WO2020194543A1 - 内燃機関用潤滑油組成物およびその製造方法 - Google Patents
内燃機関用潤滑油組成物およびその製造方法 Download PDFInfo
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- WO2020194543A1 WO2020194543A1 PCT/JP2019/012998 JP2019012998W WO2020194543A1 WO 2020194543 A1 WO2020194543 A1 WO 2020194543A1 JP 2019012998 W JP2019012998 W JP 2019012998W WO 2020194543 A1 WO2020194543 A1 WO 2020194543A1
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- lubricating oil
- internal combustion
- oil composition
- ethylene
- combustion engine
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- GZIBPKCDJTWEDE-UHFFFAOYSA-N CCC(C1(C)CCCC1)=O Chemical compound CCC(C1(C)CCCC1)=O GZIBPKCDJTWEDE-UHFFFAOYSA-N 0.000 description 1
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- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2205/00—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
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
- C10M2205/0225—Ethene used as base material
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- 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
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- 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
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2040/25—Internal-combustion engines
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Definitions
- the present invention relates to a lubricating oil composition for an internal combustion engine and a method for producing the same, particularly a lubricating oil composition for a high-power internal combustion engine and a method for producing the same.
- Petroleum products generally have a so-called temperature dependence of viscosity, in which the viscosity changes significantly when the temperature changes.
- a certain polymer soluble in the lubricating oil base is used as a viscosity modifier (also referred to as a viscosity index improver) for the purpose of reducing the temperature dependence of the viscosity.
- OCP olefin copolymer
- viscosity index improvers are used to maintain the proper viscosity of lubricating oils at high temperatures, but general viscosity index improvers used in ordinary automobile engine oils have a relatively high molecular weight and are subject to shear stress. Molecular breakage occurs, which tends to cause a decrease in the viscosity of the lubricating oil. Therefore, it is not suitable to use a general viscosity index improver for high-viscosity engine oil used under the severe conditions as described above.
- a viscosity modifier having a relatively low molecular weight is used, but although the decrease in viscosity due to shearing can be suppressed, the ability to improve the viscosity index is inferior, so the viscosity is highly temperature-dependent, and specifically in a low temperature environment.
- the fluidity of the lubricating oil at 40 ° C. or lower is poor, and the stirring resistance at the start of the internal combustion engine is extremely large as compared with the engine oil for ordinary automobiles, which adversely affects the fuel efficiency of the internal combustion engine.
- Patent Document 2 describes a specific specific application to an internal combustion engine, which has low temperature dependence of viscosity while maintaining high shear stability, that is, excellent fluidity at 40 ° C. or lower, and low stirring resistance to the engine.
- a lubricating oil composition containing a lubricating oil base oil and a specific ethylene- ⁇ -olefin copolymer is disclosed.
- Patent Document 3 describes a method for producing a liquid random copolymer of ethylene and ⁇ -olefin, and describes that this copolymer is useful as a lubricating oil.
- the conventional lubricating oil composition has low temperature dependence of viscosity while maintaining high shear stability, that is, excellent fluidity in a low temperature environment, low stirring resistance to an engine, and heat-resistant oxidation stability. There was room for further improvement from the viewpoint of providing an excellent lubricating oil composition for an internal combustion engine.
- a lubricating oil composition having excellent performance As a result of diligent studies to develop a lubricating oil composition having excellent performance, the present inventors have made an ethylene- ⁇ -olefin copolymer produced by using a specific catalyst with respect to a specific lubricating oil base oil. It has been found that a lubricating oil composition containing a coalescence and satisfying a specific condition can solve the above-mentioned problems, and has completed the present invention.
- Specific examples of the present invention include the following aspects.
- the lubricating oil base oil contains a lubricating oil base oil and a liquid random copolymer (C) of ethylene and ⁇ -olefin produced by the following method ( ⁇ ), and has a kinematic viscosity of 12.5 mm 2 / s or more at 100 ° C. 26 .1 mm less than 2 / s,
- the lubricating oil base oil is composed of a mineral oil (A) having the following characteristics (A1) to (A3) and / or a synthetic oil (B) having the characteristics (B1) to (B3).
- Lubricating oil composition is composed of a mineral oil (A) having the following characteristics (A1) to (A3) and / or a synthetic oil (B) having the characteristics (B1) to (B3).
- the kinematic viscosity at 100 ° C is 2 to 10 mm 2 / s
- the viscosity index is 95 or more
- the pour point is -10 ° C or less
- B1 The kinematic viscosity at 100 ° C Is 1 to 10 mm 2 / s
- the viscosity index is 120 or more
- the pour point is -30 ° C or less
- Method ( ⁇ )) It is selected from the group consisting of (a) a crosslinked metallocene compound represented by the following formula 1, (b) (i) an organoaluminum oxy compound, and (ii) a compound that reacts with the crosslinked metallocene compound to form an ion pair.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are independently hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups and are adjacent to each other. A plurality of groups are optionally connected to each other to form a ring structure.
- R 6 and R 11 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 7 and R 10 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 6 and R 7 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 11 and R 10 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 6 , R 7 , R 10 and R 11 are not hydrogen atoms at the same time;
- Y is a carbon atom or a silicon atom;
- R 13 and R 14 are independently aryl groups;
- M is Ti, Zr or Hf;
- Q is a neutral ligand that can independently coordinate to a halogen, a hydrocarbon group, an anionic ligand or a lone electron pair;
- j is an integer of 1 to 4.
- At least one of the substituents (R 1 , R 2 , R 3 and R 4 ) bonded to the cyclopentadienyl group of the metallocene compound represented by the above formula 1 is a hydrocarbon group having 4 or more carbon atoms.
- R e + is, H +, carbenium cation, oxonium cation, ammonium cation, a ferrocenium cation having a phosphonium cation, a cycloheptyltrienyl cation or a transition metal,
- R f ⁇ R i is , Each independently is a hydrocarbon group having 1 to 20 carbon atoms.
- the lubricating oil composition for an internal combustion engine according to the above [7] or [8], wherein the catalyst system further comprises an organoaluminum compound selected from the group consisting of trimethylaluminum and triisobutylaluminum.
- the lubricating oil base oil contains a lubricating oil base oil and a liquid random copolymer of ethylene and ⁇ -olefin having the following characteristics (C1) to (C5), and has a kinematic viscosity of 12.5 mm 2 / s or more at 100 ° C. 26. .1 mm less than 2 / s,
- the lubricating oil base oil is composed of a mineral oil (A) having the following characteristics (A1) to (A3) and / or a synthetic oil (B) having the characteristics (B1) to (B3).
- Lubricating oil composition (A1) The kinematic viscosity at 100 ° C.
- the viscosity index is 95 or more (A3)
- the pour point is -10 ° C or less (B1)
- the kinematic viscosity at 100 ° C. Is 1 to 10 mm 2 / s (B2)
- the viscosity index is 120 or more (B3)
- the pour point is -30 ° C or less (C1)
- the ethylene unit is 40 to 60 mol%, and the number of carbon atoms is 3.
- C2 Containing 60-40 mol% of ⁇ 20 ⁇ -olefin units (C2) 500-10,000 number average molecular weight (Mn) measured by gel permeation chromatography (GPC), and molecular weight distribution of 3 or less (Mw / Mn and Mw are weight average molecular weights.)
- C3 Have a 100 ° C.
- kinematic viscosity 30 to 5,000 mm 2 / s
- C4 Have a pour point of 30 to ⁇ 45 ° C.
- a diesel engine oil comprising the lubricating oil composition for an internal combustion engine according to any one of the above [1] to [13].
- a step of producing a liquid random copolymer (C) of ethylene and ⁇ -olefin by the following method ( ⁇ ), and mixing the lubricating oil base oil with the liquid random copolymer (C) to 100 kinematic viscosity at °C includes the step of producing a lubricating oil composition for an internal combustion engine is less than 12.5 mm 2 / s or more 26.1 mm 2 / s,
- the lubricating oil base oil is composed of a mineral oil (A) having the following characteristics (A1) to (A3) and / or a synthetic oil (B) having the characteristics (B1) to (B3).
- the kinematic viscosity at 100 ° C is 2 to 10 mm 2 / s
- the viscosity index is 95 or more
- the pour point is -10 ° C or less
- B1 The kinematic viscosity at 100 ° C Is 1 to 10 mm 2 / s
- the viscosity index is 120 or more
- the pour point is -30 ° C or less
- Method ( ⁇ )) It is selected from the group consisting of (a) a crosslinked metallocene compound represented by the following formula 1, (b) (i) an organoaluminum oxy compound, and (ii) a compound that reacts with the crosslinked metallocene compound to form an ion pair.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are independently hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups and are adjacent to each other. A plurality of groups are optionally connected to each other to form a ring structure.
