CN101111591A - Lubricating grease composition - Google Patents

Lubricating grease composition Download PDF

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Publication number
CN101111591A
CN101111591A CNA2005800472707A CN200580047270A CN101111591A CN 101111591 A CN101111591 A CN 101111591A CN A2005800472707 A CNA2005800472707 A CN A2005800472707A CN 200580047270 A CN200580047270 A CN 200580047270A CN 101111591 A CN101111591 A CN 101111591A
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CN
China
Prior art keywords
oil
grease composition
purposes
carbamide compounds
base oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2005800472707A
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Chinese (zh)
Inventor
加藤哲也
田中启二
沼泽幸一
大村和重
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN101111591A publication Critical patent/CN101111591A/en
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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
    • C10M169/02—Mixtures of base-materials and thickeners
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular compound
    • C—CHEMISTRY; METALLURGY
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    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/04—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a macromolecular compound
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    • 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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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Rolling Contact Bearings (AREA)

Abstract

Use of a lubricating grease composition comprising: (D) base oil selected from mineral oil, synthetic oil or mixtures thereof; (E) one or more urea compounds; and (F) one or more metal salts of a fatty acid wherein the metal is selected from the group consisting of aluminium, magnesium, zinc, calcium and mixtures thereof, in order to reduce fretting corrosion.

Description

Grease composition
Technical field
The present invention relates to a kind of grease composition with improved rubbing characteristics.
Background technology
Fretting corrosion in the grease lubrication is different from general chemical corrosion wearing and tearing.It is a class mechanical wear phenomenon.For suppressing or preventing this phenomenon, many lubricant researchs have been carried out.
Usually, the local a lot of of fretting corrosion and having nothing in common with each other appears easily.It not only appears at the wheel bearing zone of automobile but also appears at wherein two main bodys, and for example spline, shaft coupling, spring piece and bearing contacts also and relative to each other stand in the different machines zone of microvibration or slip.
The friction situation is meant microvibration or microcosmic slip wherein takes place between two main bodys respect to one another, and the abrasive dust that produces by the microvibration between steel and steel becomes thin brown iron oxide powder in atmosphere, this powder mixes with lubricating grease then makes the lubricating grease overstrike.The wearing and tearing that produced by these relative microvibrations are called as friction or microvibration wearing and tearing, and because it is accompanied by oxidation in atmosphere, therefore can be referred to as fretting corrosion.
Although fretting corrosion itself directly has little disadvantageous effect to bearing property, the known wearing and tearing that when abrasive dust enters bearing, improved on rolling contact surfaces and the raceway face, thus become the cause of noise.
The spy opens Japanese patent application 2003-231893 and has described a kind of grease composition with good low torsional performance, antifriction performance and low leaking performance, and this grease composition comprises an alkali metal salt of higher fatty acid or alkaline earth salt and has the carbonate products of different motion viscosity and the grease composition of metal organic sulfonate (wherein this metal-salt is selected from basic metal, alkaline-earth metal or zinc) as thickening material, two kinds.
The spy opens Japanese patent application 2002-265970 and has described and a kind ofly can improve the sound performance of spot contact bearing and the grease composition of antifriction performance simultaneously, it is served as reasons as the grease composition of the base oil of main ingredient and thickening material composition, and wherein thickening material is made up of the mixture of carbamide compound and lithium soap.
EP-A-1314774 has described a kind of grease composition that is used for constant-velocity joint (CVJs), it is said that said composition has anti-peeling off and the anti-jam performance.
Described grease composition comprises the soap of lubricating base oil, 0.01-10 quality %, the carbonic ether of 0.01-10 quality %, the thickening material of 2-30 quality % and the sulphur type extreme pressure reagent of 0.1-20 quality %.
EP-A-0767237 discloses a kind of grease composition that is used for constant-velocity joint, and it comprises the extreme pressure reagent of base oil, thickening material, boron nitride powder and sulfur-bearing-phosphorus.
EP-A-0767237 has set forth the life-span that described grease composition demonstrates favourable anti-spalling resistance and can prolong constant-velocity joint.
Point out that in EP-A-0767237 described grease composition can also include organic compounds for example zinc dithiophosphate, fatty acid zinc salt and zinc naphthenate in order further to improve anti-spalling resistance.
EP-A-0761806 has described a kind of grease composition, it comprises: the lubrication viscosity oil of main amount, be selected from the thickening material of single urea, two ureas, triuret and polyureas or its mixture and be selected from fatty acid zinc salt, the Whitfield's ointment zinc salt of alkyl replacement and the oil-soluble neutrality or the high alkalinity salts of carboxylic acids of oxoethanoic acid zinc.
