WO2011118814A1 - Composition de graisse - Google Patents

Composition de graisse Download PDF

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Publication number
WO2011118814A1
WO2011118814A1 PCT/JP2011/057462 JP2011057462W WO2011118814A1 WO 2011118814 A1 WO2011118814 A1 WO 2011118814A1 JP 2011057462 W JP2011057462 W JP 2011057462W WO 2011118814 A1 WO2011118814 A1 WO 2011118814A1
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Prior art keywords
grease composition
group
component
base oil
grease
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PCT/JP2011/057462
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English (en)
Japanese (ja)
Inventor
行敏 藤浪
太平 岡田
拓矢 大野
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出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to JP2012507118A priority Critical patent/JP5706883B2/ja
Priority to CN2011800137827A priority patent/CN102791841A/zh
Priority to EP11759618.9A priority patent/EP2554644A4/fr
Priority to US13/636,940 priority patent/US20130012416A1/en
Publication of WO2011118814A1 publication Critical patent/WO2011118814A1/fr

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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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C10M2207/1236—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to a grease composition.
  • the present invention relates to a grease composition used for a main bearing that receives a main shaft incorporated in a wind turbine generator and a pitch bearing that receives a blade shaft.
  • a grease composition is used for lubrication of a bearing that receives a large load, such as a main bearing that receives a main shaft and a pitch bearing that receives a blade shaft incorporated in a wind power generator.
  • a bearing that receives a large load such as a main bearing that receives a main shaft and a pitch bearing that receives a blade shaft incorporated in a wind power generator.
  • Such main bearings and pitch bearings are constantly subject to fluctuations and minute fluctuations due to changes in wind speed and minute control of the blades, and are in an environment where fretting wear is likely to occur.
  • Replacing a bearing in the event of a failure requires great effort and cost, and therefore a lubricant that has excellent fretting resistance and is unlikely to cause damage to the bearing over a long period of time is required.
  • a grease composition based on an ester synthetic oil having a kinematic viscosity at 100 ° C. of 200 to 2500 mm 2 / s has been proposed (see Patent Document 1). Furthermore, a grease composition is disclosed that uses a high-viscosity base oil for a grease composition and, if necessary, contains an extreme pressure agent to improve durability against a large load (non-patent document). 1 and 2).
  • examples of the grease composition used in the wind power generator include a composition containing a base oil, a thickener, and oleoyl sarcosine (see Patent Document 2), and a kinematic viscosity at 40 ° C. of 70 to 250 mm 2.
  • a composition containing a base oil that is / s, a thickener, and a carboxylic acid-based anticorrosive additive has been proposed (see Patent Document 3).
  • Main bearings and pitch bearings used in wind turbine generators are required to reduce not only fretting wear due to rotation of the main shaft and wing shaft, but also reduction of bearing wear due to receiving heavy spindles and wing shafts.
  • it is difficult to simultaneously suppress bearing wear and fretting wear.
  • a high-viscosity base oil is used, there is a problem that the low-temperature startability is deteriorated with respect to the low-viscosity base oil and fretting wear is increased.
  • the present invention (1) A grease composition containing a base oil and a thickening agent, wherein the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly- ⁇ -olefin ( A grease composition containing component A), (2) The grease composition according to (1), wherein the kinematic viscosity of the component A at 40 ° C. is 600 mm 2 / s or more, (3) The grease composition according to (1) or (2), wherein the component A is contained in an amount of 20% by mass or more based on the total amount of the composition, (4) The grease composition according to any one of (1) to (3) above, wherein the base oil has a kinematic viscosity at 40 ° C.
  • the base oil contains 10 to 70% by mass of a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less based on the total amount of the composition.
  • a grease composition used for a wind power generator comprising: a main bearing connected to a main shaft to which a wing of the wind power generator is connected; and a pitch bearing connected to a wing shaft incorporated in the wing.
  • the grease composition of the present invention bearing wear and fretting wear under a high load can be simultaneously suppressed, and the life of the bearing can be extended. Further, according to the present invention, it is possible to provide a grease composition capable of suppressing fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swinging direction. A grease composition that is small and excellent in low-temperature characteristics can be provided.
  • the grease composition of the present invention comprises a base oil and a thickener, and the base oil has a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more and is produced using a poly- ⁇ -olefin (component A). ).
  • the poly- ⁇ -olefin produced using a metallocene catalyst can suppress bearing wear and fretting wear at the same time, thereby prolonging the life of the bearing, particularly fretting caused by minute vibration in the swinging direction.
  • those having a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more are used from the viewpoint of suppressing fretting wear associated with load fluctuations in the thrust direction.
