WO2019188644A1 - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer Download PDF

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WO2019188644A1
WO2019188644A1 PCT/JP2019/011656 JP2019011656W WO2019188644A1 WO 2019188644 A1 WO2019188644 A1 WO 2019188644A1 JP 2019011656 W JP2019011656 W JP 2019011656W WO 2019188644 A1 WO2019188644 A1 WO 2019188644A1
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group
atom
olefin
carbon atoms
compound
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PCT/JP2019/011656
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French (fr)
Japanese (ja)
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哲志 吉富
田中　健一
郁子 恵比澤
山村　雄一
浩司 遠藤
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三井化学株式会社
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Priority to JP2020510772A priority Critical patent/JP6986138B2/en
Publication of WO2019188644A1 publication Critical patent/WO2019188644A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a novel transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer.
  • Ethylene / ⁇ -olefin rubber represented by ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) does not have an unsaturated bond in the main chain of its molecular structure. Because it is superior in heat resistance and weather resistance compared to rubber, it is widely used in applications such as automotive parts, electric wire materials, building civil engineering materials, industrial material parts, and various resin modifiers.
  • EPDM non-conjugated diene copolymer rubber
  • ethylene / ⁇ -olefin / non-conjugated polyene copolymer rubbers such as EPDM generally have a catalyst system consisting of a titanium catalyst or a combination of a vanadium catalyst and an organoaluminum compound (so-called Ziegler-Natta catalyst system).
  • a catalyst system consisting of a titanium catalyst or a combination of a vanadium catalyst and an organoaluminum compound (so-called Ziegler-Natta catalyst system).
  • This catalyst system is its productivity, and because of its low polymerization activity and short catalyst life, polymerization at low temperatures around 0 to 50 ° C. is forced. For this reason, the high viscosity of the polymerization solution becomes an obstacle, the concentration of the olefin copolymer in the polymerization vessel cannot be sufficiently increased, and there is a problem that the productivity is extremely low.
  • metallocene compounds are well known as homogeneous catalysts for olefin polymerization.
  • the metallocene catalyst system which has been actively researched since the 1980s, has excellent polymerization activity and ⁇ -olefin copolymerization ability, and is a single-site catalyst, so it has a narrow molecular weight distribution and composition distribution. It is possible to manufacture.
  • a substituent is introduced into the cyclopentadienyl ring of the ligand of the metallocene compound or two cyclopentadienyl rings are cross-linked. It has been known that the polymerization activity, the molecular weight of the resulting ⁇ -olefin polymer, and the like vary greatly, and many improvement studies have been conducted.
  • metallocene compounds having a methoxy group on fluorene are suitable for commercial use. Is disadvantageous. Therefore, existing metallocene compounds having a fluorenyl ligand are very often modified with an alkyl group at the 2, 3, 6 or 7 position where a substituent can be easily introduced, and a ring structure is formed between adjacent substituents. There is also a report example aiming at realization of an excellent olefin polymerization catalyst by forming (Patent No. 4367688, etc.).
  • Patent Document 3 discloses a process for producing an ethylene / ⁇ -olefin / non-conjugated polyene copolymer using a catalyst containing a specific bridged cyclopentadienyl-fluorenyl metallocene compound.
  • a catalyst containing a specific bridged cyclopentadienyl-fluorenyl metallocene compound to produce an ethylene / ⁇ -olefin / nonconjugated polyene copolymer with good polymerization activity, good non-conjugated polyene copolymerization ability, a very high molecular weight, and strong monomer alternating copolymerization
  • the polymerization temperature can be set higher.
  • JP 7-138275 A JP-A-6-172443 International Publication No. 2009/081794
  • the present invention provides a method for producing an olefin polymer having a high polymerization activity and a high molecular weight (especially an ethylene / ⁇ -olefin / nonconjugated polyene copolymer), and such a method. It is an object of the present invention to provide a metallocene compound and an olefin polymerization catalyst useful for the production of an olefin polymer.
  • the present inventors have intensively studied and found that a method for producing an olefin polymer using a catalyst for olefin polymerization containing a bridged metallocene compound having a specific structure, as well as a metallocene compound (transition) useful for the production of such an olefin polymer.
  • the present inventors have found that the above problems can be solved by a metal compound) and an olefin polymerization catalyst, and have completed the present invention.
  • the gist of the present invention is as follows.
  • transition metal compound [A] represented by the following general formula [I] or [II].
  • R 1 , R 2 , R 3 , R 4 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group or a nitrogen-containing group.