But EP-A-1314774, EP-A-0767237 and EP-A-0761806 all do not relate to improvement fretting corrosion performance.In this respect, one skilled in the art will know that fretting corrosion is to peel off very different phenomenons with CVJ.
The utmost point wishes the grease composition with favourable antifriction characteristic can be provided.
Summary of the invention
In the present invention, surprisingly can use the corrosion of reducing friction of specific grease composition.
Therefore, provide the grease composition corrosive purposes that is used to reduce friction among the present invention, said composition comprises:
(A) be selected from the base oil of mineral oil, synthetic oil or its mixture,
(B) one or more carbamide compounds; With
(C) one or more fatty acid metal salt, wherein said metal is selected from aluminium, magnesium, zinc, calcium and composition thereof.
Base oil in this grease composition can be selected from mineral oil, synthetic oil or its mixture.Preferred especially synthetic oil.
The mineral oil that can use easily is the refining residue of the lubricating oil that obtains by the atmospheric resids vacuum distilling that crude oil atmospheric distillation obtains, and its example is paraffin oil, naphthenic oil or n-paraffin.
The example of the synthetic oil that can use easily comprises poly-alpha-olefin (PAOs), ether oil or ester oil.Also can use a class base oil of the hydroisomerization preparation by wax, for example those that sell with trade(brand)name " XHVI " by Shell group.
Poly-alpha-olefin comprises for example oligopolymer of decene, dodecylene or tetradecene of alkene, and this oligopolymer comprises the oligomer mixture of two to six aggressiveness.Can select PAOs easily according to the viscosity and the polymerization degree.
As ether oil, can use alkyl diphenyl ether easily.Described ether is the addition reaction product that common phenyl ether of 1mol and 1-3mol contain the alpha-olefin of 10-22 carbon.According to the mole number of carbon number and use, the characteristic difference of alpha-olefin, but their normally colourless transparent liquids and itself be known product.Especially, can use and be disclosed among the open 51-44263 of Japanese Patent, the open 52-1722 of Japanese Patent and the open 52-24628 of Japanese Patent those.
Those that the example of the alkyl diphenyl ether oil of commercially available acquisition comprises can trade(brand)name " MorescoHilube LB-15 ", " Moresco Hilube LB-22 ", " Moresco Hilube LB-32 ", " Moresco Hilube LB-46 ", " Moresco Hilube LB-68 " and " MorescoHilube LB-100 " are obtained by Matsumura Oil Research Corporation.
As ester oil, can use diester oil, three ester oils and four ester oils easily.
Diester oil can be represented by general formula (1):
R 1OCO(-CH 2-) nCOOR 2 (1)
R wherein 1And R 2Expression contains the aliphatic hydrocarbyl of 3-18 carbon atom, and n is the integer of 3-12.
The example of the ester oil that can use easily comprises Diisooctyl Sebacate, di(2-ethylhexyl)azelate, di-2-ethylhexyl adipate, dioctyl sebacate, nonane diacid di-n-octyl and di n octyl adipate.
Three ester oils can be represented by general formula (2):
R 1-C(-CH 2-COOR 2) 3 (2)
R wherein 1Expression hydrogen atom or contain the aliphatic hydrocarbyl of 1-10 carbon, R 2Expression contains the aliphatic hydrocarbyl of 3-18 carbon atom.If R 2Being the aliphatic hydrocarbyl that contains 3-10 carbon atom, then is particularly preferred.
For example, three esters can be for example reaction product of TriMethylolPropane(TMP) and glycerine of lipid acid and trivalent alcohol.
Four ester oils can be represented by general formula (3):
C(-CH 2-COOR 1) 4 (3)
R wherein 1Expression contains the aliphatic hydrocarbyl of 3-18 carbon atom.If R 1Being the aliphatic hydrocarbyl that contains 3-10 carbon atom, then is particularly preferred.
For example, four esters can be for example reaction product of tetramethylolmethane of lipid acid and tetravalent alcohol.
The mixture that can also use above-mentioned mineral oil and synthetic oil is as base oil (A).
Because the kinematic viscosity of base oil helps low torsional performance, therefore preferred base oil (A) has 10-40mm 2The kinematic viscosity of/s (40 ℃).
One or more carbamide compounds (B) in the grease composition can be selected from the carbamide compound that is used as thickening material in the typical representative grease composition easily.
