WO2023167307A1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

Info

Publication number
WO2023167307A1
WO2023167307A1 PCT/JP2023/007952 JP2023007952W WO2023167307A1 WO 2023167307 A1 WO2023167307 A1 WO 2023167307A1 JP 2023007952 W JP2023007952 W JP 2023007952W WO 2023167307 A1 WO2023167307 A1 WO 2023167307A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ethylene
lubricating oil
oil composition
olefin copolymer
Prior art date
Application number
PCT/JP2023/007952
Other languages
English (en)
Japanese (ja)
Inventor
浩貴 金谷
昌太 阿部
Original Assignee
三井化学株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三井化学株式会社 filed Critical 三井化学株式会社
Publication of WO2023167307A1 publication Critical patent/WO2023167307A1/fr

Links

Classifications

    • 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
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene

Definitions

  • the present invention relates to a lubricating oil composition used for cooling electric motors and lubricating gears in electric vehicles.
  • Electric vehicles are a mainstream technology for such fuel saving, and electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles, for example, are expected to spread rapidly in the future.
  • An electric vehicle is characterized by being equipped with an electric motor, and is partially or wholly driven by the electric motor.
  • CVTF lubricating oil compositions.
  • These lubricating oil compositions contain a variety of additives in order to provide friction control of wet clutches and the property of suppressing wear between metals (wear resistance between metals).
  • the volume resistivity is 10. It is about ⁇ 7 ⁇ m.
  • lubricating oil compositions used in electric vehicles are required not only to have excellent wear resistance between metals, but also to maintain long-term reliability in terms of insulating properties of electric motors.
  • Patent Document 1 and Patent Document 2 propose a lubricating oil composition containing a specific phosphorus compound or a specific sulfur compound, and improve lubricating oil performance such as wear resistance and extreme pressure performance of the lubricating oil composition.
  • electrical properties such as volume resistivity are discussed.
  • In-wheel motors which drive inside the wheels of electric vehicles, are being installed as powertrains in electric vehicles and fuel cell vehicles. By embedding the motor in the wheel of the wheel, the driving force is transmitted directly to the wheel, so energy loss due to gears and drive shafts, etc., is reduced unlike conventional gasoline engine vehicles. In-wheel motors, which have low energy loss, are designed to dissipate less heat generated by the transmission and motor, so higher heat dissipation is required.
  • Patent Document 3 since the amount of lubricating oil used in in-wheel motors is smaller than that of ATF and CVTF, the viscosity tends to decrease due to severe shearing, and lubrication performance tends to be emphasized. is described.
  • Patent Document 4 the lubricating oil used in the in-wheel motor provides an in-wheel motor that can improve fuel efficiency in order to meet the needs of electric wheelchairs, etc., which want to extend the traveling distance per battery charge as much as possible.
  • housing-type systems In recent years, from the perspective of fuel efficiency in electric vehicles, so-called housing-type systems have been developed in which an electric motor and a transmission or speed reduction mechanism that transmits power from the electric motor to the drive unit are integrated in order to reduce the size and weight of the vehicle.
  • the lubricating oil As the number of vehicles using this oil is increasing, the lubricating oil is required to have a cooling function to suppress excessive heat generation of the electric motor in addition to the conventional lubricating function. Therefore, there is a demand for an improvement in the electric motor cooling performance of lubricating oil.
  • the problem to be solved by the present invention is to improve the fuel efficiency and energy saving of electric vehicles such as hybrid vehicles and electric vehicles.
  • a lubricating oil composition that has a high level of oil film retention performance at high temperatures and temperature-viscosity characteristics such as fluidity at low temperatures, and is excellent in balance, and cooling of electric motors.
  • the object is to provide a lubricating oil composition having high heat dissipation performance.
  • the present inventors have made intensive studies to develop a lubricating oil composition used for cooling an electric motor and lubricating gears in an electric vehicle having excellent performance.
  • the inventors have found that a lubricating oil composition that contains a specific ethylene- ⁇ -olefin (co)polymer and satisfies specific conditions can solve the above problems, and have completed the present invention. Specifically, the following aspects are mentioned.
  • Lubricating base oil made of (A) mineral oil having the following characteristics (A1) to (A3) and / or (B) synthetic oil having the following characteristics (B1) to (B3), (C) an ethylene- ⁇ -olefin copolymer having the characteristics of (C1) to (C5) and having a kinematic viscosity at 100°C of 4 to 10 mm 2 /s, for cooling an electric motor in an electric vehicle and A lubricating oil composition used for gear lubrication.
  • the B value represented by is 1.1 or more [2]
  • C6 Thermal diffusivity at 50° C. is 8.0 ⁇ 10 ⁇ -5 to 1.0 ⁇ 10 ⁇ -4 m ⁇ 2/s
  • C7 Volume resistivity at 50° C.
  • the content of the (C) ethylene- ⁇ -olefin copolymer when the total amount of the lubricating base oil and the (C) ethylene- ⁇ -olefin copolymer is 100% by mass is 1 to 10 mass %.
  • the lubricating oil composition of the present invention has extremely excellent temperature-viscosity characteristics as compared to conventional lubricating oils containing the same lubricating base oil, that is, high temperature-viscosity characteristics such as oil film retention at high temperatures and fluidity at low temperatures. It is a lubricating oil composition that is well-balanced, has extremely excellent shear stability, can maintain lubricating oil performance in long-term use, and has high heat dissipation performance. Suitable for cooling and gear lubrication.
  • lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention will be described in detail.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle comprises (A) a mineral oil and/or (B) a synthetic oil as a lubricating base oil, and (C ) and an ethylene- ⁇ -olefin copolymer, and is characterized by having a kinematic viscosity at 100° C. within a specific range.
  • the ethylene molar content is in the range of 30 to 70 mol%.
  • the ethylene molar content of the ethylene- ⁇ -olefin copolymer is usually 30 to 70 mol%, preferably 40 to 60 mol%, and particularly preferably. is 45 to 58 mol %. If the ethylene molar content is out of this range, crystals will form at low temperatures, the low-temperature viscosity will increase, and the fuel economy of the lubricating oil composition will deteriorate.
  • (C2) Kinematic viscosity at 100°C is 10 to 5,000 mm 2 /s
  • the kinematic viscosity at 100°C is measured by the method described in JIS K2283.
  • the ethylene- ⁇ -olefin copolymer has a kinematic viscosity at 100° C. of 10 to 5,000 mm 2 /s, preferably 20 to 4,000 mm 2 /s, more preferably 25 to 3,500 mm 2 /s. , more preferably 30 to 3,000 mm 2 /s, particularly preferably 35 to 2,500 mm 2 /s. If the kinematic viscosity at 100° C.
  • (C3) Hazen chromaticity is 30 or less This value of Hazen chromaticity is measured by the method described in JIS K0071.
  • the ethylene- ⁇ -olefin copolymer has a Hazen color of 30 or less, preferably 0-30, more preferably 0-25, still more preferably 0-20.
  • the fact that the Hazen chromaticity of the (C) ethylene- ⁇ -olefin copolymer exceeds this range means that there are too many oxygen-containing functional groups in the molecule of the (C) ethylene- ⁇ -olefin copolymer. This means that the obtained lubricating oil composition has poor heat resistance and electrical insulation.
  • the molecular weight distribution is 2.5 or less.
  • the molecular weight distribution of the ethylene- ⁇ -olefin copolymer is measured by gel permeation chromatography (GPC) according to the method described later, and is obtained by standard polystyrene conversion. It is calculated as the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained. This Mw/Mn is 2.5 or less, preferably 1.0 to 2.5, more preferably 1.0 to 2.3, still more preferably 1.0 to 2.2.
  • the molecular weight distribution exceeds this range means that it contains a large amount of low molecular weight components and high molecular weight components, and if it contains a large amount of low molecular weight components, the easily volatile components increase, and the evaporation loss increases in the lubricating oil composition. In addition, the thickening effect is lowered, and when a large amount of high molecular weight components is contained, the shear stability and heat stability of the lubricating oil composition are deteriorated.
  • the B value is 1.1 or more.
  • the B value represented by the following formula [1] of the ethylene- ⁇ -olefin copolymer is 1.1 or more, preferably 1.1 to 1. .5, more preferably 1.2 to 1.4.
  • the fact that the B value exceeds this range means that the alternating polymerization property of ethylene or ⁇ -olefin in the (C) ethylene- ⁇ -olefin copolymer is lowered, and (C) the ethylene- ⁇ -olefin copolymer
  • the coalescence crystallizes at low temperatures, deteriorating the low-temperature properties of the lubricating oil composition and significantly deteriorating fuel economy.
  • P E represents the molar fraction of the ethylene component
  • PO represents the molar fraction of the ⁇ -olefin component
  • P OE represents the molar fraction of the ethylene- ⁇ -olefin chains of all the dyad chains. rate.
  • the B value is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer
  • P E , P O and P OE in the above formula [1] are measured by 13 C-NMR spectrum, J Reports by C. Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and other known documents such as "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170) can be determined based on The larger the B value, the less chain structures of ethylene and ⁇ -olefins, the more uniform the distribution of ethylene and ⁇ -olefins, and the narrower the composition distribution of the copolymer.
  • Specific measurement conditions for the B value are as described in Examples.
  • the ethylene- ⁇ -olefin copolymer preferably further has at least one characteristic of (C6) to (C8).
  • Thermal conductivity is measured at a test temperature of 50° C. in accordance with JIS R2616.
  • the specific heat is measured continuously under adiabatic conditions between 30 ° C. and 80 ° C. in an air atmosphere using a specific heat measuring device (for example, Shinku Riko SH-3000 specific heat measuring device), and the specific heat at 50 ° C. is adopted.
  • Density is measured at 50° C. in accordance with JIS K2249.
  • the thermal diffusivity at 50° C. of the ethylene- ⁇ -olefin copolymer is preferably 8.5 ⁇ 10 ⁇ -5 to 9.8 ⁇ 10 ⁇ -5m ⁇ 2/s, more preferably 8.8. ⁇ 10 ⁇ -5 to 9.6 ⁇ 10 ⁇ -5m ⁇ 2/s, more preferably 9.0 ⁇ 10 ⁇ -5 to 9.4 ⁇ 10 ⁇ -5m ⁇ 2/s.
  • the thermal diffusivity at 50° C. of (C) the ethylene- ⁇ -olefin copolymer is at least the above lower limit, the heat generation of the motor can be suppressed, and the heat resistance and electrical insulation of the lubricating oil composition are good.
  • the volume resistivity at 50°C and 250V is 1.0 x 10 ⁇ 15 to 1.0 x 10 ⁇ 17 ⁇ cm. measured at a test temperature of 50°C and 250V.
  • the volume resistivity of the ethylene- ⁇ -olefin copolymer at 50° C. and 250 V is 1.0 ⁇ 10 ⁇ 15 to 1.0 ⁇ 10 ⁇ 17 ⁇ cm, preferably 2.0 ⁇ 10 ⁇ 15 to 9.0 ⁇ 10 ⁇ 16 ⁇ cm, more preferably 3.0 ⁇ 10 ⁇ 15 to 8.0 ⁇ 10 ⁇ 16 ⁇ cm.
  • the electrical insulation of the lubricating oil composition is high, so that the safety of the electric vehicle can be maintained. can be done.
  • (C8) Relative permittivity at 50°C is 2.00 to 2.30 This value of relative permittivity at 50°C is measured at a test temperature of 50°C by the method described in JIS C2138.
  • the ethylene- ⁇ -olefin copolymer has a dielectric constant at 50°C of 2.00 to 2.30, preferably 2.00 to 2.27, and more preferably 2.00 to 2.25. is desirable.
  • the dielectric constant at 50° C. of the ethylene- ⁇ -olefin copolymer (C) is equal to or less than the above upper limit, the electrical insulation of the lubricating oil composition is high, so the safety of the electric vehicle can be maintained. .
  • the ethylene- ⁇ -olefin copolymer further preferably has at least one of the characteristics of (C9) and (C10).
  • the weight average molecular weight is 1,000 to 30,000.
  • the weight average molecular weight (Mw) of the ethylene- ⁇ -olefin copolymer is determined by gel permeation chromatography (GPC) according to the method described later. Measured and obtained by standard polystyrene conversion.
  • the weight average molecular weight (Mw) is preferably 1,200 to 25,000, more preferably 1,400 to 20,000, still more preferably 1,500 to 16,000.
  • the ethylene- ⁇ -olefin copolymer has no observed melting point in differential scanning calorimetry (DSC).
  • the melting point (Tm) is not observed means that the heat of fusion ( ⁇ H) (unit: J/g) measured by differential scanning calorimetry (DSC) is substantially not measured.
  • the fact that the heat of fusion ( ⁇ H) is not substantially measured means that no peak is observed in differential scanning calorimetry (DSC), or that the heat of fusion observed is 1 J/g or less.
  • the melting point (Tm) and heat of fusion ( ⁇ H) of the ethylene- ⁇ -olefin copolymer were measured by differential scanning calorimetry (DSC), cooled to ⁇ 100° C., and then heated at a rate of 10° C./min. It is obtained by analyzing the DSC curve with reference to JIS K7121 when the temperature is raised to 150°C. If the melting point is not observed, crystalline components do not occur at low temperatures, so an increase in low-temperature viscosity is suppressed, and the lubricating oil composition has excellent low-temperature viscosity properties.
  • DSC differential scanning calorimetry
  • (C) ⁇ -olefins used in the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, C 3-20 linear or A branched ⁇ -olefin can be exemplified.
  • the ⁇ -olefin is preferably a linear or branched ⁇ -olefin having 3 to 10 carbon atoms, more preferably propylene, 1-butene, 1-hexene and 1-octene.
  • Propylene is most preferred from the standpoint of shear stability of the lubricating oil.
  • At least one other monomer selected from polar group-containing monomers, aromatic vinyl compounds, and cyclic olefins can coexist in the reaction system to proceed with polymerization.
  • Other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on a total of 100 parts by mass of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • Polar group-containing monomers include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate; can be exemplified.
  • aromatic vinyl compounds examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, Examples include p-chlorostyrene, divinylbenzene, ⁇ -methylstyrene and allylbenzene.
  • cyclic olefins examples include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.
  • the origin of the monomer used in the ethylene- ⁇ -olefin copolymer is not particularly limited.
  • a fossil fuel-derived monomer or a biomass-derived monomer can be used. They may be used, or two or more of them may be used in combination.
  • the ethylene/ ⁇ -olefin copolymer may be composed only of a fossil fuel-derived monomer, may be composed only of a biomass-derived monomer, or may be composed of a fossil fuel-derived monomer and a biomass-derived monomer. may be used together.
  • Fossil fuels are oil, coal, natural gas, shale gas, or combinations thereof.
  • Biomass is any renewable natural raw material and its residues, such as of plant or animal origin, including fungi, yeasts, algae and bacteria.
  • the method for producing (C) the ethylene- ⁇ -olefin copolymer in the present invention is not particularly limited. and a method using a vanadium-based catalyst consisting of a compound.
  • a method for producing a copolymer with high polymerization activity metallocene compounds such as zirconocene and organic
  • a method using a catalyst system comprising an aluminum oxy compound (aluminoxane) may also be used. This method is more preferred because the chlorine content of the resulting copolymer and the 2,1-insertion of propylene can be reduced.
  • the method using a vanadium catalyst uses a greater amount of chlorine compounds in the co-catalyst, so a trace amount of chlorine may remain in the resulting ethylene- ⁇ -olefin copolymer (C). have a nature.
  • the chlorine content is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 20 ppm or less, and particularly preferably 5 ppm or less.
  • Chlorine content can be determined by various known methods. A specific measuring method in the present invention is as described in Examples.
  • the 2,1-insertion reduction of propylene makes it possible to further reduce the ethylene chains in the copolymer molecule, and the intramolecular crystallinity of ethylene can be suppressed, so the viscosity temperature characteristics of the lubricating oil composition, Low temperature viscosity characteristics can be improved.
  • an ethylene- ⁇ -olefin copolymer (C) having a good performance balance in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can be obtained.
  • the (C) ethylene- ⁇ -olefin copolymer includes a bridged metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), and an organoaluminumoxy compound (b-2). ) and a compound (b-3) that forms an ion pair by reacting with the bridged metallocene compound (a) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -olefin having 3 to 20 carbon atoms.
  • a bridged metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), and an organoaluminumoxy compound (b-2).
  • a compound (b-3) that forms an ion pair by reacting with the bridged metallocene compound (a) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -ole
  • the bridged metallocene compound (a) is represented by the above formula [I]. Y, M, R 1 to R 14 , Q, n and j in formula [I] are explained below.
  • Y is a Group 14 atom, such as carbon atom, silicon atom, germanium atom and tin atom, preferably carbon atom or silicon atom, more preferably carbon atom.
  • M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
  • R 1 to R 12 are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , may be the same or different. Adjacent substituents of R 1 to R 12 may or may not be bonded to each other to form a ring.
  • the hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, Examples include a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like.
  • alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl.
  • the number of carbon atoms in the alkyl group is preferably 1-6.
  • saturated cyclic hydrocarbon group having 3 to 20 carbon atoms examples include a saturated cyclic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4, which are groups in which the hydrogen atoms of a cyclic saturated hydrocarbon group are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 2-adamantyl group -cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like.
  • the cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
  • chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). and the like, which are alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group (propargyl group).
  • the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
  • cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group.
  • alkylene group having 1 to 20 carbon atoms examples include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, methylethylene group, n-propylene group and the like.