  • the kinematic viscosity at 40 ° C. of the component A is preferably 600 mm 2 / s or more, and more preferably 1000 mm 2 / s or more.
  • the upper limit is not particularly limited, but is about 200,000 mm 2 / s from the viewpoint of keeping the viscosity of the base oil moderate.
  • the kinematic viscosity at 100 ° C. is preferably 32 mm 2 / s or more, more preferably 90 mm 2 / s or more, from the same viewpoint as described above.
  • Examples of the metallocene catalyst for obtaining the component A include a catalyst containing a combination of a metallocene compound and a promoter.
  • a metallocene compound a compound represented by the general formula (I) (RC 5 H 4 ) 2 MX 2 (I)
  • the metallocene compound represented by these is preferable.
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • M represents a transition metal element of Group 4 of the periodic table
  • X represents a covalent bond or an ionic bond. Represents a ligand.
  • R is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • M include titanium, zirconium, and hafnium. Among these, zirconium is preferable.
  • Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 to 20 carbon atoms.
  • 1 to 12 phosphorus-containing hydrocarbon groups for example, diphenylphosphine group
  • 1 to 20 carbon atoms preferably 1 to 12 silicon-containing hydrocarbon groups (for example, trimethylsilyl group)
  • 1 to 20 carbon atoms are preferable Includes boron compounds containing 1 to 12 hydrocarbon groups or halogens (for example, B (C 6 H 5 ) 4 , BF 4, etc.).
  • halogens for example, B (C 6 H 5 ) 4 , BF 4, etc.
  • hydrogen atoms, halogen atoms, hydrocarbons A group selected from a group and an alkoxy group is preferred.
  • metallocene compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (Iso-propylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride , Bis (texylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylmethylcyclopentadienyl) zirco Um dichloride, bis (cyclopent
  • methylaluminoxane is preferable.
  • the methylaluminoxane is not particularly limited and conventionally known methylaluminoxane can be used.
  • the general formula (II) or the general formula (III) can be used.
  • p represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.
  • the method for producing methylaluminoxane include a method in which methylaluminum and a condensing agent such as water are brought into contact with each other, but the means is not particularly limited and may be carried out according to a known method.
  • the compounding ratio of the metallocene compound and methylaluminoxane is usually 15 to 150, preferably 20 to 120, more preferably 25 to 100 for the methylaluminoxane / metallocene compound (molar ratio). If it is 15 or more, catalytic activity is exhibited, and the yield of a trimer or more suitable as a base oil for a lubricating oil does not decrease due to the formation of an ⁇ -olefin dimer. On the other hand, if it is 150 or less, deashing removal of the catalyst will not be incomplete.
  • metallocene catalysts other than those mentioned above include metallocene catalysts that use a metallocene compound having a crosslinking group.
  • a metallocene compound having two crosslinking groups is preferable, and a metallocene compound having meso symmetry is particularly preferable.
  • Examples of the metallocene catalyst using the metallocene compound having meso symmetry include, for example, (a) a metallocene compound represented by the following formula (IV), and (b) (b-1) a metallocene compound of the component (a) Alternatively, a metallocene catalyst containing at least one component selected from a compound capable of reacting with a derivative thereof to form an ionic complex and (b-2) aluminoxane may be mentioned.
  • the compound represented by the formula (IV) is a mesosymmetric compound, and in the formula (IV), M represents a metal element belonging to Groups 3 to 10 of the periodic table.
  • X represents a ⁇ -binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y are the same or different It may be.
  • A represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, — SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - and -AlR 1 - shows a bridging group selected from 2 in the formula (IV) Two A's may be the same or different.
  • R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms.
  • q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
  • E is a group represented by the following formulas (V) and (VI), and two Es in the formula (IV) are the same.
  • the mesosymmetric compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1,1 ′) (2,2 ′).
  • R 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group or a heteroatom-containing group. Represents a group selected from: When several R ⁇ 2 > exists, they may mutually be same or different.
  • the bond indicated by the wavy line represents the bond with the bridging group A.
  • crosslinking group A in the formula (IV) a group represented by the following formula (VII) is preferable.
  • B in the formula (VII) is a skeleton of a bridging group and represents a carbon atom, a silicon atom, a boron atom, a nitrogen atom, a germanium atom, a phosphorus atom, or an aluminum atom.
  • R 3 represents a hydrogen atom, a carbon atom, an oxygen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an amine-containing group, or a halogen-containing group.
  • n is 1 or 2.
  • metallocene compound represented by the formula (IV) include (1,1′-ethylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2 , 2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2 , 2′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1 , 1′-ethylene) (2,2′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2 2′-ethylene) -bis (5,6-dimethylin
  • any compound can be used as long as it can react with the metallocene compound of the component (a) to form an ionic complex.