Preferred carbamide compound is two carbamide compounds, three carbamide compounds and four carbamide compounds.
Two carbamide compounds are reaction product of vulcabond and monoamine, and this monoamine can be aliphatic amine, cycloaliphatic amines and/or aromatic amine.
The example of the monoamine that can use easily comprises octylame, decyl amine, lauryl amine, tetradecylamine, hexadecylamine, octadecylamine, oleyl amine, aniline, right-Tolylamine, hexahydroaniline.
In addition, the example of the vulcabond that can use easily comprises aliphatic vulcabond, alicyclic diisocyanate and aromatic diisocyanate: for example 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), naphthalene diisocyanate, right-phenylene vulcabond, anti-form-1,4-cyclohexyl diisocyanate (CHDI), 1,3-pair-(isocyanato methylbenzene), 4,4 '-dicyclohexyl methane diisocyanate (H12MDI), 1,3-pair-(isocyanato methyl) hexanaphthene (H6XDI), hexamethylene diisocyanate (HDI), 3-isocyanato methyl-3,3,5 '-3-methyl cyclohexanol based isocyanate (IPDI), phenylene vulcabond, between-tetramethylxylene diisocyanate (m-TMXDI) and right-tetramethylxylene diisocyanate (p-TMXDI).Especially, preferred 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), anti-form-1,4-cyclohexyl diisocyanate (CHDI) and 4,4 '-dicyclohexyl methane diisocyanate (H12MDI).
Three carbamide compounds can be represented by general formula (4):
Figure A20058004727000081
R wherein 1And R 2The expression alkylene, R 3And R 4The expression alkyl.
These compounds are reaction product of 2mol aliphatic series, alicyclic or aromatic diisocyanate, 1mol aliphatic series, alicyclic or aromatic diamine, 1mol aliphatic series, alicyclic or aromatic amine and 1mol aliphatic series, cyclic aliphatic or aromatic alcohol.They obtain by above-claimed cpd being mixed in base oil obtaining corresponding aforementioned proportion and to react.For example, they can obtain by 2mol toluylene group diisocyanate, 1mol ethylidene diisocyanate, 1mol octadecylamine and 1mol Stearyl alcohol are reacted in base oil.
The aliphatic series that can use easily, example alicyclic or aromatic diisocyanate comprises 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), naphthalene diisocyanate, right-phenylene vulcabond, anti-form-1,4-cyclohexyl diisocyanate (CHDI), 1,3-pair-(isocyanato methylbenzene), 4,4 '-dicyclohexyl methane diisocyanate (H12MDI), 1,3-pair-(isocyanato methyl) hexanaphthene (H6XDI), hexamethylene diisocyanate (HDI), 3-isocyanato methyl-3,3,5 '-3-methyl cyclohexanol based isocyanate (IPDI), phenylene vulcabond, between-tetramethylxylene diisocyanate (m-TMXDI) and right-tetramethylxylene diisocyanate (p-TMXDI).Especially, preferred 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), anti-form-1,4-cyclohexyl diisocyanate (CHDI) and 4,4 '-dicyclohexyl methane diisocyanate (H12MDI).
The example of the monoamine that can use easily comprises aliphatic series, alicyclic and aromatic monoamine.Aliphatic monoamine preferably has the saturated of 8-24 carbon atom or unsaturated aliphatic amine and can use with side chain or linear form, but preferred especially linear form.
Octylame, decyl amine, lauryl amine, tetradecylamine, hexadecylamine, octadecylamine, oleyl amine, aniline, right-Tolylamine, hexahydroaniline are preferred.
For aliphatic, alicyclic or aromatic diamine, the aliphatic diamine that can use easily is ethylene diamine, trimethylene diamines, tetramethylene-diamine, hexamethylene-diamine, eight methylene diamine and decamethylene diamine, alicyclic diamine is diamino-cyclohexane for example, with aromatic diamine for example phenylenediamine, p-diaminodiphenyl, diaminostilbene and tolidine, these all are the diamines that wherein has 2-12 carbon atom.
The example of the monohydroxy-alcohol that can use easily is the aliphatic series of side chain or straight chain, alicyclic or aromatic alcohol.The fatty alcohol that can use easily is C 8-C 24Saturated or unsaturated aliphatic is pure.Preferred especially linear form.
Preferred especially octanol, decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol and oleyl alcohol.
The example of the alicyclic alcohol that can use easily is a hexalin.The example of the aromatic alcohol that can use easily comprises benzylalcohol, saligenol, phenylethyl alcohol, styryl carbinol and hydrocinnamyl alcohol.
