antioxidant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Oil blend B 91.5 90.5 91.9 91.7 91.0 91.0 91.0 91.0
The Li soap 6 6 6 6 6 6 6 6
Embodiment B 1 and B2 are similar to embodiment A 1 and A2.The result that the SRV that is carried out for frictional coefficient and wearing and tearing tests can be as seen from Figure 2.
Be appreciated that from the value of the frictional coefficient of Fig. 2 the frictional coefficient of the grease composition of whole Embodiment B 1 to B8 is about 0.08 or is lower than 0.08.Because the TNMoS compound concentrations is changed to 1.5wt% from 0.3wt% for the grease composition total amount, appear at least a TNMoS compound should be present in according in the grease composition of the present invention with the about 2wt% of about 0.25wt%-.Lowest friction coefficient is to add grease composition to by at least a TNMoS compound with about 0.5wt% to obtain.MoDTP and/or MoDTC do not cause the noticeable change of frictional coefficient to the amount interpolation of about 1wt% with the about 0.5wt% for the grease composition total amount.
In addition, as can be seen from Figure 2, at least a ZnDTP is favourable with the interpolation at least about the amount of 0.5wt% to 1wt% for the grease composition total amount, because the Embodiment B 2 without any the ZnDTP additive demonstrates higher frictional coefficient, when comparing with B3-B8 with Embodiment B 1.For the wear measurement value, Embodiment B 1 and B3 do not demonstrate measurable wearing and tearing, and the interpolation of the MoDTP of about 1wt% and/or MoDTC can cause higher attrition value, and this can be from Embodiment B 2, and B7 and B8 find out.
The different slightly value of the frictional coefficient of embodiment A 1 and A2 and wearing and tearing is owing to the use of different base oil composition and the use of lithium soap-thickened agent replacement used calcium complex soap thickener in embodiment A 1-A7 when with Embodiment B 1 and B2 contrast.As if show, the interpolation of calcium complex soap thickener than the interpolation of lithium soap-thickened agent a little more preferably, for frictional coefficient and wearing and tearing.
In addition, measure axial force according to the grease composition of Embodiment B 1 and B2, and with diagrammatic representation in Fig. 3.
This axial force should be lower than the requirement that the applicant sets.Can derive out from Fig. 3, the value that Embodiment B 1 obtains for axial force be lower than the value of requirement, and the angle about 13 degree, the grease composition of Embodiment B 2 will cause axial force to be higher than this requirement.Therefore, the grease composition B1 that also contains ZnDTP reagent in addition is most preferred.
In the 3rd series of trials, the interpolation of other component is to investigate according to the grease composition of table 3 by preparation for the influence according to grease composition of the present invention.
Table 3
Grease composition [wt%] Embodiment C 1 Embodiment C 2 Embodiment C 3 Embodiment C 4 Embodiment C 5 Embodiment C 6
TNMoS 0.5 0.5 0.5 0.5 0.5 0.5
ZnDTP 0.5 0.5 0.5 0.5 0.5 0.5
MoDTP 0.5 0.5 0.5 0.5 0.5 0.5
MoDTC 0.5 0.5 0.5 0.5 0.5 0.5
EP additive 1 0.5
EP additive 2 0.5
Anticorrosive agent 2.0
The calcium compound soap 5
Ca-S lubricating grease 3
Antioxidant 0.5 0.5 0.5 0.5 0.5 0.5
Oil blend B 91.5 91.0 91.0 89.5 86.5 88.5
The Li soap 6.0 6.0 6.0 6.0 6.0 6.0
All be shown among Fig. 4 for the result of the SRV test that frictional coefficient carried out and the observed value of loading for the fusion (welding) of Embodiment C 1-C6.The grease composition of Embodiment C 1 is equal to Embodiment B 1.
Can derive from Fig. 4, more the interpolation of the extreme-pressure additive of a large amount (EP reagent) is preferred, and this can find out from the fusion load of Embodiment C 2 especially.Yet this frictional coefficient has improved a little by the interpolation of extreme-pressure additive.The other interpolation of calcium double composition grease causes the further reduction of frictional coefficient except that Lithium soap grease, and this can find out in Embodiment C 5.Yet the fusion load improves a little for Embodiment C 1.In addition, the interpolation of calcium sulphonate grease (Ca-S grease) can improve the value of fusion load and reduce the frictional coefficient of grease composition, and this can find out from Embodiment C 6.The interpolation of corrosion inhibitor can the remarkably influenced frictional coefficient, yet the value of fusion load significantly improves, and this can infer out during with Embodiment C 4 contrasts with Embodiment C 1.
Therefore, extreme-pressure additive is with the interpolation of the amount of the about 1.0wt% of about 0.1wt%-, and corrosion inhibitor is with the interpolation of the amount of the about 3wt% of about 0.3wt%-, with the calcium sulphonate grease be preferred with the interpolation of the amount of the about 15wt% of about 0.5wt%-, under each situation with respect to the total amount of this grease composition.
In a word, grease composition according to the present invention has favourable material impact for frictional coefficient and wearing and tearing and for fusion load and axial force, therefore cause wearing and tearing lower in CVJ and lower friction, can reduce or prevent noise, vibration in transmission line and coarse (harshness) (NVH).

