CN1260825A - Grease composition for constant velocity joint - Google Patents

Grease composition for constant velocity joint Download PDF

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Publication number
CN1260825A
CN1260825A CN98806285A CN98806285A CN1260825A CN 1260825 A CN1260825 A CN 1260825A CN 98806285 A CN98806285 A CN 98806285A CN 98806285 A CN98806285 A CN 98806285A CN 1260825 A CN1260825 A CN 1260825A
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China
Prior art keywords
urine
grease composition
base oil
metal salt
grease
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CN98806285A
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Chinese (zh)
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CN1097630C (en
Inventor
尾崎幸洋
宗像智郎
吉田强
益森隆一
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
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    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
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    • C10M2201/081—Inorganic acids or salts thereof containing halogen
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    • C10M2201/082—Inorganic acids or salts thereof containing nitrogen
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
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    • C10M2207/02—Hydroxy compounds
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/026—Amines, e.g. polyalkylene polyamines; Quaternary amines used as thickening agents
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    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A grease composition for a constant velocity joint, characterised in that it contains from 0.05 to 30% by weight of sodium thiosulphate with respect to a base oil and urea-based thickener.

Description

The grease composition that is used for constant velocity joint
The present invention relates to be specially adapted to also be called the grease composition of the constant velocity joint of CVJ (constant velocity joint).Grease lubrication to CVJ is very harsh, carries out under the friction condition because it slides in to-and-fro movement and rolls under the high surface pressure that mixes.The present invention relates to be used to have the constant velocity joint of extremely long weather resistance and prevent to produce inordinate wear and exfoliate grease composition.
In the automobile of the vehicle of the vehicle of front-wheel drive and four-wheel drive and rear wheel drive, use CVJ, and its requirement is increasing.Because automobile need obtain fair speed, higher output and than light weight, it is littler that CVJ becomes, under higher speed, use and keep higher torque simultaneously.Therefore, this lubricating grease must satisfy ever-increasing performance technologies requirement.According to its mechanism, CVJ can be divided into permanent universal joint and plunging coupling.For the permanent universal joint condition is very harsh, because they generally are used for wheel, and uses in very big angle with under very high surface pressure.
Usually, CVJ lubricating grease contains lithium soap as thickening material, and contains for example sulphur/phosphorus base extreme pressure additive and molybdenumdisulphide of additive.Recently, it is very common to contain the urine base grease of various extreme pressure additives.They have outstanding resistance toheat.
JP-A (Japanese Patent Application Publication) H 6-57284 (1994) discloses a kind of grease composition that is used for constant velocity joint, wherein urinate lubricating grease and contain (A) dialkyl dithio urea moly-sulfide, (B) contain the extreme pressure additive of specific phosphorodithioic acid zn cpds and (C) epoxide modified aliphatic acid ester or epoxide modified aliphatic acid glyceryl ester as basal component.
In addition, at JP-B (patent documentation of examining) H4-34590 (1992), JP-AH6-57283 (1994), JP-AH6-100878 (1994), JP-AH7-197072 (1995), JP-AH8-41485 (1996), US-A 4840740, among US-A 5160645 and the US-A5449471 by the agency of other urine lubricating grease.These documents are pointed out organic molybdenum and used so far other additive (for example zinc dithiophosphate) are added in the basic lubricating grease together, and with the wearing and tearing of reducing friction, the result has just prevented to scale off.
But these compositions still can not be avoided scaling off, and this situation of scaling off is owing to cause in the to-and-fro movement of the complexity of inside and outside race and ball and the rolling and the caused metallic surface of the sliding friction fatigue of ball cage in CVJ mechanism and ball.
In US-A 4923625, introduced the grease composition that is used to cut with grinding action.Said composition contains the mixture of thiosulfuric acid metal salt and phosphate metal salt, so that extreme pressure and abrasion resistance to be provided to basic lubricating grease.