Four carbamide compounds can be represented by general formula (5):
Figure A20058004727000091
R wherein 1And R 2The expression alkylene, R 3The expression alkyl.
These compounds are reaction product of 2mol aliphatic series, alicyclic or aromatic diisocyanate, 1mol aliphatic series, alicyclic or aromatic diamine and 2mol aliphatic series, alicyclic or aromatic amine.They obtain by above-claimed cpd being mixed in conventional base oil obtaining corresponding aforementioned proportion and to react.For example, they can obtain by 2mol toluylene group diisocyanate, 1mol ethylene diamine and 2mol octadecylamine are reacted in base oil.
The example of the vulcabond that can use easily comprises aliphatic vulcabond, alicyclic diisocyanate and aromatic diisocyanate: for example 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), naphthalene diisocyanate, right-phenylene vulcabond, anti-form-1,4-cyclohexyl diisocyanate (CHDI), 1,3-pair-(isocyanato methylbenzene), 4,4 '-dicyclohexyl methane diisocyanate (H12MDI), 1,3-pair-(isocyanato methyl) hexanaphthene (H6XDI), hexamethylene diisocyanate (HDI), 3-isocyanato methyl-3,3,5 '-3-methyl cyclohexanol based isocyanate (IPDI), phenylene vulcabond, between-tetramethylxylene diisocyanate (m-TMXDI) and right-tetramethylxylene diisocyanate (p-TMXDI).Especially, preferred 4,4 '-diphenylmethanediisocyanate (MDI), toluylene group diisocyanate (TDI), anti-form-1,4-cyclohexyl diisocyanate (CHDI) and 4,4 '-dicyclohexyl methane diisocyanate (H12MDI).
For aliphatic, alicyclic or aromatic diamine, can use aliphatic diamine such as ethylene diamine, trimethylene diamines, tetramethylene-diamine, hexamethylene-diamine, eight methylene diamine and decamethylene diamine easily, alicyclic diamine is diamino-cyclohexane for example, with aromatic diamine such as phenylenediamine, p-diaminodiphenyl, diaminostilbene and tolidine, these all are the diamines with 2-12 carbon atom.
For monoamine, can use aliphatic series, alicyclic and aromatic monoamine easily.Preferred side chain or linear aliphatic monoamine are to have the saturated of 8-24 carbon atom or unsaturated aliphatic amine.Saturated or the unsaturated aliphatic amine of straight chain that especially preferably has 8-24 carbon atom.
As the example of alicyclic monoamine, can enumerate hexahydroaniline.
As the example of aromatic monoamine, can enumerate aniline and right-Tolylamine.
Based on the gross weight of grease composition, preferably with the amount blend of one or more carbamide compounds (B) with 2-30wt%, more preferably 2-20wt%.If the amount of described one or more carbamide compounds (B) is less than 2wt%, then the effect of this thickening material may be too little and denseness may not be consistency of grease.If the amount of described one or more carbamide compounds (B) surpasses 30wt%, then lubricating grease may become too hard and may can not get enough lubricant effects.
One or more fatty acid metal salt in the grease composition are preferably by having the saturated of 4-18 carbon atom or metal-salt that unsaturated fatty acids is formed, wherein said metal is selected from aluminium, magnesium, zinc, calcium and composition thereof, and described lipid acid can also comprise one or more hydroxyls.
Preferred wherein metal is selected from the fatty acid metal salt of zinc, aluminium and magnesium.Particularly preferred fatty acid metal salt is that wherein metal is selected from those of zinc and aluminium.
The lipid acid that can be advantageously used in fatty acid metal salt comprises: as the caproic acid of straight chain saturated acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and 12-oxystearic acid; As 4 of branching saturated acid, the 6-dimethyl is sad, 2-methyl undecanoic acid, 2-methyl tetradecanoic acid and 2-ethyl pentadecylic acid; 3-octylenic acid, 2-decylenic acid, decylenic acid, myristoleic acid, 2-methyl-2-dodecenoic acid, oleic acid, elaidic acid, linolic acid, linolenic acid and ricinolic acid (risinolic acid) as unsaturated acid.
Based on the grease composition gross weight, by being preferably 0.1-25wt%, more preferably described one or more fatty acid metal salt blends of 0.5-20wt% grease composition of obtaining to have fabulous antifriction performance, wherein said metal is selected from aluminium, magnesium, zinc, calcium and composition thereof.