- R 6 and R 11 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 7 and R 10 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 6 and R 7 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 11 and R 10 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 6 , R 7 , R 10 and R 11 are not hydrogen atoms at the same time;
- Y is a carbon atom or a silicon atom;
- R 13 and R 14 are independently aryl groups;
- M is Ti, Zr or Hf;
- Q is a neutral ligand that can independently coordinate to a halogen, a hydrocarbon group, an anionic ligand or a lone electron pair;
- j is an integer of 1 to 4.
- the lubricating oil composition of the present invention is a lubricating oil composition that maintains high shear stability, exhibits extremely excellent temperature-viscosity characteristics and excellent low-temperature fluidity, and is also excellent in heat-resistant oxidation stability, and is an internal combustion engine oil. Contributes to fuel efficiency.
- lubricating oil composition for an internal combustion engine according to the present invention (hereinafter, also simply referred to as “lubricating oil composition”) will be described in detail.
- the lubricating oil composition for an internal combustion engine is a liquid random copolymer (C) of ethylene and ⁇ -olefin produced by a lubricating oil base oil and the method ( ⁇ ) (“ethylene- ⁇ ” in the present specification. -. be described as olefin copolymer (C) ”) contains a kinematic viscosity at 100 ° C. of less than 12.5 mm 2 / s or more 26.1 mm 2 / s, the lubricating oil base oil is a mineral oil It is characterized by consisting of (A) and / or synthetic oil (B).
- the lubricating base oil used in the present invention has different performances and qualities such as viscosity characteristics, heat resistance, and oxidation stability depending on the manufacturing method, refining method, and the like.
- the API American Petroleum Institute
- the mineral oil (A) has the following characteristics (A1) to (A3).
- the mineral oil (A) in the present invention belongs to groups I to III in the API category described above.
- the kinematic viscosity at 100 ° C. is 2 to 10 mm 2 / s This kinematic viscosity value is measured according to the method described in JIS K2283.
- the kinematic viscosity of the mineral oil (A) at 100 ° C. is 2 to 10 mm 2 / s, preferably 2.5 to 8 mm 2 / s, and more preferably 3.5 to 6.5 mm 2 / s.
- the lubricating oil composition of the present invention is excellent in terms of volatility and temperature viscosity characteristics.
- Viscosity index is 95 or more The value of this viscosity index is measured according to the method described in JIS K2283.
- the viscosity index of the mineral oil (A) is 95 or more, preferably 105 or more, and more preferably 120 or more. When the viscosity index is in this range, the lubricating oil composition of the present invention has excellent temperature viscosity properties.
- the pour point is ⁇ 10 ° C. or lower The value of this pour point is measured according to the method described in ASTM D97.
- the pour point of the mineral oil (A) is ⁇ 10 ° C. or lower, preferably ⁇ 12 ° C. or lower.
- the lubricating oil composition of the present invention has excellent low temperature viscosity properties when the mineral oil (A) is used in combination with a pour point lowering agent.
- the quality of mineral oil is as described above, and each of the above quality mineral oils can be obtained by the refining method.
- the mineral oil (A) specifically, the lubricating oil distillate obtained by distilling the atmospheric residual oil obtained by atmospheric distillation of crude oil under reduced pressure is subjected to solvent removal, solvent extraction, and hydrocracking. Examples thereof include those refined by performing one or more treatments such as solvent dewaxing and hydrorefining, and lubricating oil base oils such as wax isomerized mineral oil.
- the gas-to-liquid (GTL) base oil obtained by the Fischer-Tropsch method 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 + lubricating oil base oils, for example, the patent documents EP0776959, EP0668342, WO97 / 21788, WO00 / 15736, WO00 / 14188, WO00 / 14187, WO00 / 14183. , WO00 / 14179, WO00 / 08115, WO99 / 41332, EP1029029, WO01 / 18156 and WO01 / 57166.
- the mineral oil (A) may be used alone as the lubricating oil base oil, or two or more kinds selected from the synthetic oil (B) and the mineral oil (A). Any mixture of lubricating oils and the like may be used.
- the synthetic oil (B) has the following characteristics (B1) to (B3).
- the synthetic oil (B) in the present invention belongs to Group IV or Group V in the API category described above.
- the kinematic viscosity at 100 ° C. is 1 to 10 mm 2 / s This kinematic viscosity value is measured according to the method described in JIS K2283.
- the kinematic viscosity of the synthetic oil (B) at 100 ° C. is 1 to 10 mm 2 / s, preferably 2 to 8 mm 2 / s, and more preferably 3.5 to 6 mm 2 / s.
- the lubricating oil composition of the present invention is excellent in terms of volatility and temperature viscosity characteristics.
- Viscosity index is 120 or more The value of this viscosity index is measured according to the method described in JIS K2283.
- the viscosity index of the synthetic oil (B) is 120 or more, preferably 125 or more. When the viscosity index is in this range, the lubricating oil composition of the present invention has excellent temperature viscosity properties.
- (B3) Pour point is ⁇ 30 ° C. or lower The value of this pour point is measured according to the method described in ASTM D97.
- the pour point of the synthetic oil (B) is ⁇ 30 ° C. or lower, preferably ⁇ 40 ° C. or lower, more preferably ⁇ 50 ° C. or lower, still more preferably ⁇ 60 ° C. or lower.
- the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
- Poly- ⁇ -olefins belonging to Group IV are acid catalysts as described in US Pat. Nos. 3,780,128, US Pat. No. 4,032,591, JP-A-1-163136, etc. It can be obtained by oligomerizing the higher ⁇ -olefin.
- a low molecular weight oligomer of at least one olefin selected from olefins having 8 or more carbon atoms can be used.
- a poly- ⁇ -olefin is used as the lubricating oil base oil, a lubricating oil composition having extremely excellent temperature viscosity characteristics, low temperature viscosity characteristics, and heat resistance can be obtained.
- Poly- ⁇ -olefins are also industrially available, and those having a kinematic viscosity of 100 ° C. of 2 mm 2 / s to 10 mm 2 / s are commercially available.
- NESTE 2000 series ExxonMobil Chemical Co., Ltd. Spectrasyn, Ineos Oligmers Co., Ltd. Duracin, Chevron Phillips Chemical Co., Ltd. Synfluid and the like can be mentioned.
- Examples of synthetic oils belonging to Group V include alkylbenzenes, alkylnaphthalene, isobutylene oligomers or hydrides thereof, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, esters and the like.
- alkylbenzenes and alkylnaphthalene are usually dialkylbenzene or dialkylnaphthalene having an alkyl chain length of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalene are free of benzene or naphthalene and olefin.
- the alkylated olefin used in the production of alkylbenzenes or alkylnaphthalene may be a linear or branched olefin or a combination thereof.
- ester is preferably a fatty acid ester from the viewpoint of compatibility with the ethylene- ⁇ -olefin copolymer (C).
- the fatty acid ester is not particularly limited, and examples thereof include the following fatty acid esters consisting only of carbon, oxygen, and hydrogen.
- examples thereof include a polyol ester produced by reacting with.
- esters examples include ditridecylglutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, tridecylpelargonate, di-2-ethylhexyl adipate, di-2.
- the alcohol moiety constituting the ester is preferably an alcohol having a hydroxyl group of bifunctional or higher, and the fatty acid moiety is a fatty acid having 8 or more carbon atoms. Is preferable.
- fatty acids fatty acids having 20 or less carbon atoms, which are easily available industrially, are superior in terms of production cost. The effect of the present invention may be sufficiently exhibited even if one type of fatty acid constituting the ester or a fatty acid ester produced by using a mixture of two or more types of acids is used.
- fatty acid ester examples include trimethylolpropane lauric acid stearic acid mixed trimester and diisodecyl adipate, which are combined with a saturated hydrocarbon component such as ethylene- ⁇ -olefin copolymer (C).
- C ethylene- ⁇ -olefin copolymer
- the fatty acid ester is 5 to 20 when the total lubricating oil composition is 100% by mass. It is preferably contained in an amount of% by mass.
- the amount of ester is preferably 20% by mass or less.
- the ethylene- ⁇ -olefin copolymer (C) is a liquid random copolymer (C) of ethylene and ⁇ -olefin produced by the following method ( ⁇ ).
- Method ( ⁇ ) It is selected from the group consisting of (a) a crosslinked metallocene compound represented by the following formula 1, (b) (i) an organoaluminum oxy compound, and (ii) a compound that reacts with the crosslinked metallocene compound to form an ion pair.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are independently hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups and are adjacent to each other. A plurality of groups are optionally connected to each other to form a ring structure.
- R 6 and R 11 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 7 and R 10 are identical to each other and are hydrogen atoms, hydrocarbon groups or silicon-containing hydrocarbon groups.
- R 6 and R 7 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 11 and R 10 optionally combine with hydrocarbons having 2 to 3 carbon atoms to form a ring structure.