Produce the manufacturers of CVJ and provide the manufacturers of lubricating grease to attempt to estimate exfoliate situation among the CVJ by means of the friction-wear test of for example testing according to the described four ball EP of ASTMD2596.When investigating the weather resistance of CVJ, just can not use above-mentioned testing apparatus to select suitable lubricating grease.It is believed that this is the reason owing to the complicacy of lubricating condition.Therefore, use the scale off performances such as state of life-span, wearing and tearing of the bench test device evaluation of using actual CVJ therein.
The material that shows outstanding result in general friction-wear test can not prevent effectively that CVJ from scaling off or have the fact of long wearing, just makes it be difficult to develop the CVJ resist technology that scales off.
The purpose of this invention is to provide a kind of new constant velocity joint grease composition, can prevent that thus CVJ from scaling off.
Have been found that using the lubricating grease that contains thiosulfuric acid metal salt to reduce scales off.The present invention relates to a kind of grease composition that is used for constant velocity joint, this grease composition comprises base oil and the basic thickening material of urine, and based on the weight of base oil and the basic thickening material of urine, said composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%.
The invention still further relates to the application of the grease composition of lubricated constant velocity joint, this grease composition comprises base oil and the basic thickening material of urine, and based on the weight of base oil and the basic thickening material of urine, said composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%.
In addition, the invention still further relates to a kind of constant velocity joint that contains grease composition, this grease composition comprises base oil and the basic thickening material of urine, weight based on base oil and the basic thickening material of urine, this grease composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%, and the present invention relates to use thiosulfuric acid metal salt to reduce and contain the scaling off of lubricating grease of base oil and the basic thickening material of urine.
Used in embodiments of the invention base oil can be mineral oil or synthetic oil, for example ester oil, ether oil or hydrocarbon ils, or these oily mixtures.Preferably this base oil is a mineral oil.
Can use any urine base thickening material.The example of urinating basic thickening material comprises two urine, three urine and four urine.Also can use the various thickening materials of urinating compound that contain in addition, for example urine-urethane compounds and urine-imino-compound.
Used in the present invention thiosulfuric acid metal salt can contain any metal that can form thiosulfuric acid metal salt.Typical example is lithium, sodium, potassium, manganese, calcium, barium, strontium, titanium, zirconium, cadmium, zinc, nickel, cobalt, copper, iron, magnesium, lead, tin, silver or their mixture.
The useful thiosulfuric acid metal salt of one class is represented by following general formula:
Figure A9880628500051
Wherein, R represents to contain the alkyl of 1-30 carbon atom, and M is the metal that can form thiosulfuric acid metal salt, and n is the valence mumber of M.The example of such thiosulfuric acid metal salt is ethylenebis dithiocarbamate sodium sulfate, dibenzylsulfide potassium thiosulfate and isopentyl barium thiosulfate barium hyposulflte.Can react by alkyl halide and Sulfothiorine and prepare this compound.
Preferably, used in the present invention thiosulfuric acid metal salt is Sulfothiorine.Most preferably be that this Sulfothiorine is Na 2S 2O 3(anhydrous), Na 2S 2O 3.5H 2O (pentahydrate) or their mixture.In addition, also can use the industrial additive that contains Sulfothiorine, for example Desilube 88, Desilube Technology, Inc.USA.
Based on the weight of base oil and the basic thickening material of urine, the addition of Sulfothiorine is that 0.05-30% is heavy, and it is heavy to be preferably 0.2-20%, and more preferably 0.2-10% is heavy, and also more preferably 0.2-8% is heavy, and it is heavy most preferably to be 0.5-6%.If this amount is less than 0.05% weight, prevent that exfoliate effect is just not enough.If should measure greater than 30% weight, its effect also no longer increases.
Composition of the present invention also can contain one or more known additives, for example based on phenol with based on the fat of the antioxidant of amine, organic molybdenum, molybdenumdisulphide, sulphur modification and oil, the alkene of sulphur modification, dithiophosphates, thiophosphate, phosphite, phosphoric acid salt and polysulfide and other this class extreme pressure additive/anti-wear additive, polybutene, polymethacrylate and other this class viscosity promotor of zinc.