  • Those represented by the following general formulas (VIII) and (IX) can be preferably used.
  • L 1 represents a Lewis base
  • L 2 represents M 2 , R 5 R 6 M 3 , R 7 3 C or R 8 M 3
  • [Z] ⁇ represents a non-coordinating anion [Z 1 ] ⁇ or [Z 2 ] ⁇ .
  • [Z 1 ] ⁇ is an anion in which a plurality of groups are bonded to the element, that is, [M 1 G 1 G 2 ...
  • G f ] ⁇ (where M 1 is a group 5-15 element in the periodic table, Preferably, it represents a group 13 to 15 element of the periodic table, G 1 to G f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, or 1 to carbon atoms.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R 5 and R 6 are a cyclopentadienyl group and a substituted group, respectively.
  • R 7 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
  • R 8 represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
  • M 2 includes elements in groups 1 to 3, 11 to 13, and 17 of the periodic table, and M 3 represents elements in groups 7 to 12 of the periodic table.
  • L 1 examples include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
  • R 4 examples include hydrogen, methyl group, ethyl group, benzyl group, and trityl group.
  • R 5 and R 6 include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
  • R 7 examples include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R 8 include tetraphenylporphyrin, phthalocyanine, allyl, methallyl and the like. .
  • M 2 include Li, Na, K, Ag, Cu, Br, I, and I 3.
  • M 3 include Mn, Fe, Co, Ni, and Zn. And so on.
  • [Z 1 ] ⁇ that is, [M 1 G 1 G 2 ... G f ]
  • specific examples of M 1 include B, Al, Si, P, As, Sb, etc., preferably B and Al.
  • G 1 and G 2 to G f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like.
  • Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Romechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, di
  • Noncoordinating anions i.e. pKa of -10 or less Bronsted acid alone or Bronsted acid and Lewis acid combined conjugate base [Z 2] -
  • Examples of trifluoromethanesulfonic acid anion (CF 3 SO 3 ) ⁇ bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO 4 ) ⁇ , trifluoroacetate anion (CF 3 CO 2 ) ⁇ , Hexafluoroantimony anion (SbF 6 ) ⁇ , fluorosulfonic acid anion (FSO 3 ) ⁇ , chlorosulfonic acid anion (ClSO 3 ) ⁇ , fluorosulfonic acid anion / 5-antimony fluoride (FSO 3 / SbF 5 ) -
  • an ionic compound that reacts with the metallocene compound (a) to form an ionic complex, ie, (b-1) component compound include tetrakis (pentafluorophenylboric acid) N, N -Dimethylanilinium, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (Tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl tetrakis
  • R 9 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom
  • w represents an average degree of polymerization, Usually an integer of 2 to 50, preferably 2 to 40, wherein each R 9 may be the same or different, and a chain aluminoxane represented by the general formula (XI)
  • Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
  • the aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
  • the use ratio of (a) catalyst component to (b) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (b-1) compound is used as (b) catalyst component.
  • the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high, which is not practical.
  • the compound (b-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.
  • the catalyst component (b), (b-1) and (b-2) can be used alone or in combination of two or more.
  • the catalyst in the present invention may contain the components (a) and (b) as main components, and (a) component, (b) component and (c) organoaluminum compound. May be contained as a main component.
  • organoaluminum compound of component (c) the general formula (XII) (R 20 ) v AlQ 3-v (XII) (Wherein R 20 represents an alkyl group having 1 to 10 carbon atoms, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms) Which is an integer).
  • Specific examples of the compound represented by the general formula (XII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used singly or in combination of two or more.
  • the use ratio of the component (a) to the component (c) is a molar ratio, preferably 1: 1 to 1: 10,000, more preferably 1: 5 to 1: 2,000, and still more preferably 1: 10 to 1: 1,000.
  • the activity per transition metal can be improved.
  • the amount is too large, the organoaluminum compound is wasted and a large amount remains in the ⁇ -olefin polymer, which is not preferable.
  • an ⁇ -olefin having 3 to 14 carbon atoms is usually used.
  • ⁇ -olefins selected from 1-octene, 1-decene, and 1-dodecene are preferred, and 1-decene is particularly preferred because an ⁇ -olefin having the desired kinematic viscosity is easily obtained.
  • the A component may be a copolymer using two or more kinds of ⁇ -olefins having 3 to 14 carbon atoms, in which case an ⁇ -olefin selected from 1-octene, 1-decene and 1-dodecene is particularly preferred. preferable.
  • the mixing ratio of the metallocene compound represented by the general formula (I) or (IV) and the ⁇ -olefin having 3 to 14 carbon atoms is usually 0.01 to 0. .4, preferably 0.05 to 0.3, and more preferably 0.1 to 0.2.