- R 6 , R 7 , R 10 and R 11 are not hydrogen atoms at the same time;
- Y is a carbon atom or a silicon atom;
- R 13 and R 14 are independently aryl groups;
- M is Ti, Zr or Hf;
- Q is a neutral ligand that can independently coordinate to a halogen, a hydrocarbon group, an anionic ligand or a lone electron pair;
- j is an integer of 1 to 4.
- the hydrocarbon group has 1 to 20, preferably 1 to 15, more preferably 4 to 10, and means, for example, an alkyl group, an aryl group, or the like, and the aryl group has 6 carbon atoms. It is ⁇ 20, preferably 6 ⁇ 15.
- silicon-containing hydrocarbon group examples include an alkyl group or an aryl group having 3 to 20 carbon atoms containing 1 to 4 silicon atoms, and more specifically, a trimethylsilyl group and a tert-butyldimethylsilyl group. , Triphenylsilyl group and the like.
- the cyclopentadienyl group may be substituted or unsubstituted.
- the substituents (R 1 , R 2 , R 3 and R 4 ) bonded to the cyclopentadienyl group is a hydrocarbon group.
- the substituent (R 1 , R 2 , R 3 and R 4 ) is a hydrocarbon group having 4 or more carbon atoms.
- the substituent (R 2 or R 3 ) bonded to the 3-position of the cyclopentadienyl group is a hydrocarbon group having 4 or more carbon atoms (for example, an n-butyl group).
- R 1 , R 2 , R 3 and R 4 are substituents (ie, not hydrogen atoms), the above substituents may be the same or different, with at least one substituent being carbon. It is preferably a hydrocarbon group of several 4 or more.
- R 6 and R 11 bonded to the fluorenyl group are the same, R 7 and R 10 are the same, but R 6 , R 7 , R 10 and R 11 are simultaneously. Is not a hydrogen atom.
- R 6 nor R 11 is preferably a hydrogen atom, and more preferably all of R 6 , R 7 , R 10 and R 11 are hydrogen. Not an atom.
- R 6 and R 11 attached to the 2- and 7 positions of the fluorenyl group are the same hydrocarbon groups having 1 to 20 carbon atoms, preferably all tert-butyl groups, and R 7 and R 10 are.
- the main chain portion (bonding portion, Y) connecting the cyclopentadienyl group and the fluorenyl group is a single carbon as a structural cross-linking portion that imparts steric rigidity to the crosslinked metallocene compound represented by the formula 1. It is a cross-linked portion of two covalent bonds containing an atom or a silicon atom.
- the crosslinked atom (Y) in the crosslinked portion has two aryl groups (R 13 and R 14 ) which may be the same or different. Therefore, the cyclopentadienyl group and the fluorenyl group are bonded by a covalently bonded cross-linked portion containing an aryl group.
- aryl groups include phenyl groups, naphthyl groups, anthracenyl groups, and substituted aryl groups, which are substituents on one or more aromatic hydrogens (sp type 2 hydrogen) of phenyl, naphthyl or anthracenyl groups. It is formed by substitution.).
- substituent contained in the substituted aryl group include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogen atom and the like, and a phenyl group is preferable.
- R 13 and R 14 are preferably the same from the viewpoint of ease of production.
- Q is preferably a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- the halogen atom include fluorine, chlorine, bromine and iodine
- examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl and 1,1-dimethylpropyl.
- Examples include compounds in which the zirconium atom of these compounds is replaced with a hafnium atom or compounds in which a chloro ligand is replaced with a methyl group, but the crosslinked metallocene compound (a) is not limited to these examples.
- organoaluminum oxy compound used in the catalyst system in the present invention conventional aluminoxane can be used.
- a linear or cyclic aluminoxane represented by the following formulas 2 to 5 can be used.
- the organoaluminum oxy compound may contain a small amount of the organoaluminum compound.
- R is independently a hydrocarbon group having 1 to 10 carbon atoms
- Rx is independently a hydrocarbon group having 2 to 20 carbon atoms
- m and n are independently 2 or more. It is preferably an integer of 3 or more, more preferably 10 to 70, and most preferably 10 to 50.
- R c is a hydrocarbon group having 1 to 10 carbon atoms
- R d is independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R is a methyl group (Me) of an organoaluminum oxy compound conventionally called "methylaluminoxane”.
- methylaluminoxane Since the methylaluminoxane is easily available and has high polymerization activity, it is generally used as an activator in polyolefin polymerization.
- methylaluminoxane has been used as a solution of environmentally undesirable aromatic hydrocarbons such as toluene or benzene because it is difficult to dissolve in saturated hydrocarbons. Therefore, in recent years, as an aluminoxane dissolved in a saturated hydrocarbon, a flexible body of methylaluminoxane represented by the formula 4 has been developed and used.
- the modified methylaluminoxane represented by the formula 4 is prepared using alkylaluminum other than trimethylaluminum and trimethylaluminum as shown in US Pat. No. 4,960,878 and US Pat.
- No. 5,041,584, for example. Prepared using trimethylaluminum and triisobutylaluminum.
- Aluminoxane having Rx as an isobutyl group is commercially available in the form of a saturated hydrocarbon solution under the trade names of MMAO and TMAO. (See Tosoh Finechem Corporation, Tosoh Research & Technology Review, Vol 47, 55 (2003)).
- Examples of the compound (ii) that reacts with the crosslinked metallocene compound to form an ion pair (hereinafter, referred to as “ionic compound” as necessary) contained in the catalyst system include Lewis acid, an ionic compound, and borane.
- Bolan compounds and carborane compounds can be used, and these are Korean Patent No. 10-0551147, JP-A-1-501950, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703. It is described in Japanese Patent Application Laid-Open No. 3-207704, US Patent No. 5321106, and the like.
- a heteropoly compound, an isopoly compound, or the like can be used, and the ionic compound described in JP-A-2004-51676 can be used.
- the ionic compound may be used alone or in admixture of two or more. More specifically, examples of Lewis acids include compounds represented by BR 3 (R is fluoride, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms (such as methyl groups), substituted or substituted.
- An unsubstituted aryl group having 6 to 20 carbon atoms can be mentioned, and examples thereof include trifluoroborone, triphenylboron, tris (4-fluorophenyl) boron, and tris (3,5-difluoro). Examples include phenyl) boron, tris (4-fluorophenyl) boron, tris (pentafluorophenyl) boron, and tris (p-tolyl) boron.
- the ionic compound is used, the amount used and the amount of sludge generated are relatively small as compared with the organoaluminum oxy compound, which is economically advantageous.
- the compound represented by the following formula 6 is preferably used as the ionic compound.
- R e + is H +, carbenium cation, oxonium cation, ammonium cation, a ferrocenium cation having a phosphonium cation, cycloheptyltrienyl cation, or a transition metal
- R f ⁇ R i is Each is independently an organic group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an aryl group, for example, a pentafluorophenyl group.
- Examples of the carbenium cation include tris (methylphenyl) carbenium cation, tris (dimethylphenyl) carbenium cation and the like, and examples of the ammonium cation include dimethylanilinium cation and the like.
- the compound represented by the above formula 6 is preferably N, N-dialkylanilinium salt, specifically N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl).
- N, N-Dimethylanilinium Tetraphenyl (3,5-Ditrifluoromethylphenyl) Borate, N, N-Diethylanilinium Tetraphenyl Borate, N, N-Diethylanilinium Tetraphenyl (Pentafluorophenyl) Borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium Examples include tetrakis (pentafluorophenyl) borate.
- the catalyst system used in the present invention further contains (c) an organoaluminum compound, if necessary.
- the organoaluminum compound plays a role of activating the crosslinked metallocene compound, the organoaluminum oxy compound, the ionic compound and the like.
- organoaluminum compound preferably, organoaluminum represented by the following formula 7 and a complex alkylated product of a Group 1 metal represented by the following formula 8 and aluminum can be used.
- M 2 AlR a 4 ...
- Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
- organoaluminum compound represented by the formula 7 examples include easily available trimethylaluminum and triisobutylaluminum.
- alkyl complex compound of the Group 1 metal represented by the formula 8 and aluminum examples include LiAl (C 2 H 5 ) 4 , LiAl (C 7 H 15 ) 4, and the like.
- a compound similar to the compound represented by the formula 7 can be used.
- an organoaluminum compound in which at least two aluminum compounds are bonded via a nitrogen atom such as (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 , can be used.
- the amount of the (a) crosslinked metallocene compound represented by the formula 1 is preferably 5 to 50% by weight based on the total catalyst composition. Is. And preferably, (b) (i) the amount of the organoaluminum oxy compound is 50 to 500 equivalents with respect to the number of moles of the crosslinked metallocene compound used, and (b) (ii) react with the crosslinked metallocene compound.
- the amount of the compound forming an ion pair is 1 to 5 equivalents with respect to the number of moles of the crosslinked metallocene compound used, and (c) the amount of the organoaluminum compound is the number of moles of the crosslinked metallocene compound used. 5 to 100 equivalents.