If described one or more fatty acid metal salt exist with the amount less than 0.1wt%, then the effect of antifriction performance may be not enough, if surpass 25wt% with it, then may the become effect of too strong and antifriction performance of the effect of one or more fatty acid metal salt may reduce.
If desired, grease composition can comprise additional additive such as antioxidant, rust-preventive agent, metal corrosion inhibitor, oiliness improver (also being called friction modifiers), anti-wear agent, extreme-pressure additive and solid lubrication agent addition agent.
The example of additive comprises: antioxidant, and as 2,6 di tert butyl 4 methyl phenol, N-phenyl-a-naphthylamine and 2, the 6-di-t-butyl is right-cresylol; Rust-preventive agent, as oxidized petroleum wax, aminooimidazole quinoline, N, N '-trimethylene diamines dioleate, single oleic acid sorbitan ester, metal sulfonate, alkenyl succinate and derivative, ester class rust-preventive agent or amine rust-preventive agent; Wear-resisting or extreme-pressure additive, for example sulphur compound such as alkene sulfide, sulfurized oil ﹠ fat, phenylbenzene disulphide and benzyl disulfide thing, chlorine compound such as askarel or chloro paraffin, dithiophosphates such as zinc dithiophosphate and molybdenum dithiophosphate, dithiocar-bamate such as zinc dithiocarbamate and molybdenum dithiocarbamate, phosphorus compound such as phosphoric acid ester such as Tritolyl Phosphate, phosphorous acid ester, thiophosphatephosphorothioate and phosphorodithioate.
The present invention further provides a kind of for example method of fretting corrosion in bearing, spline, shaft coupling and the spring piece of equipment that reduces, described method comprises with the lubricated described equipment of aforesaid grease composition.
By method of the present invention, can provide grease composition that can greatly improve antifriction performance and bearing, spline, shaft coupling and the spring piece that uses described grease composition.
Embodiment
Describe the present invention with reference to following examples, but described embodiment does not plan to limit the scope of the invention by any way.
Embodiment
Experimental result at embodiment and comparative example is shown below.
Two carbamide compounds that are used as thickening material in grease composition are represented by general formula (6):
Figure A20058004727000121
With:
Aliphatic series A is that wherein R is two carbamide compounds that have the saturated alkyl of 8 carbon atoms;
Aliphatic series B is that wherein R is two carbamide compounds that have the saturated alkyl of 12 carbon atoms;
Aliphatic series C is that wherein R is two carbamide compounds that have the saturated alkyl of 18 carbon;
The two urea mixtures that aliphatic series D is made up of 50mol% aliphatic series A and 50mol% aliphatic series B;
The two urea mixtures that aliphatic series E is made up of 50mol% aliphatic series A and 50mol% aliphatic series C;
Aliphatic series F is two carbamide compounds as the reaction product of toluylene group diisocyanate (TDI) and octylame, Toluene-2,4-diisocyanate, and the 4-vulcabond: Toluene-2,4-diisocyanate, 80: 20 mixtures of 6-vulcabond are used for this toluylene group diisocyanate; With aromatics A be the reaction product of right-Tolylamine and MDI.
The base oil of the grease composition that is used for testing is:
Mineral oil A: 100 ℃ of following kinematic viscosity is 4mm 2The paraffin mineral oil of/s;
Mineral oil B: 100 ℃ of following kinematic viscosity is 11mm 2The paraffin mineral oil of/s;
Synthetic oil A: 100 ℃ of following kinematic viscosity is 6mm 2The poly-alpha-olefin of/s (can trade(brand)name " Hitec-166 " by Ethyl Japan Corporation obtain);
Synthetic oil B: 100 ℃ of following kinematic viscosity is 5.6mm 2The alkyl diphenyl ether of/s (can trade(brand)name " Moresco Hilube LB-32 " by Matsumura Oil Research Corporation obtain);
Synthetic oil C: 100 ℃ of following kinematic viscosity is 6mm 2The polyol ester of/s (can trade(brand)name " Kaolube " by Kao Corporation obtain).
The abbreviation of some fatty acid metal salt of the grease composition that is used for testing provides in table:
Mg-St: Magnesium Stearate
Ca-St: calcium stearate
Li-St: lithium stearate
Ca-12 (OH) St:12-oxystearic acid calcium
Li-12 (OH) St:12-hydroxy lithium stearate
Zn-St: Zinic stearas
Al-St: aluminum stearate.
The performance of result in the representative table is determined by following testing method:
Penetration degree: JIS K 2,220 5, and 3
Dropping point: JIS K2220 5,4
For antifriction, friction-wear test is carried out according to ASTM D4170.