  • An atom or a substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents from R 1 to R 4 may be bonded to each other to form a ring, R 13 and R 14 may be bonded to each other to form a ring.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom or a substituent represented by ZR (where Z is an oxygen atom or a sulfur atom)
  • R is a substituent selected from the group consisting of 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 and a halogen-containing group;
  • An atom or a substituent selected from the group consisting of a halogen atom and a halogen-containing group, and adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring, among
  • M is a titanium atom, a zirconium atom or a hafnium atom
  • j is an integer from 1 to 4
  • Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, a plurality of Q May be the same as or different from each other.
  • [2] The transition metal compound [A] of the above [1], wherein Z is an oxygen atom in the general formula [I] or [II].
  • step [9] The method for producing an olefin polymer according to [8], wherein the step [P] is a step of copolymerizing ethylene and a non-conjugated polyene.
  • R 15 , R 16 , R 17 and R 18 are each independently selected from 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.
  • the hydrocarbon group may have a double bond, Any two substituents of from R 15 to R 18 may bond to each other to form a ring, the ring may contain a double bond, with a pair of R 15 and R 16, Alternatively, R 17 and R 18 may form an alkylidene group, R 15 and R 17 , or R 16 and R 18 may be bonded to each other to form a double bond, At least one of the following requirements (i) to (iv) is satisfied. (I) At least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds. (Ii) Any two substituents from R 15 to R 18 are bonded to each other to form a ring, and the ring includes bipolymerization.
  • step [12] The method for producing an olefin polymer according to any one of [9] to [11], wherein the step [P] is a step of copolymerizing ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
  • step [15] The method for producing an olefin polymer according to the above [7], wherein the step [P] is a step of polymerizing an ⁇ -olefin having 3 to 20 carbon atoms.
  • step [16] The method for producing an olefin polymer according to [15], wherein the step [P] is a step of copolymerizing ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • an olefin polymer having a high polymerization activity and a high molecular weight particularly an ethylene / ⁇ -olefin / non-conjugated polyene copolymer can be produced.
  • transition metal compound [A] The transition metal compound [A] according to the present invention (hereinafter sometimes referred to as “bridged metallocene compound [A]” or “component (A)”) is represented by the following general formula [I] or [II].
  • R 1 to R 14 , Y, A are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group or a nitrogen-containing group.
  • R 1 to R 4 An atom or a substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents from R 1 to R 4 may be bonded to each other to form a ring (provided that from the structure formed by the cyclopentadienyl group and R 1 ⁇ R 4, except fluorenyl group and substituted fluorenyl groups.), it may not be linked to each other, not preferably bonded to each other, R 13 And R 14 may be bonded to each other to form a ring, and may not be bonded to each other;
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom or a substituent represented by ZR (where Z is an oxygen atom or a sulfur atom)
  • R is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an ary
  • hydrocarbon group having 1 to 20 carbon atoms examples include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, and 3 carbon atoms.
  • Illustrative are ⁇ 20 cyclic unsaturated hydrocarbon groups.
  • the hydrocarbon group having 1 to 20 carbon atoms that are bonded to each other to form a ring includes Examples include an alkylene group having ⁇ 20, an arylene group having 6 to 20 carbon atoms, and the like.
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl groups which are linear saturated hydrocarbon groups.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups, 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, which is a group in which a hydrogen atom of a cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms, 4 Examples include -cyclohexylcyclohexyl group and 4-phenylcyclohexyl group.
  • the number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5 to 11.
  • Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group) which are alkenyl groups. Examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), which are alkynyl groups.
  • the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
  • cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms examples include cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, anthracenyl group and the like, which are cyclic unsaturated hydrocarbon groups 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which a hydrogen atom of a cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A group in which a hydrogen atom of a linear hydrocarbon group or a
  • alkylene group having 1 to 20 carbon atoms examples include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples include 1,2-dimethylethylene group and n-propylene group.
  • the alkylene group preferably has 1 to 6 carbon atoms.
  • Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, 4,4′-biphenylylene group and the like.
  • the carbon number of the arylene group is preferably 6 to 12.
  • the aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but is a phenyl group, a 1-naphthyl group, a 2-naphthyl group which is a substituent derived from an aromatic compound.
  • Groups, 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 are exemplified.
  • a phenyl group or a 2-naphthyl group is preferable.
  • aromatic compounds examples include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, etc. Is done.
  • the substituted aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms, Examples include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group.