  • 0.01 or more sufficient catalytic activity is obtained, and when 0.4 or less, the yield of the trimer or more oligomer suitable as the base oil of the lubricating oil is improved, and the catalyst is deashed. Removal will not be incomplete.
  • the polymerization of the ⁇ -olefin having 3 to 14 carbon atoms is preferably performed in the presence of hydrogen.
  • the amount of hydrogen added is usually 0.1 to 500 kPa, preferably 0.5 to 300 kPa, and more preferably 1 to 200 kPa.
  • the amount of hydrogen added is 0.1 kPa or more, sufficient catalytic activity can be obtained.
  • it is 500 kPa or less, the production of a saturated product of raw material ⁇ -olefin can be reduced, and the desired poly- ⁇ - The olefin yield is improved.
  • the polymerization of the ⁇ -olefin having 3 to 14 carbon atoms is not limited in the reaction method, and may be performed in the absence of a solvent or in a solvent, and any method may be used.
  • a reaction solvent for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane Halogenated hydrocarbons such as chloroform and dichloromethane.
  • the temperature of the polymerization reaction is usually 0 to 200 ° C., preferably 20 to 180 ° C., more preferably 30 to 150 ° C. By being in the above range, sufficient catalytic activity can be obtained, and the yield of trimer or higher oligomer suitable as a base oil for lubricating oil can be improved. Polymerization by the above method can produce an A component having a selectivity of trimer or higher of 50% or higher.
  • component A is different from conventional poly ⁇ -olefins in terms of molecular structure and high homogeneity, and exhibits high oxidation stability and high viscosity index, and is excellent as a lubricating base oil.
  • the viscosity index of the component A is preferably from 150 to 350, more preferably from 165 to 300, from the viewpoint of increasing fluidity at low temperatures.
  • the grease composition of the present invention has a high viscosity index, which, unlike conventional grease compositions using poly ⁇ -olefins, improves low-temperature viscosity characteristics and depends on a viscosity index improver. The degree goes down.
  • the grease composition of the present invention can also suppress fretting wear due to load fluctuations in the thrust direction in addition to fretting wear due to minute vibrations in the swing direction.
  • the grease composition of the present invention preferably contains a B component having a kinematic viscosity at 40 ° C. of 70 mm 2 / s or less from the viewpoint of improving fretting wear and pumpability.
  • the kinematic viscosity at 40 ° C. of the component B is preferably 10 to 50 mm 2 / s, more preferably 20 to 45 mm 2 / s, and still more preferably 20 to 40 mm 2 / s.
  • the kinematic viscosity at 100 ° C. of the component B is preferably 13 mm 2 / s or less, more preferably 3 to 9 mm 2 / s.
  • the viscosity index of the component B is preferably from 70 to 250, more preferably from 120 to 200, from the viewpoint of improving fluidity at low temperatures.
  • Component B is, for example, an ⁇ -olefin (single or mixed) oligomer having 4 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, or an olefin such as a co-oligomer of 1-decene and ethylene. It is an oligomer, and each may be used alone or as a mixture. These olefin oligomers may be synthesized by a known production method, or may be synthesized by a production method as described in JP-A-07-133234 and JP-A-03-131612.
  • any base oil such as a diester, polyol ester, aromatic ester, alkyl-substituted diphenyl ether, or mineral oil may be used, but a synthetic oil having a pour point of ⁇ 35 ° C. or lower is preferable from the viewpoint of low temperature fluidity.
  • the base oil may further contain other synthetic oil or mineral oil, if necessary, in the A component and preferably the B component.
  • Examples of other synthetic oils include, as aromatic oils, alkylbenzenes such as monoalkylbenzene and dialkylbenzene, and alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene.
  • ester oils include dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, ditridecyl glutarate, and methyl acetyl cinnolate, or trioctyl trimellitate, Aromatic ester oils such as tridecyl trimellitate and tetraoctyl pyromellitate, and further trimethylolpropane caprylate, trimethylolpropane verargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol verargonate, etc.
  • ether oils include polyglycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, and polypropylene glycol monoether, or monoalkyl triphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, pentaphenyl ether, tetraphenyl ether, monoalkyl tetra Examples thereof include phenyl ether oils such as phenyl ether and dialkyl tetraphenyl ether, olefinic oligomers such as normal paraffin, isoparaffin, polybutene, polyisobutylene, 1-decene oligomer, and 1-decene and ethylene co-oligomer.
  • the above synthetic oils may be used alone or as a mixture.
  • the mineral oil a refined product obtained by appropriately combining vacuum distillation, oil removal, solvent extraction, hydrocracking, solvent dewaxing, sulfuric acid washing, white clay purification, hydrorefining, and the like can be used.