- the catalyst system used in the present invention may have, for example, the following [1] to [4].
- [1] A crosslinked metallocene compound represented by the formula 1 (a), and (b) (i) an organoaluminum oxy compound
- [2] a crosslinked metallocene compound represented by the formula 1 (b) (i) organic. Aluminum oxy compounds, and (c) organoaluminum compounds.
- [3] A crosslinked metallocene compound represented by the formula 1 (a), (b) (ii) a compound that reacts with the crosslinked metallocene compound to form an ion pair, and (c) an organoaluminum compound.
- [4] A crosslinked metallocene compound represented by (a) formula 1, (b) (i) an organoaluminum oxy compound, and (ii) a compound that reacts with the crosslinked metallocene compound to form an ion pair.
- the crosslinked metallocene compound represented by the formula 1 (component (a)), (b) (i) organoaluminum oxy compound (component (b)), (ii) react with the crosslinked metallocene compound to form an ion pair.
- the organoaluminum compound (component (c)) is introduced into the starting material monomer (mixture of ethylene and ⁇ -olefin having 3 to 20 carbon atoms) in an arbitrary order. May be good.
- the components (a), (b) and / or (c) are introduced alone or in any order into a polymerization reactor packed with raw material monomers.
- at least two of the components (a), (b) and / or (c) are mixed, and then the mixed catalyst composition is introduced into a polymerization reactor packed with raw material monomers.
- the ethylene- ⁇ -olefin copolymer (C) is prepared by solution polymerization of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms under the catalyst system.
- the ⁇ -olefin having 3 to 20 carbon atoms include linear ⁇ -olefins such as propylene, 1-butene, 1-pentene and 1-hexene, isobutylene, 3-methyl-1-butene and 4-methyl-1-.
- One or more of branched ⁇ -olefins such as penten and mixtures thereof can be used.
- one or more ⁇ -olefins having 3 to 6 carbon atoms can be used, and more preferably propylene can be used.
- the solution polymerization can be carried out by using an inert solvent such as propane, butane or hexane, or the olefin monomer itself as a medium.
- an inert solvent such as propane, butane or hexane, or the olefin monomer itself as a medium.
- the copolymerization temperature is usually 80 to 150 ° C., preferably 90 to 120 ° C.
- the copolymerization pressure is usually atmospheric pressure to 500 kgf / cm 2 .
- the pressure is preferably atmospheric pressure to 50 kgf / cm 2 , and these may vary depending on the reaction material, reaction conditions, and the like.
- Polymerization can be carried out in batch, semi-continuous or continuous, preferably continuous.
- the ethylene- ⁇ -olefin copolymer (C) has a liquid phase at room temperature and has a structure in which ⁇ -olefin units are uniformly distributed in the copolymer chain.
- the ethylene- ⁇ -olefin copolymer (C) contains, for example, 60-40 mol%, preferably 45-55 mol%, ethylene units derived from ethylene, and, for example, 40-60 mol%, preferably 45-55 mol%. It contains 55 mol% of 3 to 20 carbon ⁇ -olefin units derived from 3 to 20 carbon ⁇ -olefins.
- the number average molecular weight (Mn) of the ethylene- ⁇ -olefin copolymer (C) is, for example, 500 to 10,000, preferably 800 to 6,000, and the molecular weight distribution (Mw / Mn, Mw are weight average molecular weights). ) Is, for example, 3 or less, preferably 2 or less.
- the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) are measured by gel permeation chromatography (GPC).
- the ethylene- ⁇ -olefin copolymer (C) has a kinematic viscosity of 100 ° C. of, for example, 30 to 5,000, preferably 50 to 3,000 mm 2 / s, for example, 30 to -45 ° C., preferably 20 to -35. It has a pour point of ° C., for example, a bromine value of 0.1 g / 100 g or less.
- the crosslinked metallocene compound represented by the formula 1 has a particularly high polymerization activity against the copolymerization of ethylene and ⁇ -olefin, and by using this crosslinked metallocene compound, the polymerization is selectively stopped by introducing hydrogen to the molecular terminal. The unsaturated bond of the obtained ethylene- ⁇ -olefin copolymer (C) is reduced. Further, since the ethylene- ⁇ -olefin copolymer (C) has high random copolymerizability, it has a controlled molecular weight distribution and is excellent in shear stability and viscosity characteristics.
- the lubricating oil composition for an internal combustion engine of the present invention containing the ethylene- ⁇ -olefin copolymer (C) maintains high shear stability, exhibits extremely excellent temperature viscosity characteristics and excellent low temperature fluidity. Furthermore, it is considered to be excellent in heat resistance oxidation stability.
- the lubricating oil composition for an internal combustion engine contains the lubricating oil base oil composed of the mineral oil (A) and / or the synthetic oil (B) and the ethylene- ⁇ -olefin copolymer (C).
- Kinematic viscosity at 100 ° C. for an internal combustion engine lubricating oil composition of the present invention is less than 12.5 mm 2 / s or more 26.1 mm 2 / s. This kinematic viscosity value is measured by the method described in JIS K2283. If the kinematic viscosity of the lubricating oil composition for an internal combustion engine at 100 ° C. exceeds 26.1 mm 2 / s excessively, the stirring resistance of the lubricating oil to each part of the internal combustion engine increases, and the fuel saving performance is inferior. If the kinematic viscosity at 100 ° C. is excessively smaller than 12.5 mm 2 / s, metal contact may occur.
- Kinematic viscosity at 100 ° C. is preferably less than 13.0 mm 2 / s or more 26.1 mm 2 / s, more preferably 15.0 mm 2 / s or more 26.1 mm less than 2 / s, more preferably 16.3 mm 2 It is more than / s and less than 26.1 mm 2 / s. High fuel economy performance can be obtained while maintaining good shear stability in this range.
- the reduction rate of kinematic viscosity at 100 ° C. after 90 cycle test is usually 0.5%. Is less than. That is, the lubricating oil composition for an internal combustion engine of the present invention has extremely high shear stability.
- large displacement engines such as construction machinery and heavy machinery, high-power engines such as cross-head diesel engine oil for ships, ordinary automobiles, and motorcycles It can be suitably used for a racing vehicle in a car or a high-speed engine such as a large displacement motorcycle such as a large two-wheeled vehicle.
- the blending ratio of the lubricating oil base oil composed of the mineral oil (A) and / or the synthetic oil (B) and the ethylene- ⁇ -olefin copolymer (C) is
- the mass ratio of the lubricating oil base oil to the ethylene- ⁇ -olefin copolymer (C) (of the lubricating oil base oil) is usually not particularly limited as long as it satisfies the required characteristics in the intended application.
- the mass / mass of the copolymer (C)) is 99/1 to 30/70.
- the lubricating oil composition for an internal combustion engine of the present invention is a cleaning dispersant, a viscosity modifier, an antioxidant, a corrosion inhibitor, an abrasion resistant agent, a friction modifier, a pour point lowering agent, a rust preventive and a defoaming agent. Etc. may be contained.
- additives used in the lubricating oil composition of the present invention include the following, and these can be used alone or in combination of two or more.
- the cleaning dispersant examples include metal sulfonate, metal phenate, metal phosphanate, and succinimide.
- Alkaline metals and alkaline earth metal salicylates, phenates and sulfonate cleaning agents are preferred in the lubricating oil compositions of the present invention.
- calcium or magnesium sulfonate; finate; salicylate; succinimide; benzylamine and the like can be exemplified.
- the cleaning dispersant is used in the range of 0 to 18% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- the cleaning dispersant used in a high-power engine for ships has a total base value of 30 to 350 mg KOH / g measured by the method described in ISO 3771, and is 0% based on 100% by mass of the lubricating oil composition. It is blended in the range of 5 to 18% by mass, and is adjusted so that the total base value of the lubricating oil composition is 20 mg KOH / g or more.
- viscosity modifier known viscosity modifiers such as methacrylate-based copolymers having a molecular weight of less than 50,000, liquid polybutene, and bright stock, which is a mineral oil, can be used in combination.
- the viscosity modifier is used in the range of 0 to 50% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- antioxidant examples include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol.
- the antioxidant is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- the corrosion inhibitor examples include compounds such as benzotriazole, benzimidazole, and thiadiazole.
- the corrosion inhibitor is used in the range of 0 to 3% by mass with respect to 100% by mass of the grease composition, if necessary.
- abrasion resistant agent examples include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and polytetrafluoroethylene.
- the wear resistant 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.
- examples thereof include esters, fatty acid amides, and fatty acid metal salts.
- Examples of the amine compound include linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or these fats. Examples thereof include alkylene oxide adducts of group amines.
- Examples of the imide compound include succinimide having a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms and / or a modified compound thereof with a carboxylic acid, boric acid, phosphoric acid, sulfuric acid or the like. ..