  • 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, each of which is a hydrocarbon group having 1 to 20 carbon atoms in which a carbon atom is replaced with a silicon atom.
  • Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and t-butyldiphenylsilyl group, pentamethyldisiranyl group and trimethylsilylmethyl group.
  • the alkylsilyl group preferably has 1 to 10 carbon atoms
  • the arylsilyl group preferably has 6 to 18 carbon atoms.
  • a dimethylamino group and an N-morpholinyl group are preferable
  • oxygen-containing group examples include a hydroxyl group, a group in which the —CH 2 — structural unit is replaced with an oxygen atom or a carbonyl group in the above-described hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group, or — A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, hydroxymethyl, which is a group in which a CH 3 structural unit is replaced by an oxygen atom bonded with a hydrocarbon group having 1 to 20 carbon atoms 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-oxabuty
  • halogen atoms include group 17 elements such as fluorine, chlorine, bromine and iodine.
  • halogen-containing group examples include a trifluoromethyl group, a tribromo group in which a hydrogen atom is substituted with a halogen atom in the above-described hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, nitrogen-containing group or oxygen-containing group.
  • examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.
  • the substituent represented by ZR partially overlaps the oxygen-containing group described above.
  • Z is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • R is a substituent selected from the group consisting of 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 and a halogen-containing group;
  • the atom bonded to is a carbon atom or a silicon atom.
  • R 1 to R 4 , R 13 and R 14 examples thereof include those exemplified as R 1 to R 4 , R 13 and R 14 , preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert
  • An alkyl group having 1 to 20 carbon atoms such as -butyl group, cyclohexyl group and cycloheptyl group, or an aryl group such as phenyl group and 2-naphthyl group, a substituted aryl group such as m-tolyl group and p-tolyl group, Alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl
  • the substituent represented by ZR is bonded to the fluorenyl ligand through Z.
  • Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.
  • A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A includes two rings including a ring formed with Y.
  • the above ring structure may be included.
  • Examples of the divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms include those exemplified as R 1 to R 14 .
  • Cyclopentadienyl group The cyclopentadienyl group having substituents R 1 to R 4 in the above general formulas [I] and [II] is an unsubstituted cyclopentadienyl group in which R 1 to R 4 are hydrogen atoms, 3-t- Butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group Group, 3-position cyclopentadienyl group such as 3-cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl Group, 3-phenyl-5-methylcyclopentadienyl group, 3,5
  • a cyclopentadienyl group which is unsubstituted (R 1 to R 4 are hydrogen atoms) is preferable.
  • Substituted fluorenyl group In the general formulas [I] and [II], at least one of R 5 to R 12 is a substituent represented by ZR.
  • R 6 and R 11 are ZR, more preferably both R 6 and R 11 are ZR.
  • R 5 , R 8 , R 9 and R 12 are preferably hydrogen atoms from the viewpoint of easy synthesis of the bridged metallocene compound.
  • R 7 and R 10 when not ZR, are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of ease of synthesis, and from the viewpoint of realizing higher polymerization activity.
  • a hydrogen atom is particularly preferable.
  • the hydrocarbon group having 1 to 20 carbon atoms include those exemplified as the hydrocarbon group having 1 to 20 carbon atoms of R 1 to R 14 , such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Alkyl groups such as n-butyl group and tert-butyl group are preferred, and tert-butyl group is more preferred.
  • R 13 and R 14 may be the same or different from each other.
  • R 13 and R 14 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, m- A tolyl group, p-tolyl group, 4-t-butylphenyl group, p-chlorophenyl group, 4-biphenyl group, 2-naphthyl group, xylyl group, benzyl group, m-trifluoromethylphenyl group is a high molecular weight ethylene. This is preferable because a / ⁇ -olefin / non-conjugated polyene copolymer is produced.
  • A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and Y is bonded to this A.
  • a cycloalkylidene group such as a cyclohexylidene group represented by the formula [IIa] and a cyclomethylenesilylene group such as a cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by the following formula [IIb] .
  • A may include two or more ring structures including a ring formed with Y.
  • cyclohexylidene group represented by the above [IIa] a cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cycloheptylidene group, cyclooctylidene group, bicyclo [3.3 .1]
  • Nonylidene group, norbornylidene group, adamantylidene group, tetrahydronaphthylidene group, dihydroindanilidene group and the like a cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cycloheptylidene group, cyclooctylidene group, bicyclo [3.3 .1]
  • cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by [IIb] above
  • cyclodimethylenesilylene group 1,3-silacyclopentylidene group
  • cyclotrimethylenesilylene group 1,3-silacyclopentylidene group
  • cyclopentamethylenesilylene group 1,3-silacyclopentylidene group
  • cyclohexamethylene examples thereof include a silylene group and a cycloheptamethylenesilylene group.