  • the alkylene group preferably has 1 to 6 carbon atoms.
  • arylene groups having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group.
  • the arylene group preferably has 6 to 12 carbon atoms.
  • Examples of the silicon-containing group include alkyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are hydrocarbon groups having 1 to 20 carbon atoms in which the carbon atoms are replaced with silicon atoms.
  • Examples include a silyl group, an arylsilyl group such as a dimethylphenylsilyl group, a methyldiphenylsilyl group, a t-butyldiphenylsilyl group, a pentamethyldisilanyl group, and a trimethylsilylmethyl group.
  • the alkylsilyl group preferably has 1 to 10 carbon atoms
  • the arylsilyl group preferably has 6 to 18 carbon atoms.
  • examples include amino group, diethylamino group, N-morpholinyl group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, N-morpholinyl group and nitro group.
  • the nitrogen-containing group a dimethylamino group and an N-morpholinyl group are preferred.
  • the oxygen-containing group includes a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which the —CH 2 — structural unit is replaced with an oxygen atom or a carbonyl group, or — Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl, which is a group in which the CH 3 structural unit is replaced by an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n
  • halogen atoms include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.
  • halogen-containing group include a trifluoromethyl group and a tribromo group, which are groups in which hydrogen atoms are substituted by halogen atoms in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group or oxygen-containing group having 1 to 20 carbon atoms. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.
  • Q is selected in the same or different combination from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands and neutral ligands capable of coordinating with lone electron pairs.
  • the details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above.
  • a chlorine atom is preferred when Q is a halogen atom.
  • Q is a hydrocarbon group having 1 to 20 carbon atoms
  • the hydrocarbon group preferably has 1 to 7 carbon atoms.
  • anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
  • Neutral ligands capable of coordinating with a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like. Ether compounds and the like can be exemplified.
  • j is an integer of 1 to 4, preferably 2;
  • n is an integer of 1 to 4, preferably 1 or 2, more preferably 1.
  • R 13 and R 14 are selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; atoms or substituents, each of which may be the same or different. Also, R 13 and R 14 may be bonded to each other to form a ring, or may not be bonded to each other.
  • hydrocarbon group having 1 to 20 carbon atoms The details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group are as described above.
  • the aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but is a substituent derived from an aromatic compound, namely a phenyl group, a 1-naphthyl group and a 2-naphthyl group. group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like.
  • a phenyl group or a 2-naphthyl group is preferred.
  • aromatic compounds examples include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.
  • the substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but at least one hydrogen atom of the aryl group is a hydrocarbon group having 1 to 20 carbon atoms,
  • bridged metallocene compound (a) represented by formula [I] above n is preferably 1.
  • bridged metallocene compound (a-1) is represented by the following general formula [II].
  • the bridged metallocene compound (a-1) has a simpler production process and a lower production cost than the compound in which n is an integer of 2 to 4 in the above formula [I].
  • the use of 1) provides the advantage of reducing the production cost of (C) the ethylene- ⁇ -olefin copolymer.
  • bridged metallocene compound (a-2) represented by the above formula [II]
  • R 1 , R 2 , R 3 and R 4 are all preferably hydrogen.
  • Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-2)”) is represented by the following general formula [III].
  • the bridged metallocene compound (a-2) has a lower manufacturing process than a compound in which one or more of R 1 , R 2 , R 3 and R 4 in the above formula [I] is substituted with a substituent other than a hydrogen atom. is simplified, the production cost is reduced, and the use of the crosslinked metallocene compound (a-2) further reduces the production cost of the ethylene- ⁇ -olefin copolymer (C). Further, it is generally known that the randomness of (C) an ethylene- ⁇ -olefin copolymer is reduced by carrying out high-temperature polymerization. When ethylene and one or more monomers selected from ⁇ -olefins having 3 to 20 carbon atoms are copolymerized in the presence of the It also has the advantage of being highly random.
  • either one of R 13 and R 14 is preferably an aryl group or a substituted aryl group.
  • Such a bridged metallocene compound (a-3) produces (C) an ethylene- ⁇ -olefin copolymer as compared with the case where both R 13 and R 14 are substituents other than an aryl group and a substituted aryl group.
  • one of R 13 and R 14 is more preferably an aryl group or a substituted aryl group, and the other is an alkyl group having 1 to 20 carbon atoms. It is particularly preferred that either one of R 14 is an aryl group or substituted aryl group and the other is a methyl group.
  • bridged metallocene compound (a- 4 ) the produced (C) ethylene -
  • the increase in the hydrogen partial pressure due to the introduction of hydrogen causes a decrease in the partial pressure of the olefin, which is the polymerization monomer, especially in the region where the hydrogen partial pressure is high. causes a problem of slowing down the polymerization rate. Since the polymerization reactor has a limited internal total pressure due to its design, if excessive hydrogen introduction is required especially when producing a low-molecular-weight olefin polymer, the olefin partial pressure will drop significantly. Polymerization activity may decrease.
  • the polymerization reactor is more The amount of hydrogen introduced into is reduced, the polymerization activity is improved, and the production cost of (C) the ethylene- ⁇ -olefin copolymer is reduced.
  • bridged metallocene compound (a-4) R 6 and R 11 are alkyl groups having 1 to 20 carbon atoms or An alkylene group is preferred.
  • Such a bridged metallocene compound hereinafter also referred to as “bridged metallocene compound (a-5)”) has a substituted Compared to a compound substituted with a group, the production process is simplified, the production cost is reduced, and the production cost of the (C) ethylene- ⁇ -olefin copolymer is reduced by using this crosslinked metallocene compound (a-5). has the advantage of being reduced.
  • the bridged metallocene compound (a) represented by the general formula [I], the bridged metallocene compound (a-1) represented by the general formula [II], the bridged metallocene compound represented by the general formula [III] ( In a-2) and the above bridged metallocene compounds (a-3), (a-4) and (a-5), M is more preferably a zirconium atom.
  • ⁇ 5 -tetramethyloctahydrodibenzofluorenyl which is a constituent part of the exemplified bridged metallocene compound (a), is 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a- ⁇ 5 ) -1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group
  • ⁇ 5 -octamethyloctahydrodibenzofluorenyl is 1,1,4,4, 7,7,10,10-octamethyl-(5a,5b,11a,12,12a- ⁇ 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl each represents a group.
  • the olefin polymerization catalyst reacts with the bridged metallocene compound (a), the organometallic compound (b-1), the organoaluminum oxy compound (b-2) and the bridged metallocene compound (a) to form an ion pair. It contains at least one compound (b) selected from the group consisting of compounds (b-3).
  • organometallic compound (b-1) specifically, the following organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table are used.
  • tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum
  • Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum
  • tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum
  • triarylaluminum such as triphenylaluminum, tri(4-methylphenyl)aluminum, dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylalum
  • alkylaluminum aryloxides such as alkylaluminum aryloxides, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminums, Part
  • (b-1b) of the general formula M 2 AlR a 4 (wherein M 2 represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms); A complex alkylate of a Group 1 metal of the periodic table and aluminum represented.
  • Examples of such compounds include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 .
  • R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; , M 3 is Mg, Zn or Cd).
  • organoaluminumoxy compound (b-2) conventionally known aluminoxanes can be used as they are. Specifically, compounds represented by the following general formula [IV] and compounds represented by the following general formula [V] can be mentioned.
  • R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
  • methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used.
  • These aluminoxanes may be mixed with a small amount of organoaluminum compounds.
  • a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687 is also applied. be able to.
  • the "benzene-insoluble organoaluminumoxy compound” that may be used in the present invention means that the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, particularly preferably 5% or less, in terms of Al atoms. It is a compound that is 2% or less and is insoluble or sparingly soluble in benzene.
  • organoaluminumoxy compound (b-2) examples include modified methylaluminoxane represented by the following general formula [VI].
  • R is a hydrocarbon group having 1 to 10 carbon atoms, m and n each independently represent an integer of 2 or more.