- Examples of the fatty acid ester include an ester of a linear or branched, preferably linear fatty acid having 7 to 31 carbon atoms and an aliphatic monohydric alcohol or an aliphatic polyhydric alcohol.
- Examples of the fatty acid amide include an amide of a linear or branched, preferably linear fatty acid having 7 to 31 carbon atoms and an aliphatic monoamine or an aliphatic polyamine.
- Examples of the fatty acid metal salt include alkaline earth metal salts (magnesium salt, calcium salt, etc.), zinc salts, and the like, which are linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms.
- the friction modifier is used in the range of 0 to 5.0% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- pour point depressant various known pour point depressants can be used. Specifically, 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.
- the vinyl polymer containing an organic acid ester group include an alkyl methacrylate (co) polymer, an alkyl acrylate (co) polymer, an alkyl fumarate (co) polymer, and an alkyl maleate (co). Examples thereof include polymers and alkylated naphthalene.
- Such a pour point lowering agent has a melting point of ⁇ 13 ° C. or lower, preferably ⁇ 15 ° C., and more preferably ⁇ 17 ° C. or lower.
- the melting point of the pour point depressant 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.
- the pour point lowering agent 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. It is in the range of ⁇ 200,000.
- the pour point lowering agent is used in the range of 0 to 2% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- rust preventive examples include various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, sulfonates, and other compounds.
- the rust preventive is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- the defoaming agent examples include silicone-based compounds such as dimethylsiloxane and silica gel dispersion, alcohol-based or ester-based compounds, and the like.
- the defoaming agent is used in the range of 0 to 0.2% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
- anti-emulsifiers In addition to the above additives, anti-emulsifiers, colorants, oil-based agents (oil-based improvers) and the like can be used as needed.
- DI packages for lubricating oils for internal combustion engines, so-called DI packages, in which various necessary additives are blended for this purpose and concentrated and dissolved in lubricating oils such as mineral oil or synthetic hydrocarbon oil, are industrially supplied. Such a DI package can also be applied to the lubricating oil composition of the present invention.
- the lubricating oil composition of the present invention can be suitably used for internal combustion engine oils having a SAE viscosity standard of 40 or more, and high fluidity can be obtained at 40 ° C. or lower while maintaining good shear stability. Therefore, construction machinery and heavy machinery High-displacement engines such as large-displacement engines for ships, high-power engines such as cross-head diesel engine oil for ships, racing vehicles in ordinary automobiles and motorcycles, or high-displacement motorcycles such as large two-wheeled vehicles. It can be suitably used as a fuel-saving engine oil for a rotary engine.
- P E represents the molar fraction of the ethylene component
- P O is ⁇ - olefin indicates molar fraction of component
- the molar fraction of P OE is the total dyad chain ethylene - ⁇ - olefin chain Shows the rate.
- the molecular weight distribution was measured using HLC-8320GPC of Tosoh Corporation as follows.
- TSKgel SuperMultipore HZ-M 4 pieces
- the column temperature was 40 ° C.
- tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
- the developing speed was 0.35 ml / min
- the sample concentration was set to 0.35 ml / min.
- the sample injection volume was 5.5 g / L
- the sample injection volume was 20 microliters
- a differential refractometer was used as a detector.
- As the standard polystyrene one manufactured by Tosoh Corporation (PStQuick MP-M) was used.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and the molecular weight distribution (Mw / Mn) was calculated from these values.
- CCS viscosity> CCS viscosities were measured at ⁇ 10 ° C., ⁇ 15 ° C., ⁇ 20 ° C., ⁇ 25 ° C. or ⁇ 30 ° C. by the method described in ASTM D5293.
- the ethylene- ⁇ -olefin copolymer (C) was produced according to the following polymerization example.
- the obtained polymer solution was washed 3 times with 100 mL of 0.2 mol / l hydrochloric acid and then 3 times with 100 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
- the obtained polymer was dried under reduced pressure at 80 ° C. overnight to obtain 1.43 g of an ethylene-propylene copolymer.
- the ethylene content of the obtained polymer was 52.4 mol%, Mw was 13,600, Mw / Mn was 1.9, B value was 1.2, and 100 ° C. kinematic viscosity was 2,000 mm 2 / s. It was.
- the obtained polymer solution was washed 3 times with 100 mL of 0.2 mol / l hydrochloric acid and then 3 times with 100 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
- the obtained polymer was dried under reduced pressure at 80 ° C. overnight to obtain 1.43 g of an ethylene-propylene copolymer.
- the ethylene content of the obtained polymer was 52.1 mol%, Mw was 13,800, Mw / Mn was 2.0, B value was 1.2, and 100 ° C. kinematic viscosity was 2,000 mm 2 / s. It was.
- copolymer obtained in Polymerization Example 1 and the copolymer obtained in Polymerization Example 2 are hereinafter referred to as Polymer 1 and Polymer 2, respectively.
- Lubricating oil base oil The following lubricating oil base oil was used as the mineral oil (A).
- Mineral oil-A API Group I mineral oil with 100 ° C. kinematic viscosity of 6.8 mm 2 / s, viscosity index of 97, and pour point of -12.5 ° C. (JX Nikko Nisseki Co., Ltd. Super Oil N-46)
- Mineral oil-B API Group I mineral oil with 100 ° C.
- Mineral oil ⁇ D API Group III mineral oil having a kinematic viscosity of 4.2 mm 2 / s at 100 ° C., a viscosity index of 122, and a pour point of -15 ° C. (Yubase-4 manufactured by SK Lubricants).
- Mineral oil-E API Group III mineral oil having a kinematic viscosity of 6.5 mm 2 / s at 100 ° C., a viscosity index of 131, and a pour point of -12 ° C. (Yubase-6 manufactured by SK Lubricants).
- Synthetic oil (B) The following lubricating oil base oil was used as the synthetic oil (B).
- Synthetic oil-A Synthetic oil poly- ⁇ -olefin having a kinematic viscosity of 4.0 mm 2 / s at 100 ° C., a viscosity index of 123, and a pour point of -60 ° C. or lower (NEXBASE 2004 manufactured by Nest).
- Synthetic oil-B Synthetic oil poly- ⁇ -olefin having a kinematic viscosity of 5.8 mm 2 / s at 100 ° C., a viscosity index of 138, and a pour point of -60 ° C. or less (NEXBASE 2006 manufactured by Nest).
- Synthetic oil-C Fatty acid ester, diisodecyl adipate DI package (DI) manufactured by Daihachi Chemical Co., Ltd., which has a kinematic viscosity of 3.7 mm 2 / s at 100 ° C., a viscosity index of 156, and a pour point of -60 ° C. or less; Company P-5202 Pour point depressant (PPD); BASF IRGAFLO 720P Brightstock; API Group I mineral oil with 100 ° C. kinematic viscosity of 29.9 mm 2 / s, viscosity index of 97, and pour point of -10.0 ° C.
- DI diisodecyl adipate DI package
- Example 1 The copolymer (polymer 1) obtained in Polymerization Example 1 by using mineral oil-A and mineral oil-B, which are mineral oils (A), as the lubricating oil base oil as the ethylene- ⁇ -olefin copolymer (C). , A DI package (DI), and a flow point lowering agent (PPD) were mixed by a conventional method to prepare a lubricating oil composition for internal combustion engine oil.
- the amount of each component added and the physical properties of the obtained lubricating oil composition are as shown in Table 3.
- Examples 2 to 6, Comparative Examples 1 to 5 The lubricating oil composition was blended and prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 3. The physical properties of the obtained lubricating oil composition are as shown in Table 3.
- Example 7 Mineral oil-D and mineral oil-E, which are mineral oils (A), are used as the lubricating oil base oil, and polymer 1 is used as the ethylene- ⁇ -olefin copolymer (C), and these and the DI package (DI), And a flow point lowering agent (PPD) were mixed by a conventional method to prepare a lubricating oil composition for internal combustion engine oil.
- the amount of each component added and the physical properties of the obtained lubricating oil composition are as shown in Table 4.
- Example 8 to 15 The lubricating oil composition for internal combustion engine oil was blended and prepared in the same manner as in Example 7 except that the types and amounts of the components were changed as shown in Table 4.
- the physical properties of the obtained lubricating oil composition are as shown in Table 4.