  • the base oil preferably has a kinematic viscosity at 40 ° C. of 150 to 2000 mm 2 / s, more preferably 200 to 1000 mm 2 / s, from the viewpoint of excellent fretting wear and bearing wear. More preferably, it is 300 to 700 mm 2 / s.
  • the kinematic viscosity at 100 ° C. of the base oil is preferably 14 to 300 mm 2 / s, more preferably 16 to 150 mm 2 / s.
  • the viscosity index of the base oil is preferably from 90 to 350, more preferably from 120 to 350, from the viewpoint of increasing fluidity at low temperatures.
  • the grease composition of the present invention suppresses bearing wear and fretting wear at the same time, thereby prolonging the life of the bearing, and in addition to fretting wear due to minute vibrations in the swinging direction, in addition to load fluctuations in the thrust direction.
  • the component A is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total amount of the composition.
  • the upper limit is not particularly limited, but is usually 90% by mass from the viewpoint of the blend ratio of the base oil.
  • the content of component A in the base oil is preferably 35% by mass or more, more preferably 45 to 85% by mass, from the same viewpoint as described above.
  • the base oil preferably contains 10 to 70% by mass of the component B with respect to the total amount of the composition because it is excellent in fretting wear and pumpability and can be easily adjusted to a high viscosity. Is 15 to 60% by mass, and more preferably 20 to 50% by mass.
  • the content of the B component in the base oil is preferably 12 to 65% by mass, more preferably 12 to 60% by mass, and still more preferably 17 to 55% by mass, from the same viewpoint as described above. .
  • the content ratio of the A component and the B component in the base oil is expressed as a mass ratio (A component / B component) from the viewpoint of ease of grease production and the appropriate viscosity of the base oil. It is preferably 0.45 to 9.0, and more preferably 1.0 to 5.0.
  • the grease composition of the present invention contains a thickener.
  • a thickener both organic and inorganic thickeners can be used, and a soap-based thickener is preferable from the viewpoint of wear resistance.
  • Li soap, Li complex soap, Ca soap, Ca sulfonate complex soap, or Ca complex soap is more preferable.
  • the fatty acid constituting the soap contains 12-hydroxystearate. It is a waste.
  • soap contains Li, More preferably, it is Li complex soap.
  • Li complex soap is excellent in performance balance from low temperature to high temperature.
  • As the thickener urea compounds, bentonite, silica, carbon black, PTFE, etc. may be used. These may be used alone or in combination.
  • the content of the thickener is not limited as long as grease can be formed and maintained with the above base oil, but in addition to fretting wear due to minute vibrations in the swing direction, fretting wear due to load fluctuations in the thrust direction. From the viewpoint of suppressing the amount and the excellent pumpability, it is preferably 17% by mass or less based on the total amount of the composition of the present invention. From the above viewpoint, the blending amount of the thickener is more preferably 14% by mass or less, and particularly preferably 12% by mass or less, based on the total amount of the composition.
  • the content of the thickener is expressed as the amount of carboxylic acid constituting the thickener for the soap-type thickener.
  • the urea-based thickener is expressed as a reaction amount of isocyanate and amine.
  • Carboxylic acids include crude fatty acids obtained by hydrolyzing fats and oils to remove glycerol, monocarboxylic acids such as stearic acid, monohydroxycarboxylic acids such as 12-hydroxystearic acid, dibasic acids such as azelaic acid, terephthalic acid, Examples include aromatic carboxylic acids such as salicylic acid and benzoic acid. In addition, you may use ester of carboxylic acid. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the alkali include metal hydroxides such as alkali metals or alkaline earth metals. Examples of the metal include sodium, calcium, lithium, and aluminum.
  • an extreme pressure agent containing sulfur is preferably blended in an amount of 0.01 to 10% by mass based on the total amount of the composition from the viewpoint of obtaining blending effects such as prevention of seizure.
  • extreme pressure agents include zinc dialkyldithiophosphate (ZnDTP), molybdenum dialkyldithiophosphate (MoDTP), zinc dithiocarbamate (ZnDTC), molybdenum dithiocarbamate (MoDTC), dithiocarbamine (DTC), thiophosphate, sulfurized oil, Examples include dibenzyl disulfide and thiadiazole. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the grease composition of the present invention may contain a resin / wax soluble in a base oil such as petroleum resin or polyethylene, and among them, a petroleum resin is preferable.
  • the blending amount of the petroleum resin is preferably 0.5 to 35% by mass based on the total amount of the composition from the viewpoint of maintaining an appropriate viscosity and obtaining good low-temperature torque properties. From the above viewpoint, the blending amount of the petroleum resin is more preferably 1 to 30% by mass, and more preferably 2 to 25% by mass based on the total amount of the composition.