  • This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • Such compounds are commonly referred to as MMAO.
  • Such MMAOs can be prepared by methods set forth in US Pat. Nos. 4,960,878 and 5,041,584.
  • Tosoh Finechem Co., Ltd. and the like also sell products prepared using trimethylaluminum and triisobutylaluminum under the names of MMAO and TMAO, in which R is an isobutyl group.
  • MMAO is an aluminoxane with improved solubility in various solvents and storage stability.
  • the compounds represented by the above formula [IV] and [V] Unlike insoluble or sparingly soluble compounds, it dissolves in aliphatic and alicyclic hydrocarbons.
  • organoaluminumoxy compound (b-2) an organoaluminumoxy compound containing boron represented by the following general formula [VII] can also be mentioned.
  • R c represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R d may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • the compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound” or simply “ionic compound") is JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Patent Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-5321106. In addition, heteropolycompounds and isopolycompounds may also be mentioned.
  • the ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VIII].
  • R e+ includes H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like.
  • R f to R i may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.
  • carbenium cations include triphenylcarbenium cations, tris(4-methylphenyl)carbenium cations, and trisubstituted carbenium cations such as tris(3,5-dimethylphenyl)carbenium cations. .
  • ammonium cation examples include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation.
  • N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, and dialkylammonium cations such as dicyclohexylammonium cations.
  • phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(4-methylphenyl)phosphonium cations, and tris(3,5-dimethylphenyl)phosphonium cations.
  • R e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.
  • compounds containing carbenium cations include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis ⁇ 3, 5-di-(trifluoromethyl)phenyl ⁇ borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, etc. can be exemplified.
  • compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and trimethylammonium.
  • compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl ) borate, N,N-dimethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl) Borate, N,N-diethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4 , 6-pentamethylanilinium
  • di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like can be exemplified as compounds containing dialkylammonium cations.
  • JP-A-2004-51676 can also be used without restriction.
  • the above ionic compound (b-3) may be used alone or in combination of two or more.
  • organometallic compound (b-1) trimethylaluminum, triethylaluminum and triisobutylaluminum, which are commercially available and readily available, are preferred. Among these, triisobutylaluminum is particularly preferable because it is easy to handle.
  • organoaluminumoxy compound (b-2) methylaluminoxane, which is a commercially available product and is readily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred.
  • MMAO which has improved solubility in various solvents and improved storage stability, is particularly preferred.
  • triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylaniline are readily available as commercial products and greatly contribute to the improvement of polymerization activity. Nium tetrakis(pentafluorophenyl)borate is preferred.
  • a combination of triisobutylaluminum and triphenylcarbenium tetrakis(pentafluorophenyl)borate, and a combination of triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are used, since they significantly improve the polymerization activity.
  • a combination with fluorophenyl)borate is particularly preferred.
  • a carrier (c) may optionally be used as a component of the olefin polymerization catalyst.
  • the carrier (c) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid.
  • inorganic compounds porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds are preferred.
  • porous oxides include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and the like, or composites or mixtures containing these, such as Using natural or synthetic zeolite, SiO2 - MgO, SiO2 - Al2O3 , SiO2 - TiO2 , SiO2 - V2O5 , SiO2 - Cr2O3 , SiO2 - TiO2 - MgO , etc. can do. Among these, those containing SiO 2 and/or Al 2 O 3 as main components are preferred. The properties of such porous oxides vary depending on the type and manufacturing method.
  • a carrier is in the range of 50-1000 m 2 /g, preferably 100-700 m 2 /g, and the pore volume is in the range of 0.3-3.0 cm 3 /g.
  • Such a carrier is used after being calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.
  • inorganic chlorides MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 and the like are used.
  • the inorganic chloride may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic chloride in a solvent such as alcohol, the inorganic chloride may be precipitated in the form of fine particles using a precipitating agent.
  • Clay is usually composed mainly of clay minerals.
  • An ion-exchangeable layered compound is a compound having a crystal structure in which planes are stacked in parallel with a weak bonding force due to ionic bonds or the like, and the ions contained therein can be exchanged.
  • Most clay minerals are ion exchange layered compounds.
  • these clays, clay minerals, and ion-exchangeable layered compounds not only naturally occurring ones but also artificially synthesized ones can be used.
  • Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds.
  • Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite.
  • the ion-exchangeable layered compounds include ⁇ -Zr(HAsO 4 ) 2.H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr(KPO 4 ) 2.3H 2 O, ⁇ -Ti( HPO4 ) 2 , ⁇ -Ti( HAsO4 )2.H2O, ⁇ -Sn( HPO4 ) 2.H2O , ⁇ -Zr( HPO4 ) 2 , ⁇ - Ti ( HPO4 ) 2 and crystalline acid salts of polyvalent metals such as ⁇ -Ti(NH 4 PO 4 ) 2 ⁇ H 2 O and the like.
  • any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like.
  • Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.
  • the ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability.
  • Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars.
  • the introduction of another substance (guest compound) between the layers of a layered compound is called intercalation.
  • Guest compounds include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon groups), [ Al13O4 ( OH) 24 ] 7+ , [ Zr4 (OH) 14 ] 2+ , [ Fe3O ( OCOCH3 ) 6 ] + , metal hydroxide ions such as . These compounds are used singly or in combination of two or more.
  • metal alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 are hydrolyzed and polycondensed.
  • the resulting polymer a colloidal inorganic compound such as SiO 2 , etc., can also coexist.
  • pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.
  • clays or clay minerals preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
  • Examples of the organic compound as the carrier (c) include granular or particulate solids with a particle size in the range of 0.5 to 300 ⁇ m.
  • (co)polymers produced mainly from ⁇ -olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.
  • High-temperature polymerization is possible with a polymerization method that uses an olefin polymerization catalyst capable of producing (C) ethylene- ⁇ -olefin copolymer with high randomness. That is, by using the olefin polymerization catalyst, it is possible to suppress the decrease in the randomness of the (C) ethylene- ⁇ -olefin copolymer produced during high-temperature polymerization.
  • the viscosity of the polymerization solution containing the (C) ethylene- ⁇ -olefin copolymer produced decreases at high temperatures, so the (C) ethylene- ⁇ -olefin copolymer in the polymerization vessel is lower than during low-temperature polymerization.
  • Copolymerization of ethylene and ⁇ -olefin in the present invention can be carried out by either liquid phase polymerization method such as solution polymerization or suspension polymerization (slurry polymerization) or gas phase polymerization method.
  • Solution polymerization is particularly preferred from the viewpoint of being able to enjoy the maximum.
  • each component of the olefin polymerization catalyst is arbitrarily selected. At least two or more of each component in the catalyst may be contacted in advance.
  • the amount of the bridged metallocene compound (a) (hereinafter also referred to as “component (a)”) is generally 1 ⁇ 10 -9 to 1 ⁇ 10 -1 mol, preferably 1 ⁇ 10 -8 to 1 ⁇ 10 -1 mol, per liter of reaction volume. It is used in an amount to give 10 -2 mol.
  • the organometallic compound (b-1) (hereinafter also referred to as “component (b-1)”) has a molar ratio [( b-1)/M] is usually 0.01 to 50,000, preferably 0.05 to 10,000.
  • the organoaluminumoxy compound (b-2) (hereinafter also referred to as “component (b-2)”) is composed of the aluminum atom in component (b-2) and the transition metal atom (M) in component (a). is used in such an amount that the molar ratio [(b-2)/M] of is usually 10 to 5,000, preferably 20 to 2,000.
  • the ionic compound (b-3) (hereinafter also referred to as “component (b-3)”) has a molar ratio [( b-3)/M] is usually 1 to 10,000, preferably 1 to 5,000.
  • the polymerization temperature is usually -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, still more preferably 130°C to 200°C. In the polymerization temperature range within the above range, the higher the temperature, the lower the viscosity of the solution during polymerization, making it easier to remove the heat of polymerization.
  • the polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
  • the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
  • the molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of component (b) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of copolymer produced.