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Abstract
Description
潤滑油基油と、以下の方法(α)により製造されるエチレンとα-オレフィンとの液状ランダム共重合体(C)とを含有し、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満であり、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(方法(α))
(a)下記式1で表される架橋メタロセン化合物、ならびに
(b)(i)有機アルミニウムオキシ化合物、および
(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物
からなる群から選択される少なくとも1つの化合物
を含む触媒系の下で、エチレンと炭素数3~20のα-オレフィンとの溶液重合を行う工程を含む、
エチレンとα-オレフィンとの液状ランダム共重合体を製造するための方法(α)
R6およびR11は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R7およびR10は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R6およびR7は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R11およびR10は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R6、R7、R10およびR11は、同時には水素原子ではなく;
Yは、炭素原子またはケイ素原子であり;
R13およびR14は、独立してアリール基であり;
Mは、Ti、ZrまたはHfであり;
Qは、独立してハロゲン、炭化水素基、アニオン性配位子または孤立電子対に配位可能な中性配位子であり;
jは、1~4の整数である。〕
〔2〕
上記式1で表されるメタロセン化合物のシクロペンタジエニル基に結合した置換基(R1、R2、R3およびR4)のうちの少なくとも1つが炭素数4以上の炭化水素基である前記〔1〕の内燃機関用潤滑油組成物。
R6およびR11が同一であり、炭素数1~20の炭化水素基である前記〔1〕または〔2〕の内燃機関用潤滑油組成物。
上記式1で表されるメタロセン化合物のシクロペンタジエニル基の3位に結合した置換基(R2またはR3)が炭化水素基である前記〔1〕~〔3〕のいずれかの内燃機関用潤滑油組成物。
上記式1で表されるメタロセン化合物のシクロペンタジエニル基の3位に結合した炭化水素基(R2またはR3)がn-ブチル基である前記〔4〕の内燃機関用潤滑油組成物。
上記式1で表されるメタロセン化合物のフルオレニル基の2位および7位に結合した置換基(R6およびR11)がすべてtert-ブチル基である前記〔1〕~〔5〕のいずれかの内燃機関用潤滑油組成物。
前記架橋メタロセン化合物と反応してイオン対を形成する前記化合物が、下記式6で表される化合物である前記〔1〕~〔6〕のいずれかの内燃機関用潤滑油組成物。
〔8〕
前記アンモニウムカチオンがジメチルアニリニウムカチオンである前記〔7〕の内燃機関用潤滑油組成物。
前記触媒系がトリメチルアルミニウムおよびトリイソブチルアルミニウムからなる群から選択される有機アルミニウム化合物をさらに含む前記〔7〕または〔8〕の内燃機関用潤滑油組成物。
前記液状ランダム共重合体(C)のα-オレフィンがプロピレンである上記〔1〕~〔9〕のいずれかに記載の内燃機関用潤滑油組成物。
潤滑油基油と、以下の(C1)~(C5)の特徴を有するエチレンとα-オレフィンとの液状ランダム共重合体とを含有し、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満であり、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(C1)エチレン単位を40~60モル%、および炭素数3~20のα-オレフィン単位を60~40モル%含有すること
(C2)ゲル浸透クロマトグラフィー(GPC)により測定される、500~10,000の数平均分子量(Mn)、および3以下の分子量分布(Mw/Mn、Mwは重量平均分子量である。)を有すること
(C3)30~5,000mm2/sの100℃動粘度を有すること
(C4)30~-45℃の流動点を有すること
(C5)0.1g/100g以下の臭素価を有すること
〔12〕
前記合成油(B)として、エステル、およびエステル以外の合成油を含有する上記〔1〕~〔11〕のいずれかに記載の内燃機関用潤滑油組成物。
少なくとも20mg-KOH/gの全塩基価を有する上記〔1〕~〔12〕のいずれかに記載の内燃機関用潤滑油組成物。
上記〔1〕~〔13〕のいずれかに記載の内燃機関用潤滑油組成物からなるディーゼルエンジン油。
以下の方法(α)によりエチレンとα-オレフィンとの液状ランダム共重合体(C)を製造する工程、および
潤滑油基油と、前記液状ランダム共重合体(C)とを混合して、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満である内燃機関用潤滑油組成物を製造する工程
を含み、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物の製造方法。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(方法(α))
(a)下記式1で表される架橋メタロセン化合物、ならびに
(b)(i)有機アルミニウムオキシ化合物、および
(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物
からなる群から選択される少なくとも1つの化合物
を含む触媒系の下で、エチレンと炭素数3~20のα-オレフィンとの溶液重合を行う工程を含む、
エチレンとα-オレフィンとの液状ランダム共重合体を製造するための方法(α)
R6およびR11は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R7およびR10は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R6およびR7は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R11およびR10は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R6、R7、R10およびR11は、同時には水素原子ではなく;
Yは、炭素原子またはケイ素原子であり;
R13およびR14は、独立してアリール基であり;
Mは、Ti、ZrまたはHfであり;
Qは、独立してハロゲン、炭化水素基、アニオン性配位子または孤立電子対に配位可能な中性配位子であり;
jは、1~4の整数である。〕
本発明に使用される潤滑油基油は、その製造方法や精製方法等により粘度特性や耐熱性、酸化安定性等の性能・品質が異なる。API(American Petroleum Institute)では、潤滑油基油をグループI、II、III、IV、Vの5種類に分類している。これらAPIカテゴリーはAPI Publication 1509、15th Edition、Appendix E、April 2002において定義されており、表2に示すとおりである。
この動粘度の値はJIS K2283に記載の方法に従い測定した場合のものである。鉱物油(A)の100℃における動粘度は、2~10mm2/s、好ましくは2.5~8mm2/s、より好ましくは3.5~6.5mm2/sである。100℃における動粘度がこの範囲にあると、本発明の潤滑油組成物は、揮発性、温度粘度特性の点において優れる。
この粘度指数の値はJIS K2283に記載の方法に従い測定した場合のものである。鉱物油(A)の粘度指数は、95以上、好ましくは105以上、より好ましくは120以上である。粘度指数がこの範囲にあると、本発明の潤滑油組成物は、優れた温度粘度特性を有する。
この流動点の値はASTM D97に記載の方法に従い測定した場合のものである。鉱物油(A)の流動点は、-10℃以下、好ましくは-12℃以下である。流動点がこの範囲にあると、本発明の潤滑油組成物は、鉱物油(A)を流動点降下剤と併用した際に優れた低温粘度特性を有する。
合成油(B)は以下(B1)~(B3)の特徴を有する。本発明における合成油(B)は、上述のAPIカテゴリーにおけるグループIVまたはグループVに帰属される。
この動粘度の値はJIS K2283に記載の方法に従い測定した場合のものである。合成油(B)の100℃における動粘度は、1~10mm2/s、好ましくは2~8mm2/s、より好ましくは3.5~6mm2/sである。100℃における動粘度がこの範囲にあると、本発明の潤滑油組成物は、揮発性、温度粘度特性の点において優れる。
この粘度指数の値はJIS K2283に記載の方法に従い測定した場合のものである。合成油(B)の粘度指数は、120以上、好ましくは125以上である。粘度指数がこの範囲にあると、本発明の潤滑油組成物は、優れた温度粘度特性を有する。
この流動点の値はASTM D97に記載の方法に従い測定した場合のものである。合成油(B)の流動点は、-30℃以下、好ましくは-40℃以下、より好ましくは-50℃以下、さらに好ましくは-60℃以下である。流動点がこの範囲にあると、本発明の潤滑油組成物は、優れた低温粘度特性を有する。
エチレン-α-オレフィン共重合体(C)は、以下の方法(α)により製造されるエチレンとα-オレフィンとの液状ランダム共重合体(C)である。
(方法(α))
(a)下記式1で表される架橋メタロセン化合物、ならびに
(b)(i)有機アルミニウムオキシ化合物、および
(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物
からなる群から選択される少なくとも1つの化合物
を含む触媒系の下で、エチレンと炭素数3~20のα-オレフィンとの溶液重合を行う工程を含む、
エチレンとα-オレフィンとの液状ランダム共重合体を製造するための方法(α)。
R6およびR11は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R7およびR10は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R6およびR7は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R11およびR10は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R6、R7、R10およびR11は、同時には水素原子ではなく;
Yは、炭素原子またはケイ素原子であり;
R13およびR14は、独立してアリール基であり;
Mは、Ti、ZrまたはHfであり;
Qは、独立してハロゲン、炭化水素基、アニオン性配位子または孤立電子対に配位可能な中性配位子であり;
jは、1~4の整数である。〕
ここで、前記炭化水素基は、炭素数が1~20、好ましくは1~15、より好ましくは4~10であり、例えばアルキル基、アリール基等を意味し、アリール基は、炭素数が6~20、好ましくは6~15である。