  • a cyclopentadiene type is preferable, a product obtained by thermal copolymerization of a cyclopentadiene and an ⁇ -olefin or a monovinyl aromatic hydrocarbon, and a product obtained by hydrogenating these by a usual method as necessary. Or a mixture thereof.
  • cyclopentadiene cyclopentadiene, a multimer thereof, an alkyl-substituted product thereof, or a mixture thereof can be used.
  • Industrially, about 30 mass of cyclopentadiene obtained by steam cracking such as naphtha is used.
  • a cyclopentadiene fraction containing at least%, preferably at least about 50% by weight.
  • This CPD fraction may contain an olefin monomer copolymerizable with these alicyclic dienes.
  • the olefinic monomer include aliphatic diolefins such as isoprene, piperylene and butadiene, and alicyclic olefins such as cyclopentene.
  • concentration of these olefins is preferably low, but is acceptable if it is about 10% by mass or less per cyclopentadiene.
  • ⁇ -olefins which are raw materials for copolymerization with cyclopentadiene
  • ⁇ -olefins having 4 to 18 carbon atoms, preferably 4 to 12 carbon atoms, and mixtures thereof are used, among which ethylene, propylene or 1- A derivative from butene or the like, or a decomposition product of paraffin wax is preferably used. It is industrially preferred that the ⁇ -olefins be blended in less than about 4 moles per mole of cyclopentadiene.
  • monovinyl aromatic hydrocarbons include styrene, o, m, p-vinyltoluene, ⁇ , ⁇ -methylstyrene, and the like. These monovinyl aromatic hydrocarbons may contain indenes such as indene, methylindene and ethylindene, and industrially, it is advantageous to use a so-called C9 fraction obtained by steam cracking such as naphtha. . When monovinyl aromatic hydrocarbons are used as a copolymerization raw material, it is industrially preferable to add less than about 3 moles per mole of cyclopentadiene.
  • the grease composition of the present invention preferably has a blending degree of 220 to 350 from the viewpoint of adjusting the hardness of the grease to maintain good low temperature torque characteristics and preventing bearing wear and fretting wear. From the above viewpoint, the penetration is preferably 250 to 340, more preferably 265 to 320.
  • an antioxidant in the grease composition of the present invention, an antioxidant, a rust preventive agent, a solid lubricant, a filler, an oily agent, a metal deactivator, if necessary, within the range where the object of the present invention is achieved.
  • blend additives such as a water-resistant agent, another extreme pressure agent, an antiwear agent, a viscosity index improver, and a coloring agent.
  • antioxidants examples include amine-based antioxidants such as alkylated diphenylamine, phenyl- ⁇ -naphthylamine, alkylated- ⁇ -naphthylamine, 2,6-di-t-butyl-4-methylphenol, 4,4 ′ -Phenolic antioxidants such as methylene bis (2,6-di-t-butylphenol), peroxide decomposition agents such as sulfur and ZnDTP, etc., and these are usually in the proportion of 0.05 to 10% by mass Used in.
  • amine-based antioxidants such as alkylated diphenylamine, phenyl- ⁇ -naphthylamine, alkylated- ⁇ -naphthylamine, 2,6-di-t-butyl-4-methylphenol
  • 4,4 ′ -Phenolic antioxidants such as methylene bis (2,6-di-t-butylphenol), peroxide decomposition agents such as sulfur and ZnDTP
  • rust inhibitor examples include sodium nitrite, sulfonate, sorbitan monooleate, fatty acid soap, amine compound, succinic acid derivative, thiadiazole, benzotriazole, and benzotriazole derivative.
  • Other extreme pressure agents and antiwear agents include, for example, phosphate ester, acid phosphate, phosphite ester, acid phosphite, alkyl hydrogen phosphite, phosphate ester amine salt, phosphite amine salt, etc.
  • Phosphorus compounds chlorinated oils and fats, chlorinated paraffins, chlorinated fatty acid esters, chlorinated fatty acid esters and other chlorinated compounds, alkyl or alkenyl maleic acid esters, alkyl or alkenyl succinic acid ester compounds, alkyl or alkenyl maleic acids And organic acid compounds such as alkyl or alkenyl succinic acid, and organic metal compounds such as naphthenate.
  • solid lubricant examples include polyimide, PTFE, graphite, metal oxide, boron nitride, melamine cyanurate (MCA), and molybdenum disulfide.
  • MCA melamine cyanurate
  • the various additives as described above may be blended alone or in combination, and the lubricating oil additive of the present invention does not inhibit these effects.
  • FIG. 1 is a schematic view showing a wind power generator in which the grease composition of the present invention is used.