  • the polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure.
  • the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. and particularly preferably hexane, heptane, octane, decane, and cyclohexane.
  • the ⁇ -olefin to be polymerized itself can also be used as a polymerization solvent.
  • Aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents. From the viewpoint of minimizing the impact of
  • the kinematic viscosity of olefin polymers at 100°C depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity will be high, and if the molecular weight is low, the viscosity will be low.
  • the molecular weight distribution (Mw/Mn) of the resulting polymer can be adjusted by removing low molecular weight components from the polymer obtained by a conventionally known method such as vacuum distillation.
  • the obtained polymer may be hydrogenated (hereinafter also referred to as hydrogenation) by a conventionally known method. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.
  • the obtained (C) ethylene- ⁇ -olefin copolymer may be used alone, or two or more of them having different molecular weights or different monomer compositions may be used in combination.
  • the ethylene- ⁇ -olefin copolymer may be graft modified with functional groups, or these may be further modified secondary.
  • the methods described in JP-A-61-126120, JP-A-2593264, etc., and secondary modification include the methods described in JP-A-2008-508402.
  • (A) Mineral oil has the following characteristics (A1) to (A3).
  • Kinematic viscosity at 100° C. is 2 to 6 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283.
  • the kinematic viscosity at 100° C. of mineral oil is 2 to 8 mm 2 /s, preferably 2.3 to 5.5 mm 2 /s, more preferably 2.8 to 5 mm 2 /s.
  • the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
  • Viscosity index is 105 or more This value of viscosity index is measured according to the method described in JIS K2283.
  • the mineral oil has a viscosity index of 105 or higher, preferably 110 or higher, and more preferably 115 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
  • pour point is ⁇ 5° C. or less This value of pour point is measured according to the method described in ASTM D97.
  • the pour point of the mineral oil is -5°C or lower, more preferably -10°C or lower, and still more preferably -12°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
  • the synthetic oil has the following characteristics (B1) to (B3).
  • Kinematic viscosity at 100° C. is 1 to 9 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283.
  • the kinematic viscosity at 100° C. of the synthetic oil is 1 to 9 mm 2 /s, preferably 1.5 to 7 mm 2 /s, more preferably 1.8 to 5 mm 2 /s.
  • the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
  • Viscosity index is 110 or more This value of viscosity index is measured according to the method described in JIS K2283.
  • the synthetic oil has a viscosity index of 110 or higher, preferably 115 or higher, more preferably 120 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
  • pour point is ⁇ 30° C. or lower This value of pour point is measured according to the method described in ASTM D97.
  • the pour point of the synthetic oil is -30°C or lower, preferably -40°C or lower, more preferably -50°C or lower, and still more preferably -60°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
  • the lubricating base oil used in the present invention varies in performance and quality such as viscosity characteristics, heat resistance, and oxidation stability depending on the manufacturing method and refining method, but is generally divided into mineral oil and synthetic oil.
  • API American Petroleum Institute
  • (A) Mineral oils may be any of Groups I-III in the API category and
  • Synthetic oils may be any of Groups IV and V in the API category. Details are given below.
  • the quality of the mineral oil is as described above, and the mineral oil of each quality described above can be obtained by the refining method.
  • the mineral oil specifically, the lubricating oil fraction obtained by vacuum distillation of the atmospheric residue obtained by atmospheric distillation of crude oil is subjected to solvent deasphalting, solvent extraction, hydrocracking, solvent deasphalting.
  • Lubricating base oils such as those refined by one or more treatments such as waxes, hydrorefining, or wax isomerized mineral oils can be exemplified.
  • a gas-to-liquid (GTL) base oil obtained by the Fischer-Tropsch process is also a base oil that can be suitably used as a Group III mineral oil.
  • Such GTL base oils may also be treated as Group III+ lubricant base oils, e.g. , WO00/14179, WO00/08115, WO99/41332, EP1029029, WO01/18156 and WO01/57166.
  • Poly- ⁇ -olefins belonging to Group IV are disclosed in US Pat. No. 3,382,291, US Pat. No. 3,763,244, US Pat. 780,128, US Pat. No. 4,032,591, JP-A-1-163136, US Pat. No. 4,967,032, US Pat. No. 4,926,004 It can be obtained by oligomerization with an acid catalyst such as boron trifluoride or a chromic acid catalyst. Further, a metallocene compound as described in JP-A-63-037102, JP-A-2005-200447, JP-A-2005-200448, JP-A-2009-503147, JP-A-2009-501836.
  • Poly- ⁇ -olefins are also commercially available, and those with kinematic viscosities at 100° C. of 2 mm 2 /s to 300 mm 2 /s are commercially available. Among them, it is preferable to use a poly- ⁇ -olefin of 2 to 6 mm 2 /s in that a lubricating oil composition having excellent temperature-viscosity characteristics can be obtained. Examples include the NEXBASE2000 series manufactured by NESTE, the Spectrasyn series manufactured by ExxonMobil Chemical, the Durasyn series manufactured by Ineos Oligmers, and the Synfluid series manufactured by Chevron Phillips Chemical.
  • Synthetic oils belonging to Group V include, for example, alkylbenzenes, alkylnaphthalenes, isobutene oligomers or hydrides thereof, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, and esters.
  • alkylbenzenes and alkylnaphthalenes are usually dialkylbenzenes or dialkylnaphthalenes having an alkyl chain length of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalenes are free from benzene or naphthalene and olefins. It is produced by the Delcraft alkylation reaction.
  • Alkylated olefins used in the production of alkylbenzenes or alkylnaphthalenes can be linear or branched olefins or combinations thereof. These manufacturing methods are described, for example, in US Pat. No. 3,909,432.
  • the ester is preferably a fatty acid ester from the viewpoint of compatibility with (C) the ethylene- ⁇ -olefin copolymer.
  • Fatty acid esters are not particularly limited, but include the following fatty acid esters consisting only of carbon, oxygen, and hydrogen.
  • esters include ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, tridecyl pelargonate, di-2-ethylhexyl adipate, di-2 -ethylhexyl azelate, trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane triheptanoate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, pentaerythritol tetraheptanoate, etc. .
  • the alcohol moiety constituting the ester is preferably an alcohol having a hydroxyl group of two or more functional groups, and the fatty acid moiety is a fatty acid having 8 or more carbon atoms. is preferred.
  • fatty acids with 20 or less carbon atoms which are industrially readily available, are superior in terms of production cost.
  • the fatty acid constituting the ester may be of one kind, or the effect of the present invention can be sufficiently exhibited even if a fatty acid ester produced by using a mixture of two or more kinds of acids is used.
  • fatty acid esters include trimethylolpropane lauric stearic acid mixed triesters and diisodecyl adipate, which are combined with saturated hydrocarbon components such as (C) ethylene- ⁇ -olefin copolymers.
  • saturated hydrocarbon components such as (C) ethylene- ⁇ -olefin copolymers.
  • stabilizers such as antioxidants, corrosion inhibitors, antiwear agents, friction modifiers, pour point depressants, rust inhibitors and antifoaming agents having polar groups, which will be described later.
  • the lubricating oil composition of the present invention contains 1 to 20 fatty acid esters when the total lubricating oil composition is 100% by mass when (B) synthetic oil, particularly poly- ⁇ -olefin, is used as the lubricating base oil. It is preferably included in the amount of % by mass.
  • By containing 1% by mass or more of fatty acid ester good compatibility with lubricating oil sealing materials such as resins and elastomers in electric vehicles can be obtained. Specifically, swelling of the lubricating oil sealing material can be suppressed. From the viewpoint of oxidation stability or heat resistance, the amount of ester is preferably 20% by mass or less.
  • the mineral oil itself has the effect of suppressing the swelling of the lubricating oil sealant, so the fatty acid ester is not necessarily required.
  • (B) Synthetic oil is preferable in that it is superior to (A) mineral oil in terms of heat resistance and temperature-viscosity characteristics.
  • (A) mineral oil or (B) synthetic oil may be used alone as the lubricating base oil, and (A) mineral oil and (B) synthetic oil Any mixture of two or more lubricating oils selected from may be used.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention includes (A) mineral oil and/or (B) synthetic oil and (C) ethylene- ⁇ - It contains an olefin copolymer and has the following characteristics of (D1).
  • Kinematic viscosity at 100°C is 4 to 10 mm 2 /s
  • the kinematic viscosity at 100°C (kinematic viscosity measured according to the method described in JIS K2283) is 4 to 10 mm 2 /s, preferably 4 ⁇ 7.5 mm 2 /s, more preferably 4 to 6.5 mm 2 /s, still more preferably 4.2 to 6 mm 2 /s. If the kinematic viscosity at 100° C. of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle excessively exceeds 10 mm 2 /s, the stirring resistance of the lubricating oil to the gears, metal chains, etc. If it is excessively smaller than 4 mm 2 /s, metal contact may occur between gears or metal chains.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention preferably further has characteristics (D2) and (D3).