  • M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.
  • J is an integer of 1 to 4, preferably 2.
  • Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, a plurality of Q May be the same as or different from each other.
  • halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above.
  • Q is a halogen atom
  • a chlorine atom is preferable.
  • 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 that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc.
  • organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc.
  • An ether compound etc. can be illustrated.
  • transition metal compound [A] Preferable embodiments of the transition metal compound [A] include, for example, dimethylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, dimethylsilylene ( ⁇ 5- Cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diethylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2 , 7-Dimethoxyfluorenyl)] zirconium dichloride, diethylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride Di-n-propylsilylene ( ⁇ 5 -
  • di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride di-p-tolylsilylene ( ⁇ 5 -Cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl
  • diphenylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dime
  • the transition metal compound [A] according to the present invention can be produced by, for example, using the production method described on pages 84 to 92 of WO 01/27124 as a compound represented by formula (12).
  • R 5 ⁇ R 12 in is by carried out using compounds conforming respectively R 5 ⁇ R 12 as defined in formula [I] or [II] described above in the present invention, can be produced.
  • the catalyst for olefin polymerization according to the present invention contains the transition metal compound [A] of the present invention.
  • the olefin polymerization catalyst of the present invention is preferably [B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] transition metal compounds [A] to form ion pairs. At least one compound (hereinafter also referred to as “compound [B]”) Is further contained.
  • the olefin polymerization catalyst of the present invention is preferably, if necessary, (C) It further contains a carrier.
  • the olefin polymerization catalyst of the present invention if necessary, (D) An organic compound component may be further contained.
  • the olefin polymerization catalyst according to the present invention can be used for polymerization of olefin (ethylene, ⁇ -olefin having 3 to 20 carbon atoms, etc.) described later.
  • Compound [B] Compound [B] (hereinafter sometimes referred to as “component (B)”) [B-1]
  • Organometallic compound (hereinafter also referred to as “component (B-1)”), preferably an organoaluminum compound [B-1a] represented by the following general formula (B-1a), B-1b) complex alkylated product of group 1 metal and aluminum [B-1b], or dialkyl compound of group 2 or group 12 metal represented by the following general formula (B-1c) [ B-1c], R a m Al (OR b ) n H p X q (B-1a) [In the general formula (B-1a), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m represents 0 ⁇ M ⁇ 3, n is 0 ⁇ n ⁇ 3, p is 0 ⁇ p ⁇ 3, q is a number of
  • M a AlR a 4 (B-1b) [In the general formula (B-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms. ] R a r M b R b s X t (B-1c) [In the general formula (B-1c), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other, and M b is selected from Mg, Zn and Cd.
  • X is a halogen atom
  • r is 0 ⁇ r ⁇ 2
  • s is 0 ⁇ s ⁇ 1
  • t is 0 ⁇ t ⁇ 1
  • r + s + t 2.
  • component hereinafter referred to as “component”.
  • B-3 At least one compound selected from the group consisting of:
  • Organic metal compound [B-1] As organoaluminum compound [B-1a], Tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, Tri-branched alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri-t-butyl aluminum, tri-2-methylbutyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum , Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, Triarylaluminum such as triphenylaluminum, tri (4-methylphenyl) aluminum, Dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylalumin
  • Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, Alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride and other partially hydrogenated alkyl aluminums, Examples thereof include partially alkoxylated and
  • a compound similar to the compound represented by the general formula R a m Al (OR b ) n H p X q can also be used.
  • a compound can be mentioned. Specific examples of such a compound include (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 .
  • Examples of the complex alkylated product [B-1b] of Group 1 metal and aluminum include LiAl (C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
  • Examples of the group 2 or group 12 metal dialkyl compound [B-1c] include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, and din. -Butyl zinc and diphenyl zinc are mentioned.
  • organoaluminum compound [B-1a] is preferred.
  • the organometallic compound [B-1] may be used alone or in combination of two or more.
  • the organoaluminum oxy compound [B-2] may be, for example, a conventionally known aluminoxane, which is insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. It may be a compound.
  • the conventionally known aluminoxane can be produced, for example, by the following methods (1) to (4), and is usually obtained as a solution in a hydrocarbon solvent.