Claims (12)

1. be used for the grease composition of constant velocity cardan joint, it comprises
A) base oil composition;
B) three of at least a following general formula nuclear molybdenum compounds
Mo 3S kL nQ z，
Wherein L is the independent ligand of selecting with organic group, this organic group has the carbon atom of sufficient amount and can be scattered in the oil so that this compound dissolves in maybe, n is 1-4, k is 4-7, Q is selected from the neutral sub-compound of power supply such as amine, alcohol, phosphine and ether, and z is 0-5 and comprises non-stoichiometric value
C) at least a other the compound that contains molybdenum; With
D) at least a simple and/or complex soap thickener.
2. according to the grease composition of claim 1, it is characterized in that other compound that contains molybdenum is selected from molybdenum dithiocarbamate and/or molybdenum dithiophosphate.
3. according to any one grease composition in the aforementioned claim, it comprises, as other molybdenum compound, under each situation with respect at least a molybdenum dithiophosphate (MoDTP) and/or the molybdenum dithiocarbamate (MoDTC) of the total amount 0.3wt%-3wt% of this grease composition.
4. according to any one grease composition in the aforementioned claim, it is characterized in that this soap thickening material is selected from lithium soap and/or calcium soap.
5. according to any one grease composition in the aforementioned claim, it further comprises at least a phosphorodithioic acid zinc additive (ZnDTP).
6. according to any one grease composition in the aforementioned claim, it further comprises at least a phosphorodithioic acid zinc additive (ZnDTP) with respect to the total amount 0.3wt%-3wt% of this grease composition.
7. according to any one grease composition in the aforementioned claim, it further comprises the additive packing batching, and this packing is prepared burden and is selected from antioxidant, corrosion inhibitor, anti-wear agent, friction modifiers, and/or extreme-pressure additive (EP agent).
8. according to any one grease composition in the aforementioned claim, it comprises, under each situation with respect to the total amount of grease composition, the base oil composition of 50wt%-98wt%, at least a three nuclear molybdenum compounds of 0.1wt%-5wt%, at least a other molybdenum compound of 0.3wt%-2wt% and at least a soap thickening material of 1wt%-25wt%.
9. according to any one grease composition in the aforementioned claim, it is characterized in that, under each situation with respect to the total amount of this grease composition, three nuclear molybdenum compounds, molybdenum dithiophosphate, molybdenum dithiocarbamate, and/or the amount that zinc dithiophosphate exists in composition is between 0.3wt%-2wt%.
10. according to any one grease composition in the aforementioned claim, it is characterized in that, with respect to the grease composition total amount, three nuclear weight percentage that molybdenum compound added are substantially equal to the weight percentage of the molybdenum dithiophosphate, molybdenum dithiocarbamate or the zinc dithiophosphate that are added.
11. according to any one grease composition in the aforementioned claim, further comprise, under each situation with respect to the total amount of this grease composition, 0.1wt%-10wt%, at least a sulfonic acid Ca lubricating grease of preferred 1wt%-5wt%, and/or 0.1wt%-3wt%, the interpolation of the extreme-pressure additive of at least a sulfur-bearing of preferred 0.2wt%-1wt%.
12. according to any one grease composition in the aforementioned claim, the coefficient of sliding friction that it is characterized in that said composition is at the most 0.08.
CNA2006800560134A 2006-10-07 2006-10-07 Grease composition including at least two different molybdenum compounds for constant velocity joints Pending CN101511986A (en)

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CN110283641A (en) * 2019-05-24 2019-09-27 清华大学天津高端装备研究院 A kind of cold-rolled steel sheet is electrostatically sprayed antirust oil and its preparation and performance test methods
CN114302941A (en) * 2019-09-18 2022-04-08 Gkn动力传动国际有限公司 Grease composition for constant velocity joints comprising zinc sulphide and molybdenum disulphide and/or tungsten disulphide

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CN101981169B (en) * 2008-04-01 2015-01-07 Gkn动力传动系统国际有限责任公司 Grease composition for use in constant velocity joints
CN110283641A (en) * 2019-05-24 2019-09-27 清华大学天津高端装备研究院 A kind of cold-rolled steel sheet is electrostatically sprayed antirust oil and its preparation and performance test methods
CN110283641B (en) * 2019-05-24 2022-03-01 清华大学天津高端装备研究院 Electrostatic spraying anti-rust oil for cold-rolled steel sheets and preparation and performance test methods thereof
CN114302941A (en) * 2019-09-18 2022-04-08 Gkn动力传动国际有限公司 Grease composition for constant velocity joints comprising zinc sulphide and molybdenum disulphide and/or tungsten disulphide

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BRPI0622181A2 (en) 2011-12-27
WO2008040382A1 (en) 2008-04-10

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