  • Viscosity index is 110 or more
  • This viscosity index (viscosity index measured according to the method described in JIS K2283) is preferably 110 or more, more preferably 120 or more, still more preferably 125 or more, and particularly preferably 130 or more.
  • the viscosity index is within this range, the lubricating oil composition has excellent temperature-viscosity characteristics, and it becomes possible to achieve both the energy saving property and lubricity over a wide range of temperatures.
  • the pour point is ⁇ 40° C. or less
  • the pour point of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention (measured according to the method described in ASTM D97)
  • the pour point) is preferably ⁇ 40° C. or lower, more preferably ⁇ 45° C. or lower, and still more preferably ⁇ 50° C. or lower.
  • a low pour point indicates that the lubricating oil composition has excellent low temperature properties.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains 90 to 99 It is preferable to contain the (C) ethylene- ⁇ -olefin copolymer in a proportion of 10 to 1% by mass. However, the total amount of the lubricating base oil and the ethylene- ⁇ -olefin copolymer (C) is 100% by mass.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention preferably contains 92 to 99% by mass of the lubricating base oil and the (C) ethylene- ⁇ -olefin co- 8 to 1% by mass of the polymer, more preferably 95 to 99% by mass of the lubricating base oil, and 5 to 1% by mass of the (C) ethylene- ⁇ -olefin copolymer, More preferably, it contains 96 to 99% by mass of the lubricating base oil and 4 to 1% by mass of the ethylene- ⁇ -olefin copolymer (C).
  • the lubricating base oil is (A) mineral oil.
  • (A) mineral oil When the proportion of (A) mineral oil in the base oil of the lubricating oil is high, the solubility of the additives described later is excellent, and the oil is easily available and economical. More preferably 50 to 100% by mass mineral oil, and even more preferably 80 to 100% by mass mineral oil.
  • group III in the API category is preferable because it has excellent temperature-viscosity characteristics and can achieve both oil film retention at high temperatures and low torque at low temperatures.
  • 30 to 100% by mass of the lubricating base oil is (B) synthetic oil, and (B) synthetic oil is poly- ⁇ -olefin and / or ester oil aspects. It is more preferably 50 to 100% by mass of synthetic oil, and even more preferably 80 to 100% by mass of synthetic oil.
  • a high proportion of the synthetic oil (B) in the base oil of the lubricating oil is preferable because the heat resistance, temperature-viscosity characteristics, and low-temperature characteristics are excellent.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains extreme pressure agents, detergent-dispersants, viscosity index improvers, antioxidants, corrosion inhibitors, anti-wear agents. additives such as agents, friction modifiers, pour point depressants, rust inhibitors and defoamers.
  • additives used in the lubricating oil composition of the present invention include the following, and these can be used singly or in combination of two or more.
  • Extreme pressure agent is a general term for substances that have an effect of preventing seizure when metals are exposed to a high load, and is not particularly limited, but includes sulfides, sulfoxides, sulfones, thiophosphinates, and thiocarbonates. Sulfur-based extreme pressure agents such as sulfurized oils and fats and sulfurized olefins; etc. can be exemplified. Also, two or more of these compounds may be used in combination.
  • hydrocarbons or other organic components constituting the lubricating oil composition are carbonized by heating and shearing before the extreme pressure lubrication conditions, forming a carbide film on the metal surface.
  • the carbide coating inhibits the contact between the extreme pressure agent and the metal surface, and there is a possibility that the extreme pressure agent cannot be expected to have a sufficient effect.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention is mainly composed of saturated hydrocarbons such as copolymers. From the standpoint of dispersibility, it is preferable to add it in a state dissolved in a lubricating base oil such as a mineral oil or a synthetic hydrocarbon oil together with other additives that are used in advance.
  • a so-called additive package in which various components such as extreme pressure agent components are blended in advance and dissolved in a lubricating base oil such as mineral oil or synthetic hydrocarbon oil, is selected and added to the lubricating oil composition. A method of adding is more preferable.
  • Lubricating oils used for cooling electric motors and lubricating gears in electric vehicles contain various necessary additives for lubricating oils for automatic transmission oils and continuously variable transmission oils, and are either mineral oils or synthetic hydrocarbon oils.
  • a so-called DI package which is concentrated and dissolved in a lubricating oil such as a lubricating oil, is industrially supplied.
  • DI packages for machine oils include Lubrizol 6373 manufactured by LUBRIZOL, and these DI packages can also be applied to the lubricating oil composition of the present invention.
  • the extreme pressure agent is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • antiwear agents include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and polytetrafluoroethylene.
  • the antiwear agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • Friction modifiers include amine compounds, imide compounds, and fatty acids having at least one alkyl or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl or alkenyl group having 6 to 30 carbon atoms in the molecule.
  • Examples include esters, fatty acid amides, fatty acid metal salts, and the like.
  • amine compound linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or these aliphatic Alkylene oxide adducts of group amines and the like can be exemplified.
  • imide compound include succinimide having a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms and/or modified compounds thereof with carboxylic acid, boric acid, phosphoric acid, sulfuric acid, etc. .
  • fatty acid esters include esters of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols.
  • fatty acid amides include amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms and aliphatic monoamines or aliphatic polyamines.
  • fatty acid metal salts include alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms.
  • the friction modifier is used in the range of 0.01 to 5.0% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • detergent-dispersants include metal sulfonates, metal phenates, metal phosphanates, and succinimides.
  • Detergency-dispersants are used in the range of 0 to 15% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • Viscosity index improvers include ethylene- ⁇ -olefin copolymers (excluding (C) ethylene- ⁇ -olefin copolymers), olefin copolymers with a molecular weight exceeding 50,000, and methacrylate-based copolymers.
  • Known viscosity index improvers such as polymers, liquid polybutene, and poly- ⁇ -olefins having a kinematic viscosity of 15 mm 2 /s or more at 100° C. can be used in combination.
  • a viscosity index improver is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • Antioxidants include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol. Antioxidants are used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • Corrosion inhibitors include compounds such as benzotriazole, benzimidazole, and thiadiazole. Corrosion inhibitors are optionally used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition.
  • rust preventives examples include compounds such as various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates.
  • the antirust agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • antifoaming agents examples include silicone-based compounds such as dimethylsiloxane and silica gel dispersions, and alcohol-based or ester-based compounds. Antifoaming agents are used in the range of 0 to 0.2% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • a polymer compound containing an organic acid ester group is used, and a vinyl polymer containing an organic acid ester group is particularly preferably used.
  • Vinyl polymers containing an organic acid ester group include, for example, alkyl methacrylate (co)polymers, alkyl acrylate (co)polymers, alkyl fumarate (co)polymers, and alkyl maleate (co)polymers. Examples include polymers, alkylated naphthalenes, etc., preferably (co)polymers of alkyl acrylates, more preferably (co)polymers of alkyl acrylates ( co) polymer.
  • Such a pour point depressant has a melting point of -13°C or lower, preferably -15°C or lower, more preferably -17°C or lower.
  • the melting point of pour point depressants is measured using a differential scanning calorimeter (DSC). Specifically, about 5 mg of the sample was packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, cooled to -40 ° C. at 10 ° C./min, and held at -40 ° C. for 5 minutes. After that, it is obtained from the endothermic curve when the temperature is raised at 10°C/min.
  • DSC differential scanning calorimeter
  • the pour point depressant further has a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography in the range of 20,000 to 400,000, preferably 30,000 to 300,000, more preferably 40,000. ⁇ 200,000.
  • the pour point depressant is optionally 0 to 2% by mass, preferably 0.01 to 1% by mass, more preferably 0.02 to 0.4% by mass, based on 100% by mass of the lubricating oil composition, and further It is preferably used in the range of 0.05 to 0.35% by mass. If the amount of the pour point depressant added exceeds the above range, the shear stability of the lubricating oil composition may decrease, and lubricity may deteriorate due to the low viscosity. Moreover, the pour point depressing ability may also be impaired.