  • a compound containing adsorbed water or a salt containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate
  • a method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension such as
  • Non-hydrolyzable compounds such as thermal decomposition reactions are produced by reacting organic aluminum such as trialkylaluminum with organic compounds having carbon-oxygen bonds such as tertiary alcohols, ketones and carboxylic acids. How to convert.
  • the aluminoxane may contain a small amount of an organometallic component.
  • the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in a solvent or suspended in a poor aluminoxane solvent.
  • organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound [B-1a]. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
  • organoaluminum oxy compound [B-2] examples include modified methylaluminoxane.
  • Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.
  • aluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and the like, in which R is an isobutyl group are commercially produced under the names MMAO and TMAO.
  • MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike MMAO, which is insoluble or hardly soluble in benzene, aliphatic hydrocarbons and It has the feature of being soluble in alicyclic hydrocarbons.
  • organoaluminum oxy compound [B-2] for example, an organoaluminum oxy compound containing a boron atom, or a halogen as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010.
  • aluminoxane examples include ionic aluminoxane as exemplified in International Publication No. WO2003 / 082879.
  • the organoaluminum oxy compound [B-2] may be used alone or in combination of two or more.
  • Compound [B-3] which reacts with transition metal compound [A] to form an ion pair >> As compound [B-3] (hereinafter also referred to as “ionic compound [B-3]”) that reacts with transition metal compound [A] to form an ion pair, for example, JP-A-1-501950 JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
  • examples of R e + include H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
  • R f to R i are each independently an organic group, preferably an aryl group.
  • carbenium cation examples include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.
  • ammonium cation examples include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; N N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation And dialkyl ammonium cations.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropy
  • Examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tris (methylphenyl) phosphonium cation, and a tris (dimethylphenyl) phosphonium cation.
  • R e + for example, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.
  • carbenium salt examples include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl).
  • ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.
  • trialkyl-substituted ammonium salt examples include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o- Tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylpheny
  • N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenyl borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoro) Methylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.
  • dialkylammonium salt examples include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
  • ionic compound [B-3] other ionic compounds disclosed in JP-A-2004-51676 can be used without limitation.
  • the ionic compound [B-3] may be used alone or in combination of two or more.
  • Carrier [C] examples include inorganic or organic compounds, and granular or fine particle solids.
  • the transition metal compound [A] is preferably used in a form supported on a carrier [C].
  • the inorganic compound in the carrier [C] is preferably a porous oxide, inorganic chloride, clay, clay mineral or ion-exchangeable layered compound.
  • porous oxide examples include oxides such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, and ThO 2 , or composites containing these, Mixtures can be used.
  • natural or synthetic zeolite SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , SiO 2 —TiO 2 —MgO Can be used.
  • a porous oxide containing SiO 2 and / or Al 2 O 3 as a main component is preferable.
  • the properties of porous oxides vary depending on the type and production method.
  • the carrier preferably used in the present invention has a particle size of preferably 1 to 300 ⁇ m, more preferably 3 to 100 ⁇ m; a specific surface area of preferably 50 to 1300 m 2 / g, more preferably 200 to 1200 m 2 / g.
  • the pore volume is preferably 0.3 to 3.0 cm 3 / g, more preferably 0.5 to 2.0 cm 3 / g.
  • Such a carrier is used after being dried and / or calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
  • the particle shape is not particularly limited, but is particularly preferably spherical.
  • the inorganic chloride for example, MgCl 2 , MgBr 2 , MnCl 2 , and MnBr 2 are used.
  • the inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvent, such as alcohol, what was made to precipitate into a fine particle form with a depositing agent can also be used.
  • Clay is usually composed mainly of clay minerals.
  • An ion-exchange layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged.
  • Most clay minerals are ion-exchangeable layered compounds.
  • these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.
  • clay, clay mineral or ion-exchangeable layered compound clay, clay mineral, or ion crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl 2 type, CdI 2 type, etc. It can be illustrated.
  • clay and clay minerals examples include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, pectolite, teniolite.
  • Examples of the ion-exchangeable layered compound include ⁇ -Zr (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2 ⁇ 3H 2 O, ⁇ -Ti (HPO 4 ) 2 , ⁇ -Ti (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Sn (HPO 4 ) 2 ⁇ H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Ti (HPO 4 ) 2 , ⁇ - Examples include crystalline acidic salts of polyvalent metals such as Ti (NH 4 PO 4 ) 2 .H 2 O.