The prescription shown in the table 1 and 2 is processed by additive is added in the basic lubricating grease and in the three-roller type barreling below using, and obtains the lubricating grease of lubricating grease of the present invention and comparing embodiment.Provide the composition of basic lubricating grease below.This base oil is that the viscosity at 100 ℃ of purifying is 15 millimeters 2The mineral oil of/second.I. two urinate lubricating grease
Ditan-4,4 '-vulcabond (295.2g) and octyl amine (304.8g) react in base oil (5400g), and disperse formed urine compound equably, obtain a kind of lubricating grease.The content of this urine compound is 10% weight.II. four urinate lubricating grease
Ditan-4,4 '-vulcabond (334.2g), stearic amine (345.6g) and quadrol (40.2g) react in base oil (5280g), and disperse formed urine compound equably, obtain a kind of lubricating grease.The content of this urine compound is 12% weight.III. Lithium soap grease
Be dissolved in 12-hydroxy lithium stearate (540g) in the base oil (5460g) and dispersion equably, obtain a kind of lubricating grease.The content of this lithium soap is 9% weight.
Use actual CVJ, on stand, resulting lubricating grease is carried out endurance test, and detect exfoliate degree.Test conditions
Rotating speed 1400rpm
Load torque 294Nm
Universal joint operating angle 6 degree
Universal joint type B urfield universal joint
In addition, use the synthetic load (N) of four ball EP test determinations of ASTM D2596 regulation.The results are shown in table 1-4.
It should be noted that in these tables, * 1-7 and * * are as follows.
* 1 Desilube 88 (trade mark, Desilube Technology Inc. makes) is the inorganic additives that contains Sulfothiorine.
* 2 moliban A (trade mark, Vanderbilt Company makes) are molybdenum dithiocarbamates.
* 3 Sakura Lube 600 (trade mark, Asahi Denka makes) are molybdenum dithiocarbamates.
* 4 Sakura Lube 300 (trade mark, Asahi Denka makes) are molybdenum dithiophosphates.
5*Lubrizol 1395 (trade mark, Lubrizol Company makes) is a zinc dithiophosphate.
6*Anguramoru 33 (trade mark, Lubrizol Company makes) is the sulphur modified olefin.
7*Iruga Lube TPPT (trade mark, Ciba-Geigy Company makes) is the triphenyl thiophosphatephosphorothioate.
* is for exfoliate degree, and 12,600,000 changes later condition and 25,200,000 changes later condition to CVJ, and it is as follows to carry out O﹠A.
◇ does not scale off
Zero scales off on a small quantity
△ is medium to scale off
* scale off in a large number
Table 1
Embodiment 1 ?2 ?3 ?4
Form weight % Basic lubricating grease Two urine lubricating grease 97 ?95 ?97
Four urine lubricating grease 95
Additive Na 2S 2O 3(anhydrous) 3 ?5 5
Na 2S 2O 3·5H 2O ?3
Desilube?88*1
Amount to 100 ?100 ?100 ?100
Test-results Four ball EP test Synthetic load (N) 6076 ?7840 ?7840 ?6076
Degree of scaling off ** 12,600,000 changes ◇ ?◇ ?◇ ?○
25,200,000 changes ○ ?◇ ?◇ ?△
Table 2
Embodiment 5 6 ?7 ?8
Form weight % Basic lubricating grease Two urine lubricating grease 97 ?99
Four urine lubricating grease 97 ?97
Additive Na 2S 2O 3(anhydrous)
Na 2S 2O 3·5H 2O ?3
Desilube?88*1 3 ?3 ?1
Amount to 100 100 ?100 ?100
Test-results Four ball EP test Synthetic load (N) 6076 ＞7840 ?7840 ?6076
Degree of scaling off ** 12,600,000 changes ○ ◇ ?◇ ?○
25,200,000 changes △ ◇ ?◇ ?△
Table 3
Embodiment ??1 ??2 ??3 ??4
Form weight % Basic lubricating grease Two urine lubricating grease, four urine lubricating grease lithium soap greases ??97 ??97 ??97 ??93
Additive ??Na 2S 2O 3(anhydrous) Na 2S 2O 3·5H 2O Desilube 88 * 1 Moliban A * 2 Sakura Lube 600 * 3 Sakura Lube 300 * 4 Lubrizol 1395 * 5 Anguramoru 33 * 6 Iruga Lube TPPT * 7 molybdenum bisuphide ??3 ??3 ??3 ??3 ??2 ??1
Amount to ??100 ??100 ??100 ??100
Test-results Four ball EP test Synthetic load (N) ??6076 ??3920 ??6076 ??3087
Degree of scaling off ** 12,600,000 changes ??× ??△ ??△ ??×
25,200,000 changes ??- ??× ??△ ??-
Table 4
Embodiment 5 ?6 ?7 ?8
Form weight % Basic lubricating grease Two urine lubricating grease, four urine lubricating grease lithium soap greases 96???????96 ?????????????????93??????96
Additive Na 2S 2O 3(anhydrous) Na 2S 2O 3·5H 2O Desilube 88*1 Moliban A * 2 Sakura Lube 600*3 Sakura Lube 300*4 Lubrizol 1395 * 5 Anguramoru 33 * 6 Iruga Lube TPPT*7 molybdenum bisuphide ?????????????????5 3????????3 ?????????????????????????3 ?????????1???????????????1 1????????????????1 ?????????????????1
Amount to 100 ?100 ?100 ?100
Test-results Four ball EP test Synthetic load (N) 2450 ?2450 ?3087 ?2450
Degree of scaling off ** 12,600,000 changes △ ?× ?× ?×
25,200,000 changes × ?- ?- ?-
Can clearly find out by the result shown in the table 1-4, the grease composition that is used for constant velocity joint of the present invention, the lubricating grease comparison with routine has outstanding extreme pressure performance, and the more effective protective value that scales off is provided.This effect has just been improved the weather resistance of constant velocity joint.