(i)シクロペンタジエニル基に結合した置換基(R1、R2、R3およびR4)のうち少なくとも1つが炭化水素基であることが好ましく、
(ii)置換基(R1、R2、R3およびR4)のうち少なくとも1つが炭素数4以上の炭化水素基であることがより好ましく、
(iii)シクロペンタジエニル基の3位に結合した置換基(R2またはR3)が炭素数4以上の炭化水素基(例えば、n-ブチル基)であることが最も好ましい。
エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
エチレン[η5-(3-tert-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
エチレン[η5-(3-n-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、エチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチル-5-メチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-tert-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、
ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](η5-フルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタメチルオクタヒドロジベンズフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](ベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](ジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](オクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)](2,7-ジフェニル-3,6-ジ-tert-ブチルフルオレニル)ジルコニウムジクロリド、ジ(p-トリル)メチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジメチル-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド等が挙げられる。
式7において、Ra及びRbは、それぞれ独立に、炭素数1~15、好ましくは炭素数1~4の炭化水素基であり、Xはハロゲン原子であり、mは0<m≦3の整数であり、nは0≦n≦3の整数であり、pは0<p≦3の整数であり、qは0≦q<3の整数であり、m+n+p+q=3である。
式8において、M2はLi、NaまたはKを表し、Raは炭素数1~15、好ましくは炭素数1~4の炭化水素基である。
[1](a)式1で表される架橋メタロセン化合物、および(b)(i)有機アルミニウムオキシ化合物
[2](a)式1で表される架橋メタロセン化合物、(b)(i)有機アルミニウムオキシ化合物、および(c)有機アルミニウム化合物。
[3](a)式1で表される架橋メタロセン化合物、(b)(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物、および(c)有機アルミニウム化合物。
[4](a)式1で表される架橋メタロセン化合物、ならびに(b)(i)有機アルミニウムオキシ化合物、および(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物。
本発明に係る内燃機関用潤滑油組成物は、前記鉱物油(A)および/または合成油(B)からなる潤滑油基油ならびに前記エチレン-α-オレフィン共重合体(C)を含有する。
本発明の潤滑油組成物は、SAE粘度規格40以上の内燃機関油に好適に使用でき、良好な剪断安定性を維持しながら40℃以下において高い流動性が得られるため、建設機械や重機械等の大排気量エンジンや船舶用クロスヘッド型ディーゼルエンジン油といった高出力型エンジンや、普通自動車、自動2輪車におけるレース用車両、もしくは大型2輪等の大排気量自動2輪車等の高回転型エンジンの省燃費エンジン油として好適に使用できる。
下記実施例および比較例等において、エチレン-α-オレフィン共重合体および内燃機関油用潤滑油組成物の物性等は以下の方法で測定した。
日本分光社製フーリエ変換赤外分光光度計FT/IR-610またはFT/IR-6100を用い、長鎖メチレン基の横揺れ振動に基づく721cm-1付近の吸収とプロピレンの骨格振動に基づく1155cm-1付近の吸収との吸光度比(D1155cm-1/D721cm-1)を算出し、予め作成しておいた検量線(ASTM D3900での標準試料を使って作成)よりエチレン含有量(重量%)を求めた。次に、得られたエチレン含有量(重量%)を用い、下記式に従ってエチレン含有量(mol%)を求めた。
o-ジクロロベンゼン/ベンゼン-d6(4/1[vol/vol%])を測定溶媒とし、測定温度120℃、スペクトル幅250ppm、パルス繰り返し時間5.5秒、かつパルス幅4.7μ秒(45oパルス)の測定条件下(100MHz、日本電子ECX400P)、または測定温度120℃、スペクトル幅250ppm、パルス繰り返し時間5.5秒、かつパルス幅5.0μ秒(45oパルス)の測定条件下(125 MHz、ブルカー・バイオスピンAVANCEIIIcryo-500)にて13C-NMRスペクトルを測定し、下記式[1]に基づきB値を算出した。
分子量分布は、東ソー株式会社HLC-8320GPCを用いて以下のようにして測定した。分離カラムとして、TSKgel SuperMultiporeHZ-M(4本)を用い、カラム温度を40℃とし、移動相にはテトラヒドロフラン(和光純薬社製)を用い、展開速度を0.35ml/分とし、試料濃度を5.5g/Lとし、試料注入量を20マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンとしては、東ソー社製(PStQuick MP-M)のものを用いた。汎用校正の手順に従い、ポリスチレン分子量換算として重量平均分子量(Mw)並びに数平均分子量(Mn)を算出し、これらの値から分子量分布(Mw/Mn)を算出した。
100℃動粘度および粘度指数は、JIS K2283に記載の方法により、測定、算出した。
CCS粘度はASTM D5293に記載の方法により-10℃、-15℃、-20℃、-25℃または-30℃において測定した。
ASTM D6278に記載の方法によりBoschインジェクターを用いたKurt Orbahn剪断試験にて90サイクルの試験を行い、下式で表される剪断による100℃動粘度の低下率(剪断試験粘度低下率)を評価した。
<耐熱酸化安定性>
耐熱酸化安定性に関しては、JIS K2514に記載の内燃機関用潤滑油酸価安定度試験(ISOT)の方法に準拠し、試験時間72時間後のラッカー度を評価した。
エチレン-α-オレフィン共重合体(C)は以下の重合例に従い製造した。
充分に窒素置換した内容積1Lのガラス製重合器にヘプタン250mLを装入し、系内の温度を50℃に昇温した後、エチレンを25L/h、プロピレンを75L/h、水素を100L/hの流量で連続的に重合器内に供給し、撹拌回転数600rpmで撹拌した。次にトリイソブチルアルミニウム0.2mmolを重合器に装入し、およびN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート0.023mmolとジフェニルメチレン[η5-(3-n-ブチルシクロペンタジエニル)][η5-(2,7-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド0.00230mmolをトルエン中で15分以上予備混合したものを重合器に装入することにより重合を開始した。その後、エチレン、プロピレン、水素の連続的供給を継続し、50℃で15分間重合を行った。少量のイソブチルアルコールを系内に添加することにより重合を停止した後、未反応のモノマーをパージした。得られたポリマー溶液を、0.2mol/lの塩酸100mLで3回、次いで蒸留水100mLで3回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを80℃の減圧下で一晩乾燥し、エチレン-プロピレン共重合体1.43gを得た。得られたポリマーのエチレン含有量は52.4mol%、Mwは13,600、Mw/Mnは1.9、B値は1.2であり、100℃動粘度は2,000mm2/sであった。
充分に窒素置換した内容積1Lのガラス製重合器にヘプタン250mLを装入し、系内の温度を50℃に昇温した後、エチレンを25L/h、プロピレンを75L/h、水素を100L/hの流量で連続的に重合器内に供給し、撹拌回転数600rpmで撹拌した。次にトリイソブチルアルミニウム0.2mmolを重合器に装入し、次いでMMAO0.688mmolとジメチルシリルビス(インデニル)ジルコニウムジクロリド0.00230mmolをトルエン中で15分以上予備混合したものを重合器に装入することにより重合を開始した。その後、エチレン、プロピレン、水素の連続的供給を継続し、50℃で15分間重合を行った。少量のイソブチルアルコールを系内に添加することにより重合を停止した後、未反応のモノマーをパージした。得られたポリマー溶液を、0.2mol/lの塩酸100mLで3回、次いで蒸留水100mLで3回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを80℃の減圧下で一晩乾燥し、エチレン-プロピレン共重合体1.43gを得た。得られたポリマーのエチレン含有量は52.1mol%、Mwは13,800、Mw/Mnは2.0、B値は1.2であり、100℃動粘度は2,000mm2/sであった。
以下の潤滑油組成物の調製において用いられたエチレン-α-オレフィン共重合体(C)以外の成分は以下のとおりである。
潤滑油基油;鉱物油(A)として以下の潤滑油基油を用いた。
鉱物油-A:100℃動粘度が6.8mm2/s、粘度指数が97、流動点が-12.5℃であるAPI Group I鉱物油(JX日鉱日石社製スーパーオイルN-46)
鉱物油-B:100℃動粘度が8.8mm2/s、粘度指数が101、流動点が-12.5℃であるAPI Group I鉱物油(JX日鉱日石社製スーパーオイルN-68)
鉱物油-C:100℃動粘度が5.3mm2/s、粘度指数が106、流動点が-12.5℃であるAPI Group I鉱物油(JX日鉱日石社製スーパーオイルN-32)
鉱物油-D:100℃動粘度が4.2mm2/s、粘度指数が122、流動点が-15℃であるAPI Group III鉱物油(SK Lubricants社製Yubase-4)
鉱物油-E:100℃動粘度が6.5mm2/s、粘度指数が131、流動点が-12℃であるAPI Group III鉱物油(SK Lubricants社製Yubase-6)
合成油(B);合成油(B)として以下の潤滑油基油を用いた。
合成油-A:100℃動粘度が4.0mm2/s、粘度指数が123、流動点が-60℃以下である合成油ポリ-α-オレフィン(Neste社製NEXBASE2004)
合成油-B:100℃動粘度が5.8mm2/s、粘度指数が138、流動点が-60℃以下である合成油ポリ-α-オレフィン(Neste社製NEXBASE2006)