  • demulsifiers In addition to the above additives, demulsifiers, colorants, oiliness agents (oiliness improvers), etc. can be used as necessary.
  • DI packages are industrially supplied.
  • DI packages for automatic transmission oils include HITEC3419D manufactured by AFTON CHEMICAL and HITEC2426 manufactured by AFTON CHEMICAL
  • DI packages for continuously variable transmission oils include Lubrizol6373 manufactured by LUBRIZOL. but these DI packages can also be applied to the lubricating oil composition of the present invention.
  • the lubricating oil composition of the present invention can be used, for example, for cooling electric motors and lubricating gears mounted in electric vehicles such as electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles.
  • electric vehicles such as electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles.
  • the lubricating oil has extremely excellent temperature-viscosity properties, that is, oil film retention at high temperatures and low-temperature viscosity properties, and can greatly contribute to the energy saving of electric vehicles.
  • the distance between the gear and the electric motor is short, that is, it is particularly useful for an electric vehicle equipped with an in-wheel motor that requires high heat dissipation.
  • the lubricating oil composition of the present invention has extremely excellent heat dissipation performance, it has not only lubricating performance for gears and bearings of electric vehicles but also high cooling performance for electric motors.
  • the lubricating oil composition of the present invention is extremely useful for cooling electric motors and lubricating gears in electric vehicles.
  • Mw Weight average molecular weight
  • Mw/Mn molecular weight distribution
  • Molecular weight distribution was measured as follows using Tosoh Corporation HLC-8320GPC.
  • TSKgel SuperMultiporeHZ-M 4 columns
  • the column temperature was set to 40 ° C.
  • tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • the development rate was set to 0.35 ml / min
  • the sample concentration was set to The concentration was 5.5 g/L
  • the sample injection amount was 20 microliters
  • a differential refractometer was used as a detector.
  • ⁇ B value> o-Dichlorobenzene/benzene-d 6 (4/1 [vol/vol%]) was used as the measurement solvent, the measurement temperature was 120°C, the spectrum width was 250 ppm, the pulse repetition time was 5.5 seconds, and the pulse width was 4.7 ⁇ s ( 45 ° pulse) measurement conditions (100 MHz, JEOL ECX400P), or measurement temperature 120 ° C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, and pulse width 5.0 ⁇ s (45 ° pulse) measurement conditions 13 C-NMR spectrum was measured at (125 MHz, Bruker Biospin AVANCE IIIcryo-500), and the B value was calculated based on the following formula [1]. Attribution of peaks was performed with reference to the above-mentioned known literature.
  • P E represents the molar fraction of the ethylene component
  • PO represents the molar fraction of the ⁇ -olefin component
  • P OE represents the molar fraction of the ethylene- ⁇ -olefin chains of all the dyad chains. rate.
  • the thermal diffusivity is expressed by the following formula by determining the thermal conductivity, specific heat, and density of the lubricating oil composition.
  • Thermal conductivity was measured at a test temperature of 50° C. in accordance with JIS R2616.
  • the specific heat was measured continuously under adiabatic conditions between 30°C and 80°C in an air atmosphere using a specific heat measuring device SH-3000 manufactured by SHINKU RIKO, and the specific heat at 50°C was adopted. Density was measured at 50° C. in accordance with JIS K2249.
  • volume resistivity was measured at a test temperature of 50° C. and 250 V according to JIS C2101.
  • ⁇ Dielectric constant> The dielectric constant was measured at a test temperature of 50°C in accordance with JIS C2138.
  • ⁇ Melting point> Using Seiko Instruments X-DSC-7000, put about 8 mg of ethylene- ⁇ -olefin copolymer in an aluminum sample pan that can be easily sealed and place it in the DSC cell. The temperature was raised to 150° C. at 10° C./min, then held at 150° C. for 5 minutes, and then lowered at 10° C./min to cool the DSC cell to ⁇ 100° C. (temperature drop process). Next, after holding at 100° C. for 5 minutes, the temperature is raised at 10° C./min. The temperature at which the enthalpy curve obtained in the heating process shows the maximum value is defined as the melting point (Tm), and the sum of the endothermic amounts accompanying melting is the melting point.
  • Tm melting point
  • Chlorine content was determined by using ICS-1600 from Thermo Fisher Scientific Co., Ltd., and ethylene- ⁇ -olefin copolymer was placed in a sample boat and burned and decomposed in an Ar/O 2 stream at a combustion furnace setting temperature of 900°C. . The generated gas at this time was absorbed into the absorbent and quantified by ion chromatography.
  • ⁇ Shear stability> The lubricating oil composition was subjected to ultrasonic irradiation for 60 minutes in accordance with JASO M347, which is an automatic transmission oil shear stability test method, and the reduction rate of kinematic viscosity at 100 ° C. due to irradiation represented by the following formula. (Viscosity reduction rate after shear test) was evaluated.
  • Ethylene- ⁇ -olefin copolymer (B) was produced according to the following polymerization examples.
  • the obtained ethylene- ⁇ -olefin copolymer (B) was hydrogenated by the following method, if necessary.
  • ⁇ Hydrogenation operation 100 mL of a hexane solution of 0.5% by mass Pd/alumina catalyst and 500 mL of a 30% by mass hexane solution of an ethylene- ⁇ -olefin copolymer were added to a 1 L stainless steel autoclave, and the autoclave was sealed and then purged with nitrogen. Ta. Then, the temperature was raised to 140° C. with stirring, and after the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.
  • the solid obtained by evaporating the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After concentrating by distilling off the solvent under reduced pressure, a small amount of hexane was added, and the mixture was allowed to stand at -20°C to precipitate a reddish orange solid. This solid was washed with a small amount of hexane and then dried under reduced pressure to obtain [methylphenylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -2,7-di-t-butylphenyl) as a reddish-orange solid. 1.20 g of olenyl)]zirconium dichloride are obtained.
  • Polymerization was initiated by charging a polymerization vessel with 0.00230 mmol of zirconium dichloride premixed in toluene for 15 minutes or longer. After that, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 50° C. for 15 minutes. After stopping the polymerization by adding a small amount of isobutyl alcohol into the system, unreacted monomer was purged. The resulting polymer solution was washed with 100 mL of 0.2 mol/l hydrochloric acid three times and then with 100 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 1.43 g of an ethylene-propylene copolymer. Furthermore, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 4.
  • PMA Polymethacrylate
  • PAO Evonik Poly ⁇ olefin
  • PIB Spectrasyn PAO-100 from ExxonMobil Chemical Polybutene
  • A Mineral oil; 100° C. kinematic viscosity: 3.1 mm 2 /s, viscosity index: 115, pour point: -24° C. API (American Petroleum Institute) Group II mineral oil (SK Lubricants Yubase-3)
  • Example 2 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 2 and the amount of each component added was adjusted as shown in Table 3.
  • Table 3 shows the physical properties of the lubricating oil composition.
  • Example 3 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 3 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 4 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 4 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 1 A lubricating oil composition was formulated in the same manner as in Example 1, except that polymer 1 was replaced with polymethacrylate (PMA), no pour point depressant was added, and the amount of each component added was adjusted as shown in Table 3. prepared. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 2 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with poly ⁇ olefin (PAO) and the amount of each component added was adjusted as shown in Table 3.
  • Table 3 shows the physical properties of the lubricating oil composition.
  • Example 3 A lubricating oil composition was formulated in the same manner as in Example 1, except that polybutene (PIB) was substituted for polymer 1 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • PIB polybutene
  • (A) Mineral oil is used as the lubricating base oil, and the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle contains (C) an ethylene- ⁇ -olefin copolymer. Comparing Examples 1 to 3 with Comparative Example 1 containing PMA instead of (C) ethylene- ⁇ -olefin copolymer, the lubricating oil composition of the present invention does not cause viscosity reduction even after the shear test. Therefore, the mechanism of the electric vehicle can be continuously protected for a long period of time.
  • the lubricating oil compositions of Comparative Examples 2 and 3 containing PAO or PIB instead of (C) the ethylene- ⁇ -olefin copolymer had a thermal diffusivity of less than 7.0 ⁇ 10 -2 . Therefore, sufficient motor cooling performance cannot be obtained.
  • the ethylene- ⁇ -olefin copolymer has a methylene chain as a main skeleton and has a smaller degree of freedom at the molecular ends than PAO and PIB, so heat generation due to molecular vibration is suppressed, and it was used in the lubricating oil composition. It is considered that excellent cooling or heat dissipation performance is exhibited in this case. In addition, since fluidity is poor at low temperatures, the fuel economy is remarkably inferior in low-temperature environments.