  • the clay and clay mineral it is also preferable to subject the clay and clay mineral to chemical treatment.
  • chemical treatment any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used.
  • Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like.
  • the ion-exchangeable layered compound may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchangeability.
  • Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars.
  • introducing another substance between the layers of the layered compound in this way is called intercalation.
  • Examples of the guest compounds to be intercalated include, for example, TiCl 4, ZrCl 4 cationic inorganic compounds such as, Ti (OR) 4, Zr (OR) 4, PO (OR) 3, B (OR) 3 or the like of metal Metal hydroxide such as alkoxide (R is hydrocarbon group, etc.), [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ , [Fe 3 O (OCOCH 3 ) 6 ] + Examples include physical ions. These compounds may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the pillar include an oxide generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
  • a porous oxide containing SiO 2 and / or Al 2 O 3 as a main component is preferable.
  • clays or clay minerals particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
  • Examples of the organic compound in the carrier [C] include a granular or fine particle solid having a particle size in the range of 5 to 300 ⁇ m.
  • a (co) polymer produced mainly from an ⁇ -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, vinylcyclohexane and styrene are mainly used.
  • generated as a component, and those modifications can be illustrated.
  • Organic compound component [D] is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary.
  • examples of the organic compound [D] include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.
  • a catalyst component carrying component (B) on component (C) A method of adding the component (A) to the polymerization vessel in an arbitrary order.
  • a method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization vessel.
  • At least two of the catalyst components may be contacted in advance.
  • the component (B) that is not supported may be added in any order as necessary. In this case, the component (B) may be the same or different.
  • the solid catalyst component in which the component (C) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In addition, a catalyst component may be further supported on the prepolymerized solid catalyst component.
  • the method for producing an olefin polymer of the present invention comprises a step [P] of polymerizing an olefin (ethylene, ⁇ -olefin having 3 to 20 carbon atoms, etc.) in the presence of the above-mentioned catalyst for olefin polymerization.
  • polymerization is a general term for homopolymerization and copolymerization.
  • polymerize olefin in the presence of an olefin polymerization catalyst means that each component of the olefin polymerization catalyst is added to the polymerization vessel by any method as in the above methods (1) to (5).
  • polymerizes the said olefin is included.
  • the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
  • a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like.
  • alicyclic hydrocarbons aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.
  • An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.
  • the amount of each component that can constitute the olefin polymerization catalyst is as follows.
  • the content of each component can be adjusted as follows.
  • Component (A) is generally used in an amount of 1 ⁇ 10 ⁇ 10 to 1 ⁇ 10 ⁇ 2 mol, preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 3 mol per liter of reaction volume.
  • Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of usually 1 to 50,000, preferably Can be used in an amount of 10 to 20,000, particularly preferably 50 to 10,000.
  • Component (B-2) has a molar ratio [Al / M] of aluminum atoms in component (B-2) to all transition metal atoms (M) in component (A) of usually 10 to 5,000, preferably Can be used in an amount of 20 to 2,000.
  • Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) of usually 1 to 1000, preferably 1 It can be used in an amount of 200.
  • the weight ratio of component (A) to component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5. More preferably, it can be used in an amount of 0.001 to 0.1.
  • component (D) When using component (D), When component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. , When component (B) is component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. , When component (B) is component (B-3), it is used in such an amount that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. be able to.
  • the polymerization temperature is usually ⁇ 50 to + 200 ° C., preferably 0 to 200 ° C., more preferably 80 to 200 ° C.
  • the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure. Pressure to 5 MPa gauge pressure.
  • the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.
  • the molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen or the like to exist in the polymerization system, changing the polymerization temperature, or using the component (B).
  • hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer.
  • the amount is suitably about 0.00001 to 100 NL per mole of olefin.
  • the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.
  • the olefin polymer obtained by the production method of the present invention for example, ethylene / ⁇ -olefin / non-conjugated polyene copolymer
  • it is known as necessary.
  • You may perform post-processing processes, such as a catalyst deactivation processing process, a catalyst residue removal process, and a drying process.
  • the olefin supplied to the polymerization reaction is an ⁇ -olefin having 3 to 20 carbon atoms.
  • ethylene may be homopolymerized, ethylene may be copolymerized with a nonconjugated diene, or ethylene may be copolymerized with an ⁇ -olefin having 3 to 20 carbon atoms and a nonconjugated diene. Also good.
  • the olefin supplied to the polymerization reaction is an ⁇ -olefin having 3 to 20 carbon atoms.