  • a wind turbine generator 1 is connected to a wing 5, a main shaft 4 to which the wing 5 is fixed, a generator 31 driven by the rotation of the main shaft 4, and the main shaft 4.
  • a nacelle 3 for housing the main bearing 33 and the yaw bearing 32 and a tower 2 for supporting the nacelle 3 are provided.
  • a pitch bearing 41 is connected to the wing shaft 51. For example, by rotating the wing shaft 51, it is possible to make the wing 5 easier to receive or not receive wind, so that the rotation of the main shaft 4 becomes constant. Thereby, stable electric power can be obtained from the generator 31.
  • the grease composition of the present invention is preferably used for the main bearing 33 and the pitch bearing 41.
  • wear of the roller, cage, bearing race, and the like due to heavy loads caused by the heavy wings 5 and the main shaft 4, or fretting of the bearing race due to fluctuations and swings of rotation, etc.
  • bearing wear and fretting wear can be prevented by using the grease of the present invention.
  • the wind turbine generator 1 is less effective when the output is smaller than 300 kW because the load is small.
  • the wind power generator 1 is preferably a medium or large size having an output of 300 kW or more, more preferably 700 kW or more.
  • the main bearing 33 and the pitch bearing 41 may be connected to a pump for supplying grease via a pipe (not shown). The grease can be easily supplied to the main bearing 33 and the pitch bearing 41 by operating the pump. For this reason, work at a high place becomes unnecessary, and workability is improved.
  • the grease composition of the present invention includes various gears, various bearings (ball bearings, roller bearings, slide bearings, pin-bushes, etc.), paper machine rollers, steel equipment bearings, construction machine slewing bearings, It can be used for geared motors, automobile wheel bearings, generator bearings, motor bearings, ball screws and the like.
  • it is a device that performs rolling motion, such as a rolling bearing, a ball screw, a linear guide, etc., and may be used for high load applications.
  • it can be used for an electric cylinder, an electric linear actuator, a jack, a linear actuator, and the like.
  • a component in Table 1 is the poly alpha olefin manufactured using the metallocene catalyst.
  • M-PAO-400 and M-PAO-1200 used in this example were manufactured by the following method.
  • M-PAO-400 A stainless steel reactor with an internal volume of 107 liters was thoroughly dried, and after nitrogen substitution, 16.6 liters of 1-octene, 23.4 liters of 1-dodecene, and then 20 mmol of triisobutylaluminum were added, and the temperature was raised to 105 ° C. did.
  • the contents were withdrawn 20 liters into two 100 L stainless steel containers, 20 liters of toluene and 20 liters of a 1% by weight NaOH aqueous solution were added to each container, and stirred for 1 hour. After allowing to stand for 1 hour, the aqueous phase was extracted, 20 liters of pure water was newly added, stirred for 1 hour, and then allowed to stand for 1 hour to extract the aqueous phase. This operation was repeated twice. The organic layer was filtered through a 2 micrometer filter, then transferred to a stainless steel reactor with an internal volume of 107 liters, and light, such as toluene, raw materials, methanol, etc. at 140 ° C.
  • M-PAO-1200 Except for the polymerization temperature of 90 ° C., in the same manner as in the production of M-PAO-400, after obtaining 24.2 kg of a colorless and transparent viscous liquid from which light components were removed, components having 20 or less carbon atoms were completely removed. 4.7 kg of a colorless and transparent viscous liquid was removed, and 3.0 kg of hydride (M-PAO-1200) was obtained.
  • Examples 1 to 5 and Comparative Example 1 (1) PAO-30 [or M-PAO-30, M-PAO-45], 12-hydroxystearic acid, azelaic acid and an antirust agent in the amounts shown in Table 1 were stirred in a reaction kettle. Heated to ° C. (2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes. (3) Next, the remaining base oil (M-PAO-1200 or M-PAO-400, or olefin oligomer) was added, and then cooled to 80 ° C. at 50 ° C./hour. Antioxidant and extreme pressure agent were added and mixed. (4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Examples 1 to 5 and Comparative Example 1.
  • Comparative Examples 2-4 (1) A part of the base oil shown in Table 2 (50% by mass with respect to the finished grease amount) and the amounts of 12-hydroxystearic acid, azelaic acid and rust inhibitor shown in Table 2 in the reaction kettle. And heated to 95 ° C. with stirring. (2) Lithium hydroxide (monohydrate) was dissolved in 5 times the amount (mass ratio) of water. This aqueous solution was added to the solution of (1) and mixed by heating. After the temperature of the mixture reached 195 ° C., it was held for 5 minutes. (3) Next, after the remaining base oil was added, it was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed. (4) Further, after naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Comparative Examples 2 to 4.