Landscapes

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

Abstract

Le problème décrit par la présente invention est de fournir une composition lubrifiante qui présente une excellente stabilité au cisaillement et d'excellentes caractéristiques de température-viscosité en termes d'économie de consommation de carburant et d'économie d'énergie de véhicules électriques, tout en présentant une performance de dissipation de chaleur élevée. La solution selon l'invention porte sur une composition lubrifiante qui a une viscosité cinématique à 100 °C de 4 à 10 mm2/s et contient une huile de base lubrifiante et un copolymère éthylène/α-oléfine qui a une teneur molaire en éthylène de 30 % en mole à 70 % en mole, une viscosité cinématique à 100 °C de 10 à 5000 mm2/s, un indice de couleur de trouble de 30 ou moins, une distribution de poids moléculaire de 2,5 ou moins, et une valeur B de 1,1 ou plus : l'huile de base lubrifiante est composée d'une huile minérale qui a une viscosité cinématique à 100 °C de 2 à 6 mm2/s, un indice de viscosité de 105 ou plus et un point d'écoulement de -5 °C ou moins, et/ou une huile synthétique qui a une viscosité cinématique à 100 °C de 1 à 9 mm2/s, un indice de viscosité de 110 ou plus et un point d'écoulement de -30 °C ou moins. Cette composition lubrifiante est utilisée dans le but de refroidir un moteur électrique et des engrenages de lubrification dans un véhicule électrique.
PCT/JP2023/007952 2022-03-03 2023-03-03 Composition lubrifiante WO2023167307A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-032865 2022-03-03
JP2022032865 2022-03-03

Publications (1)

Publication Number Publication Date
WO2023167307A1 true WO2023167307A1 (fr) 2023-09-07

Family

ID=87883835

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/007952 WO2023167307A1 (fr) 2022-03-03 2023-03-03 Composition lubrifiante

Country Status (1)

Country Link
WO (1) WO2023167307A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006325369A (ja) * 2005-05-20 2006-11-30 Nissan Motor Co Ltd 電動モータの冷却装置
JP2012031359A (ja) * 2009-12-28 2012-02-16 Idemitsu Kosan Co Ltd 機器冷却用基油、該基油を配合してなる機器冷却油、該冷却油により冷却される機器、および該冷却油による機器冷却方法
JP2013126280A (ja) * 2011-12-14 2013-06-24 Nissan Motor Co Ltd 回転電機
JP2016069405A (ja) * 2014-09-26 2016-05-09 三井化学株式会社 潤滑油組成物
JP2016108406A (ja) * 2014-12-04 2016-06-20 東燃ゼネラル石油株式会社 潤滑油組成物
JP2019154115A (ja) * 2018-03-01 2019-09-12 本田技研工業株式会社 回転電機の冷却システムおよびこれを備えた回転電機
JP2021500463A (ja) * 2017-10-20 2021-01-07 トタル マーケティング セルヴィス 車両の駆動システムを冷却し潤滑するための組成物
JP2021164298A (ja) * 2020-03-31 2021-10-11 日本電産株式会社 駆動装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006325369A (ja) * 2005-05-20 2006-11-30 Nissan Motor Co Ltd 電動モータの冷却装置
JP2012031359A (ja) * 2009-12-28 2012-02-16 Idemitsu Kosan Co Ltd 機器冷却用基油、該基油を配合してなる機器冷却油、該冷却油により冷却される機器、および該冷却油による機器冷却方法
JP2013126280A (ja) * 2011-12-14 2013-06-24 Nissan Motor Co Ltd 回転電機
JP2016069405A (ja) * 2014-09-26 2016-05-09 三井化学株式会社 潤滑油組成物
JP2016108406A (ja) * 2014-12-04 2016-06-20 東燃ゼネラル石油株式会社 潤滑油組成物
JP2021500463A (ja) * 2017-10-20 2021-01-07 トタル マーケティング セルヴィス 車両の駆動システムを冷却し潤滑するための組成物
JP2019154115A (ja) * 2018-03-01 2019-09-12 本田技研工業株式会社 回転電機の冷却システムおよびこれを備えた回転電機
JP2021164298A (ja) * 2020-03-31 2021-10-11 日本電産株式会社 駆動装置

Similar Documents

Publication Publication Date Title
JP6618891B2 (ja) エチレン／α−オレフィン共重合体および潤滑油
JP6320262B2 (ja) 潤滑油組成物
KR102208021B1 (ko) 자동차 기어용 윤활유 조성물
JP6326355B2 (ja) 潤滑油組成物
JP6326337B2 (ja) 工業ギア用潤滑油組成物
JP6326340B2 (ja) グリース組成物
JP6392055B2 (ja) 潤滑油組成物
JP6326339B2 (ja) 作動油用潤滑油組成物
JP6490086B2 (ja) 潤滑油組成物
JP6326354B2 (ja) 潤滑油組成物
JP6326338B2 (ja) 圧縮機油用潤滑油組成物
JP6773567B2 (ja) 自動車ギア用潤滑油組成物
WO2023167307A1 (fr) Composition lubrifiante
JP6773566B2 (ja) 自動車ギア用潤滑油組成物
JP6840544B2 (ja) 自動車変速機用潤滑油組成物
JP6496523B2 (ja) 潤滑油組成物およびその用途
JP2023096880A (ja) 自動車変速機用潤滑油組成物
WO2023002947A1 (fr) Modificateur de viscosité pour huile lubrifiante, et composition d'huile lubrifiante pour huile hydraulique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23763564

Country of ref document: EP

Kind code of ref document: A1