  • ethylene and an ⁇ -olefin having 3 to 20 carbon atoms may be copolymerized, or an ⁇ -olefin having 3 to 20 carbon atoms and a non-conjugated diene may be copolymerized. And an ⁇ -olefin having 3 to 20 carbon atoms and a non-conjugated diene may be copolymerized.
  • an olefin polymer having a high polymerization activity and a high molecular weight particularly an ethylene / ⁇ -olefin / non-conjugated polyene copolymer can be produced.
  • the ⁇ -olefin is particularly preferably an ⁇ -olefin having 3 to 10 carbon atoms.
  • Examples of the ⁇ -olefin having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc., linear or branched ⁇ having 3 to 20 carbon atoms -Olefin can be exemplified.
  • the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 10 carbon atoms, for example, a linear or branched ⁇ -olefin having 3 to 10 carbon atoms, and propylene, 1-butene, 1-hexene and 1-octene are preferred. More preferably, propylene is more preferable.
  • These ⁇ -olefins can be used alone or in combination of two or more. The selection can be made so as to be the most desirable in terms of the properties of the copolymer to be produced.
  • the type of ⁇ -olefin can be selected so that the physical properties when the ethylene polymer obtained in the present invention or a mixture containing the copolymer is vulcanized are desirable.
  • non-conjugated polyene a compound having two or more non-conjugated unsaturated bonds can be used without limitation, and examples thereof include a non-conjugated cyclic polyene and a non-conjugated chain polyene described later, and one kind alone or two It is possible to use a combination of more than one species.
  • Non-conjugated cyclic polyene Specific examples of the non-conjugated cyclic polyene include compounds represented by the following general formula [III].
  • R 15 , R 16 , R 17 and R 18 are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups or substituents Each may be the same or different, and the hydrocarbon group may have a double bond, Any two substituents of R 15 to R 18 may be bonded to each other to form a ring, and the ring may contain a double bond, and R 15 and R 16 may be combined with each other, or R 17 and R 18 may form an alkylidene group, R 15 and R 17 or R 16 and R 18 may be bonded to each other to form a double bond, At least one of the following requirements (i) to (iv) is satisfied.
  • R 15 to R 18 is a hydrocarbon group having one or more double bonds.
  • Any two substituents from R 18 to R 18 are bonded to each other to form a ring, and the ring contains a double bond.
  • R 15 and R 16 or R 17 and R 18 form an alkylidene group.
  • R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond.
  • the hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups mentioned as R 15 , R 16 , R 17 and R 18 Specific examples of the group include specific examples of these atoms and substituents mentioned in the description of the general formulas [I] and [II].
  • R 15 , R 16 , R 17 and R 18 when any one or more of R 15 , R 16 , R 17 and R 18 is a hydrocarbon group having one or more double bonds, the hydrocarbon group is an ethenyl group.
  • the hydrocarbon group is an ethenyl group.
  • 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,4-hexadienyl group Etc. are exemplified.
  • R 15 is an ethenyl group (vinyl group)
  • the compound of the general formula [III] can be represented by the following general formula [III-I].
  • R 16 , R 17 and R 18 are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from a halogen atom and a halogen-containing group;
  • Each may be the same or different, and the hydrocarbon group may have a double bond, Any two substituents of R 16 to R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 form an alkylidene group.
  • R 16 and R 18 may be bonded to each other to form a double bond.
  • R 16 , R 17 and R 18 are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from a halogen atom and a halogen-containing group;
  • Each may be the same or different, and the hydrocarbon group may have a double bond, Any two substituents of R 16 to R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 form an alkylidene group.
  • R 16 and R 18 may be bonded to each other to form a double bond.
  • the alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms.
  • the compound of the general formula [III] can be represented by the following general formula [III-IV].
  • R 17 and R 18 are each 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, or a halogen-containing group, or a substituent. They may be different, and the hydrocarbon group may have a double bond, R 17 and R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 may form an alkylidene group.
  • m is an integer of 0 to 2
  • R 16 and R 18 are substituents selected from 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, and they are the same or different.
  • the hydrocarbon group may have a double bond, R 16 and R 18 may be bonded to each other to form a ring, and the ring may contain a double bond.
  • non-conjugated cyclic polyenes represented by the above general formula [III] as a compound in which at least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds, for example, 5-vinyl-2-norbornene (VNB) and the following compounds are exemplified. Of these, 5-vinyl-2-norbornene (VNB) is preferred.