Antifriction 22 hours the result of 25 ℃ of following friction-wear tests that is illustrated in of room temperature is illustrated in 22 hours result of-30 ℃ of following friction-wear tests and low temperature is antifriction.
About the frictional wear amount, the result presses following deciding grade and level:
Θ represents the frictional wear amount below 1.5mg, and it is very big that promptly antifriction wearing and tearing suppress effect;
Zero expression frictional wear amount is 1.5-5.0mg, and it is big that promptly antifriction wearing and tearing suppress effect;
△ represents that the frictional wear amount is 5.0-15.0mg, and it is little that promptly antifriction wearing and tearing suppress effect;
* expression frictional wear amount is higher than 15.0mg, and promptly antifriction wearing and tearing suppress weak effect.
Embodiment 1-5
By thickening material shown in the table 1, base oil and additive are obtained grease composition by mixed shown in the table 1 and heating.
Measure the gained grease composition penetration degree, dropping point (℃) and the result of antifriction (room temperature) shown in the table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Thickening material Two carbamide compounds: aliphatic A
10 10 10 10 10
Base oil Mineral oil A 89 89 89 89 89
Additive Mg-St 1
Ca-St 1
Ca-12(OH)St 1
Zn-St 1
Al-St 1
The result Penetration degree (dmm) 285 282 284 283 281
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature ○ △ △ Θ Θ
Antifriction (mg), room temperature 3.9 8.3 13.2 0.2 0.3
Influence about metal pair urea grease and Metallic stearates:
Ca-St: have some frictional wears to suppress effect.
Zn-St and Al-St: it is very big that frictional wear suppresses effect.
Therefore clearly in the middle of fatty acid metal salt, wherein metal is that the salt of Zn or Al has good especially effect.
Comparative example 1-6
For wherein using single two carbamide compounds, similarly test by changing base oil as for the situation of thickening material.The results are shown in the table 2.
Table 2
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Thickening material Two urea things:
Aliphatic series A 10 10 10 10
Aliphatic series B 30
Aliphatic series C 8
Base oil Mineral oil A 90 70 92
Synthetic oil A 90
Synthetic oil B 90
Synthetic oil C 90
The result Penetration degree (dmm) 278 280 280 283 294 275
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250 185 ＞250
Antifriction grade, room temperature × × × × × ×
Antifriction result (mg), room temperature 19.3 16.1 34.1 29.4 26.4 17.9
In these results, for only not observing antifriction characteristic with the carbamide compound of base oil blend.
Comparative example 7 and 8
For the situation that wherein under heating, lithium stearate or 12-hydroxy lithium stearate is added two carbamide compounds, similarly test.The results are shown in the table 3.
Table 3
Comparative example 7 Comparative example 8
Thickening material Two carbamide compounds:
Aliphatic series A 10 10
Base oil Mineral oil A 89 89
Additive Li-St 1
Li-12(OH)St 1
The result Penetration degree (dmm) 281 286
Dropping point, ℃ ＞250 ＞250
Antifriction grade, room temperature × ×
Antifriction result (mg), room temperature 21.3 20.6
Even when adding the lipid acid lithium salts in the urea grease, almost do not observe antifriction characteristic yet.
Embodiment 6-13
Similarly test by changing base oil.The results are shown in the table 4.
Table 4
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13
Thickening material Two carbamide compounds:
Aliphatic series A 10 10 10 10 10 10 10 10
Base oil Mineral oil B 89 89
Synthetic oil A 89 89
Synthetic oil B 89 89
Synthetic oil C 89 89
Additive Zn-St 1 1 1 1
Al-St 1 1 1 1
The result Penetration degree (dmm) 270 285 284 288 270 288 286 289
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250 ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature Θ Θ Θ Θ Θ Θ Θ Θ
Antifriction result (mg), room temperature 0.7 0.2 1.1 0.9 0.9 0.3 1.3 1.2
According to these results, when being blended into two carbamide compounds and Zinic stearas or aluminum stearate in the base oil, all having great antifriction wearing and tearing and suppress effect, and observe the base oil kind and antifriction wearing and tearing are suppressed effect not have substantially to influence.
The embodiment of embodiment 14-17
Similarly test by the amount that changes the thickening material that adds.The results are shown in the table 5.