Claims (8)

1. the grease composition that is used for constant velocity joint, this grease composition comprise base oil and the basic thickening material of urine, and based on the weight of this base oil and the basic thickening material of urine, said composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%.
2. according to the grease composition of claim 1, in this grease composition, this thiosulfuric acid metal salt is Sulfothiorine.
3. the purposes that is used for the grease composition of lubricated constant velocity joint, wherein this grease composition comprises base oil and the basic thickening material of urine, based on the weight of this base oil and the basic thickening material of urine, said composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%.
4. according to the purposes of the grease composition of claim 3, wherein this thiosulfuric acid metal salt is Sulfothiorine.
5. according to the purposes of the grease composition of claim 3 or 4, wherein this grease composition contains the heavy thiosulfuric acid metal salt of 0.2-20%.
6. according to the purposes of each grease composition among the claim 3-5, wherein base oil is a mineral oil.
7. the constant velocity joint that contains grease composition, this grease composition comprise base oil and the basic thickening material of urine, and based on the weight of this base oil and the basic thickening material of urine, said composition also contains the heavy thiosulfuric acid metal salt of 0.05-30%.
8. be used to reduce the purposes of the exfoliate thiosulfuric acid metal salt of the lubricating grease that contains base oil and the basic thickening material of urine.
CN98806285A 1997-07-24 1998-07-23 Grease composition for constant velocity joint Expired - Fee Related CN1097630C (en)

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US8153053B2 (en) 2002-11-21 2012-04-10 Diamet Corporation Method for forming compact from powder and sintered product

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JP4634585B2 (en) * 2000-08-10 2011-02-16 昭和シェル石油株式会社 Grease composition with improved rust and wear resistance
JP4769456B2 (en) * 2004-12-27 2011-09-07 昭和シェル石油株式会社 Urea-based lubricating grease composition, rolling bearing and electric power steering device
JP5225354B2 (en) * 2010-10-18 2013-07-03 昭和シェル石油株式会社 Grease composition with improved rust and wear resistance

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US3505223A (en) * 1967-03-30 1970-04-07 Ethyl Corp Lubricant compositions
US4986923A (en) * 1989-06-27 1991-01-22 Amoco Corporation Front-wheel drive grease with synergistic sulfate and carbonate additive system
US4923625A (en) * 1989-09-28 1990-05-08 Desilube Technology, Inc. Lubricant compositions
US5354485A (en) * 1993-03-26 1994-10-11 The Lubrizol Corporation Lubricating compositions, greases, aqueous fluids containing organic ammonium thiosulfates

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US8153053B2 (en) 2002-11-21 2012-04-10 Diamet Corporation Method for forming compact from powder and sintered product

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