合成油-C:脂肪酸エステルである、100℃動粘度が3.7mm2/s、粘度指数が156、流動点が-60℃以下である大八化学社製ジイソデシルアジペート
DIパッケージ(DI);Infineum社製P-5202
流動点降下剤(PPD);BASF社製IRGAFLO 720P
ブライトストック;100℃動粘度が29.9mm2/s、粘度指数が97、流動点が-10.0℃であるAPI Group I鉱物油(JX日鉱日石社製ブライトストックN460)
<内燃機関用潤滑油組成物>
[実施例1]
潤滑油基油として鉱物油(A)である鉱物油-Aおよび鉱物油-Bを、エチレン-α-オレフィン共重合体(C)として重合例1で得られた共重合体(重合体1)を用い、これらと、DIパッケージ(DI)、および流動点降下剤(PPD)とを常法により混合して、内燃機関油用潤滑油組成物を調製した。それぞれの成分の添加量、および得られた潤滑油組成物の物性等は表3に示す通りである。
成分の種類および添加量を表3に記載のとおり変更した以外は実施例1と同様にして、潤滑油組成物を配合調製した。得られた潤滑油組成物の物性等は表3に示す通りである。
潤滑油基油として鉱物油(A)である鉱物油-Dおよび鉱物油-Eを、エチレン-α-オレフィン共重合体(C)として重合体1を用い、これらと、DIパッケージ(DI)、および流動点降下剤(PPD)とを常法により混合して、内燃機関油用潤滑油組成物を調製した。それぞれの成分の添加量、および得られた潤滑油組成物の物性等は表4に示す通りである。
成分の種類および添加量を表4に記載のとおり変更した以外は実施例7と同様にして、内燃機関油用潤滑油組成物を配合調製した。得られた潤滑油組成物の物性等は表4に示す通りである。
Claims (15)
- 潤滑油基油と、以下の方法(α)により製造されるエチレンとα-オレフィンとの液状ランダム共重合体(C)とを含有し、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満であり、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(方法(α))
(a)下記式1で表される架橋メタロセン化合物、ならびに
(b)(i)有機アルミニウムオキシ化合物、および
(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物
からなる群から選択される少なくとも1つの化合物
を含む触媒系の下で、エチレンと炭素数3~20のα-オレフィンとの溶液重合を行う工程を含む、
エチレンとα-オレフィンとの液状ランダム共重合体を製造するための方法(α)
R6およびR11は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R7およびR10は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R6およびR7は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R11およびR10は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R6、R7、R10およびR11は、同時には水素原子ではなく;
Yは、炭素原子またはケイ素原子であり;
R13およびR14は、独立してアリール基であり;
Mは、Ti、ZrまたはHfであり;
Qは、独立してハロゲン、炭化水素基、アニオン性配位子または孤立電子対に配位可能な中性配位子であり;
jは、1~4の整数である。〕 - 上記式1で表されるメタロセン化合物のシクロペンタジエニル基に結合した置換基(R1、R2、R3およびR4)のうちの少なくとも1つが炭素数4以上の炭化水素基である請求項1に記載の内燃機関用潤滑油組成物。
- R6およびR11が同一であり、炭素数1~20の炭化水素基である請求項1または2に記載の内燃機関用潤滑油組成物。
- 上記式1で表されるメタロセン化合物のシクロペンタジエニル基の3位に結合した置換基(R2またはR3)が炭化水素基である請求項1~3のいずれか一項に記載の内燃機関用潤滑油組成物。
- 上記式1で表されるメタロセン化合物のシクロペンタジエニル基の3位に結合した炭化水素基(R2またはR3)がn-ブチル基である請求項4に記載の内燃機関用潤滑油組成物。
- 上記式1で表されるメタロセン化合物のフルオレニル基の2位および7位に結合した置換基(R6およびR11)がすべてtert-ブチル基である請求項1~5のいずれか一項に記載の内燃機関用潤滑油組成物。
- 前記アンモニウムカチオンがジメチルアニリニウムカチオンである請求項7に記載の内燃機関用潤滑油組成物。
- 前記触媒系がトリメチルアルミニウムおよびトリイソブチルアルミニウムからなる群から選択される有機アルミニウム化合物をさらに含む請求項7または8に記載の内燃機関用潤滑油組成物。
- 前記液状ランダム共重合体(C)のα-オレフィンがプロピレンである請求項1~9のいずれかに記載の内燃機関用潤滑油組成物。
- 潤滑油基油と、以下の(C1)~(C5)の特徴を有するエチレンとα-オレフィンとの液状ランダム共重合体とを含有し、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満であり、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(C1)エチレン単位を40~60モル%、および炭素数3~20のα-オレフィン単位を60~40モル%含有すること
(C2)ゲル浸透クロマトグラフィー(GPC)により測定される、500~10,000の数平均分子量(Mn)、および3以下の分子量分布(Mw/Mn、Mwは重量平均分子量である。)を有すること
(C3)30~5,000mm2/sの100℃動粘度を有すること
(C4)30~-45℃の流動点を有すること
(C5)0.1g/100g以下の臭素価を有すること - 前記合成油(B)として、エステル、およびエステル以外の合成油を含有する請求項1~11のいずれかに記載の内燃機関用潤滑油組成物。
- 少なくとも20mg-KOH/gの全塩基価を有する請求項1~12のいずれかに記載の内燃機関用潤滑油組成物。
- 請求項1~13のいずれかに記載の内燃機関用潤滑油組成物からなるディーゼルエンジン油。
- 以下の方法(α)によりエチレンとα-オレフィンとの液状ランダム共重合体(C)を製造する工程、および
潤滑油基油と、前記液状ランダム共重合体(C)とを混合して、100℃における動粘度が12.5mm2/s以上26.1mm2/s未満である内燃機関用潤滑油組成物を製造する工程
を含み、
前記潤滑油基油が、以下の(A1)~(A3)の特徴を有する鉱物油(A)、および/または(B1)~(B3)の特徴を有する合成油(B)からなる
内燃機関用潤滑油組成物の製造方法。
(A1)100℃における動粘度が2~10mm2/sであること
(A2)粘度指数が95以上であること
(A3)流動点が-10℃以下であること
(B1)100℃における動粘度が1~10mm2/sであること
(B2)粘度指数が120以上であること
(B3)流動点が-30℃以下であること
(方法(α))
(a)下記式1で表される架橋メタロセン化合物、ならびに
(b)(i)有機アルミニウムオキシ化合物、および
(ii)前記架橋メタロセン化合物と反応してイオン対を形成する化合物
からなる群から選択される少なくとも1つの化合物
を含む触媒系の下で、エチレンと炭素数3~20のα-オレフィンとの溶液重合を行う工程を含む、
エチレンとα-オレフィンとの液状ランダム共重合体を製造するための方法(α)
R6およびR11は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R7およびR10は、互いに同一であり、水素原子、炭化水素基またはケイ素含有炭化水素基であり、
R6およびR7は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R11およびR10は、任意に、炭素数2~3の炭化水素と結合して環構造を形成し、
R6、R7、R10およびR11は、同時には水素原子ではなく;
Yは、炭素原子またはケイ素原子であり;
R13およびR14は、独立してアリール基であり;
Mは、Ti、ZrまたはHfであり;
Qは、独立してハロゲン、炭化水素基、アニオン性配位子または孤立電子対に配位可能な中性配位子であり;
jは、1~4の整数である。〕
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KR100551147B1 (ko) | 2002-10-30 | 2006-02-13 | 미쯔이가가꾸가부시끼가이샤 | 저분자량 올레핀 (공)중합체의 제조에 사용되는 중합 촉매 |
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JP2016098342A (ja) | 2014-11-25 | 2016-05-30 | 三井化学株式会社 | 潤滑油組成物 |
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JP6571965B2 (ja) * | 2015-03-30 | 2019-09-04 | 三井化学株式会社 | オレフィン重合用触媒ならびにそれを用いたオレフィン重合体の製造方法 |
-
2019
- 2019-03-26 EP EP19921757.1A patent/EP3950901A4/en not_active Withdrawn
- 2019-03-26 CN CN201980094157.6A patent/CN113574149A/zh active Pending
- 2019-03-26 WO PCT/JP2019/012998 patent/WO2020194543A1/ja unknown
- 2019-03-26 US US17/442,590 patent/US20220186134A1/en not_active Abandoned
- 2019-03-26 KR KR1020217033660A patent/KR20210139402A/ko not_active Application Discontinuation
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See also references of EP3950901A4 |
TOSOH FINECHEM CORPORATION, TOSOH RESEARCH TECHNOLOGY REVIEW, vol. 47, 2003, pages 55 |
Also Published As
Publication number | Publication date |
---|---|
EP3950901A1 (en) | 2022-02-09 |
KR20210139402A (ko) | 2021-11-22 |
US20220186134A1 (en) | 2022-06-16 |
EP3950901A4 (en) | 2022-08-17 |
CN113574149A (zh) | 2021-10-29 |
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