Table 5
Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17
Thickening material Two carbamide compounds:
Aliphatic series A 15 15
Aliphatic series C 10 10
Base oil Mineral oil A 84 84 89 89
Additive Zn-St 1 1
Al-St 1 1
The result Penetration degree (dmm) 257 256 250 253
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature Θ Θ Θ Θ
Antifriction result (mg), room temperature 0.2 0.3 0.3 0.6
According to these results, even when grease consistency is hard, it is also very big that antifriction wearing and tearing suppress effect.
The embodiment of embodiment 18-29
Similarly test by the kind that changes thickening material, and consider its effect.The results are shown in table 6 and 7.
Table 6
Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23
Thickening material Two carbamide compounds:
Aliphatic series B 30 30
Aliphatic series C 8 8
Aliphatic series D 12 12
Aliphatic series E
Aliphatic series F
Aromatics A
Base oil Mineral oil A 69 69 91 91 87 87
Additive Zn-St 1 1 1
Al-St 1 1 1
The result Penetration degree (dmm) 298 300 288 290 290 293
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature Θ Θ Θ Θ Θ Θ
Antifriction result (mg), room temperature 0.2 0.2 0.4 0.6 0.3 0.3
Table 7
Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29
Thickening material Two carbamide compounds:
Aliphatic series B
Aliphatic series C
Aliphatic series D
Aliphatic series E 9 9
Aliphatic series F 13 13
Aromatics A 22 22
Base oil Mineral oil A 90 90 86 86 77 77
Additive Zn-St 1 1 1
Al-St 1 1 1
The result Penetration degree (dmm) 297 300 288 291 299 301
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature Θ Θ Θ Θ Θ Θ
Antifriction result (mg), room temperature 0.2 0.3 0.5 0.5 0.4 0.4
Even when the kind time-like that changes the thickening material of being made up of carbamide compound, the result is also constant.
Embodiment 30
Obtain grease composition by at room temperature 7wt% aliphatic series A being mixed with 92wt% mineral oil A as two carbamide compounds and 1wt% aluminum stearate.
The penetration degree of this grease composition be 276 and dropping point be higher than 250 (℃).Antifriction wearing and tearing under the room temperature suppress effect greatly (0.3mg).
Embodiment 31-35
Research changes the effect of the amount of the aluminum stearate that adds.The results are shown in the table 8.
Table 8
Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Example 35
Thickening material Two carbamide compounds:
Aliphatic series A 7 7 6.5 6.3 5.6
Base oil Mineral oil A 92.9 92.5 88.5 83.7 74.4
Additive Al-St 0.1 0.5 5 10 20
The result Penetration degree (dmm) 278 278 270 261 235
Dropping point, ℃ ＞250 ＞250 247 244 242
Antifriction grade, room temperature ○ ○ ○ △ △
Antifriction result (mg), room temperature 4.8 3.2 4.7 13.5 14.7
Clearly, the amount of the aluminum stearate of adding should be preferably 0.1-20wt%, and amount when being 0.1-5wt% its effect big especially.
Embodiment 36-39
Research changes the effect that is included in the lipid acid in the fatty acid metal salt.The results are shown in the table 9.
Table 9
Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39
Thickening material Two carbamide compounds:
Aliphatic series A 7 7 7 7
Base oil Mineral oil A 92 92 92 92
Additive Zinc laurate is saturated 1
Zinc tetradecanoate is saturated 1
Zinc oleate, unsaturated 1
Aluminium oleate, unsaturated 1
The result Penetration degree (dmm) 282 284 281 283
Dropping point, ℃ ＞250 ＞250 ＞250 ＞250
Antifriction grade, room temperature Θ Θ Θ Θ
Antifriction result (mg), room temperature 0.1 1.4 0.1 0.1
Clearly finding out from these results, is that saturated fatty acid or unsaturated fatty acids are irrelevant with being included in lipid acid in the fatty acid metal salt, and described effect is all big.
Embodiment 40-42
When using synthetic oil A, under-30 ℃, carried out frictional wear experiment 22 hours as base oil.
The results are shown in the table 10.
Table 10
Embodiment 40 Embodiment 41 Embodiment 42
Thickening material Two carbamide compounds:
Aliphatic series A 7 7 7
Base oil Mineral oil A 92 92 92
Additive Mg-St 1
Zn-St 1
Al-St 1
The result Penetration degree (dmm) 285 288 286
Dropping point, ℃ ＞250 ＞250 ＞250
Antifriction grade, room temperature ○ ○ Θ
Antifriction result (mg), room temperature 3.8 1.6 0.5
Even also observe the raising of antifriction characteristic at low temperatures.