  • Example 6 and Comparative Example 5 (1) 1 mol of diphenylmethane-4,4′-diisocyanate (MDI) was heated and dissolved to 2/3 mass of the total amount of the base oil to obtain raw material 1. (2) Further, 2 mol of cyclohexylamine was stirred and dissolved in the remaining base oil to obtain raw material 2. (3) Next, the raw material 2 was gradually added while vigorously stirring the raw material 1 at 50 to 60 ° C. in a grease reaction kettle. The mixture was heated while stirring, and held for 1 hour after the temperature of the grease composition reached 165 ° C. (4) Thereafter, the mixture was cooled to 80 ° C. at 50 ° C./hour, and the amounts of antioxidant and extreme pressure agent shown in Table 1 were added and mixed.
  • MDI diphenylmethane-4,4′-diisocyanate
  • Example 6 After naturally cooling to room temperature, a finishing treatment was performed using a three-roll apparatus to obtain grease compositions of Example 6 and Comparative Example 5. The following properties of the grease compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated. The results are shown in Table 2.
  • the thickener blending amount was defined as the amount of carboxylic acid (12-hydroxystearic acid + azelenic acid).
  • Low temperature torque test Measured by the method defined in JIS K 2220.18. The temperature was ⁇ 40 ° C.
  • High-load bearing wear test Measured by the method specified in DIN51819-2. (Test conditions DIN51819-2-C-75 / 50-120, load 50KN, temperature 120 ° C, rotation speed 75rpm) Test the weight of the bearing ring (inner ring + outer ring), rolling elements (total of 16 rollers), and cage Measured before and after, the respective weight loss per bearing was determined as 50% probability of wear as defined in DIN 51819-2.11.
  • the grease composition of the present invention includes various gears, various bearings (ball bearings, roller bearings, sliding bearings, pin-bushings, etc.), paper machine rollers, steel equipment bearings, construction machine slewing bearings, geared motors, automobile wheel bearings, although it can be used for a generator bearing, a motor bearing, a ball screw, etc., it can be suitably used especially as a grease composition used for a main bearing and a pitch bearing incorporated in a wind power generator.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La composition de graisse ci-décrite permet de supprimer simultanément l'usure par contact et l'usure par roulement provoquées par une charge lourde et d'augmenter la durée de vie d'un palier. De plus, ladite composition de graisse peut supprimer l'usure par contact qui se produit lors d'un changement de charge dans le sens de la poussée, ainsi que l'usure par contact à caractère général qui se produit en présence de micro-vibrations dans le sens de l'oscillation. Cette composition de graisse possède, en outre, des caractéristiques supérieures à basses températures. Elle contient une huile de base et un agent épaississant, l'huile de base contenant une poly-α-oléfine (composant A) qui est préparée à l'aide d'un catalyseur de métallocène et ayant une viscosité cinématique de 300 mm2/s ou plus à 40°C.
PCT/JP2011/057462 2010-03-26 2011-03-25 Composition de graisse WO2011118814A1 (fr)

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EP11759618.9A EP2554644A4 (fr) 2010-03-26 2011-03-25 Composition de graisse
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JPWO2019131437A1 (ja) * 2017-12-27 2020-12-10 出光興産株式会社 グリース組成物及びグリース組成物の使用方法
JPWO2019189239A1 (ja) * 2018-03-30 2021-04-01 出光興産株式会社 グリース組成物、機構部品、及びグリース組成物の製造方法
JP2021161297A (ja) * 2020-03-31 2021-10-11 出光興産株式会社 グリース組成物
JP2021187911A (ja) * 2020-05-27 2021-12-13 コスモ石油ルブリカンツ株式会社 潤滑油組成物

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JP5841129B2 (ja) * 2011-04-15 2016-01-13 Thk株式会社 グリース組成物、および該グリース組成物で潤滑された運動案内装置
WO2015000510A1 (fr) * 2013-07-03 2015-01-08 Aktiebolaget Skf Ensemble palier ayant une cartouche de lubrification
CA3134368A1 (fr) 2016-12-23 2018-06-28 Saint-Gobain Abrasives, Inc. Abrasifs appliques presentant une composition d'amelioration du rendement
CN110157525A (zh) * 2019-06-13 2019-08-23 安徽和欣润滑科技有限公司 一种汽车转向组合开关润滑脂的组合物及制备方法
CN113684084A (zh) * 2021-09-15 2021-11-23 陈伟民 一种功能性润滑油及其制备方法
WO2023179897A1 (fr) * 2022-03-25 2023-09-28 Klueber Lubrication Muenchen Se & Co. Kg Utilisation d'une composition lubrifiante pour équipement de lubrification

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US20130012416A1 (en) 2013-01-10
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