Embodiment 43-44
Research uses four carbamide compounds and triuret hydride compounds to replace the effect of two carbamide compounds.
For four carbamide compounds,, 7.49g toluylene group diisocyanate prepares homogeneous solution by being added in the 100g base oil and be heated to 50 ℃.In this solution, add 11.75g oleyl amine and the 1.29g ethylene diamine that is dissolved in the 80g base oil.When mixture is stirred, make spawn immediately.
When continuing stirring, temperature is risen to 150 ℃, and the temperature maintenance is being added the 2.0g metal-salt after 30 minutes and before cooling, the mixture former state was being kept 15 minutes.Use three-roll grinder to make lubricating grease then.Obtain containing the grease composition of 10wt% four carbamide compounds thus.
For three carbamide compounds,, 9.20g toluylene group diisocyanate and 7.14g stearyl alcohol prepare homogeneous solution by being joined in the 100g base oil and be heated to 50 ℃.
Subsequently, the 4.05g tallow amine and the 1.56g ethylene diamine that will be dissolved in the 77g base oil join in this solution that remains under 90-150 ℃, and with unreacted isocyanate reaction.Add the 2.0g metal-salt then and before cooling, the mixture former state was kept 15 minutes.Use three-roll grinder to make lubricating grease then.Obtain containing the grease composition of 11wt% triuret carbamate compounds thus.
Table 11
Embodiment 43 Embodiment 43
Thickening material Four carbamide compounds: 10
The triuret carbamate compounds 11
Base oil Mineral oil A 89 88
Additive Al-St 1 1
The result Penetration degree (dmm) 271 293
Dropping point, ℃ ＞250 ＞250
Antifriction grade, room temperature Θ Θ
Antifriction result (mg), room temperature 0.7 0.9
Even when carbamide compound changes, also can obviously improve antifriction characteristic.

Claims (11)

1. the grease composition corrosive purposes that is used to reduce friction, said composition comprises:
(A) be selected from the base oil of mineral oil, synthetic oil or its mixture,
(B) one or more carbamide compounds and
(C) one or more fatty acid metal salt, wherein said metal is selected from aluminium, magnesium, zinc, calcium and composition thereof.
2. the purposes of claim 1, wherein based on the gross weight of grease composition, this grease composition comprises one or more carbamide compounds (B) that content is 2-30wt%.
3. claim 1 or 2 purposes, wherein one or more carbamide compounds (B) are two carbamide compounds.
4. claim 1 or 2 purposes, wherein one or more carbamide compounds (B) are three carbamide compounds by general formula (4) expression:
Figure A2005800472700002C1
R wherein 1And R 2The expression alkylene, R 3And R 4The expression alkyl.
5. claim 1 or 2 purposes, wherein one or more carbamide compounds (B) are four carbamide compounds by general formula (5) expression:
Figure A2005800472700002C2
R wherein 1And R 2The expression alkylene, R 3The expression alkyl.
6. each purposes of claim 1-5, wherein based on the gross weight of grease composition, this grease composition comprises one or more fatty acid metal salt (C) that content is 0.1-25wt%.
7. each purposes of claim 1-6, wherein one or more fatty acid metal salt (C) are the metal-salts that contains the saturated or unsaturated fatty acids of 4-18 carbon atom, wherein said metal is selected from aluminium, magnesium, zinc and calcium and composition thereof, and described lipid acid can also comprise one or more hydroxyls.
8. each purposes of claim 1-7, wherein base oil (A) is a poly-alpha-olefin.
9. each purposes of claim 1-7, wherein base oil (A) is an ether oil.
10. each purposes of claim 1-7, wherein base oil (A) is an ester oil.
11. reduce the method for fretting corrosion in bearing, spline, shaft coupling and the spring piece, described method comprises each the lubricated described bearing of grease composition, spline, shaft coupling and the spring piece with claim 1-10.
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CN103484225A (en) * 2013-08-29 2014-01-01 中国石油化工股份有限公司 High-temperature polyurea lubricating grease composition and preparation method thereof

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ZA200704729B (en) 2008-06-25
EP1828356A1 (en) 2007-09-05
KR20070092741A (en) 2007-09-13
US20060154833A1 (en) 2006-07-13
BRPI0519092A2 (en) 2008-12-23
AU2005315557A1 (en) 2006-06-22
JP2006169386A (en) 2006-06-29
AU2005315557B2 (en) 2009-04-23
WO2006064053A1 (en) 2006-06-22
CA2590861A1 (en) 2006-06-22

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