  • any two substituents from R 15 to R 18 are bonded to each other to form a ring, and the ring contains a double bond.
  • the compound include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds. Of these, dicyclopentadiene (DCPD) is preferred.
  • non-conjugated cyclic polyenes represented by the above general formula [III] as compounds in which an alkylidene group is formed by R 15 and R 16 or R 17 and R 18 , 5-methylene-2-norbornene , 5-ethylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene and the following compounds. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.
  • R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond. are preferred.
  • a double bond-containing ring-substituted nonconjugated cyclic polyene in which m is 0 and a double bond-containing hydrocarbon group-substituted nonconjugated cyclic polyene in which m is 0 are preferred.
  • 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are more preferable.
  • ENB 5-ethylidene-2-norbornene
  • DCPD dicyclopentadiene
  • VNB 5-vinyl-2-norbornene
  • ENB 5-ethylidene-2-norbornene
  • VNB 5-vinyl-2-norbornene
  • Non-conjugated chain polyene Specific examples of the non-conjugated chain polyene include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, and 1,12-tetradecadiene.
  • non-conjugated chain polyenes examples include ⁇ , ⁇ -dienes such as 1,7-octadiene and 1,9-decadiene.
  • examples of other non-conjugated chain polyenes include the following general formula [ Non-conjugated triene or tetraene represented by IV-I].
  • R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 26 is an alkyl group having 1 to 3 carbon atoms
  • R 27 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group represented by — (CH 2 ) n —CR 28 ⁇ C (R 29 ) R 30 (where n is an integer of 1 to 5, R 28 And R 29 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 30 is an alkyl group having 1 to 3 carbon atoms) It is. However, when both p and r are
  • non-conjugated trienes or tetraenes represented by the above general formula [IV-I] are preferable.
  • R 21 , R 22 , R 25 , R 26 and R 27 are each independently a hydrogen atom, a methyl group or an ethyl group. However, R 26 and R 27 are not hydrogen atoms at the same time.
  • the non-conjugated triene represented by the general formula [IV-II] is a non-conjugated triene or tetraene represented by the general formula [IV-I], wherein p is 0, q is 0, r is 1, and s is 2 , R 23 and R 24 are hydrogen atoms. Furthermore, among the non-conjugated trienes represented by the above general formula [IV-II], compounds in which R 25 and R 27 are both methyl groups are preferred.
  • non-conjugated triene or tetraene represented by the general formula [IV-I] include the following compounds (excluding compounds included in the general formula [IV-II]).
  • non-conjugated triene represented by the above general formula [IV-II] include the following compounds.
  • the non-conjugated triene or tetraene represented by the above general formula [IV-I] can be produced by a known method.
  • step [P] When copolymerization is performed in step [P], the supply amount of each monomer is appropriately set according to the composition of the olefin polymer to be produced.
  • the olefin polymer produced by the production method of the present invention is an ethylene / ⁇ -olefin / non-conjugated polyene copolymer will be described.
  • the ethylene / ⁇ -olefin / non-conjugated polyene copolymer produced by the production method of the present invention comprises (i) a structural unit derived from ethylene (ethylene unit) and (ii) an ⁇ -olefin having 3 or more carbon atoms.
  • the structural unit ( ⁇ -olefin unit) derived from is usually contained in the range of 99/1 to 1/99 in terms of molar ratio [(i) / (ii)], but is not particularly limited.
  • the content of structural units derived from ethylene in the ethylene / ⁇ -olefin / nonconjugated polyene copolymer produced by the production method of the present invention is usually 50 mol% or more.
  • the structural unit derived from the non-conjugated polyene compound of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer produced by the production method of the present invention is not particularly limited, but is usually 0.1 to 49 mol in all the structural units. %, Preferably 0.2 to 8 mol%, more preferably 0.3 to 5 mol%.
  • the intrinsic viscosity [ ⁇ ] of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer produced by the production method of the present invention, measured in decalin at 135 ° C., is preferably 2 dl / g or more, more preferably 4 dl / g and the upper limit may be, for example, 20 dl / g.
  • the structure of the bridged metallocene compound and its precursor was determined by measuring 1 H NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (hereinafter FD-MS) spectrum (JEOL SX-102A), etc. .
  • the physical properties / properties of the ethylene / ⁇ -olefin / non-conjugated polyene copolymer were measured by the following methods.
  • di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-di-tert -Butylfluorenyl)] zirconium dichloride was obtained.
  • the yield was 151 mg (0.30 mmol), and the yield was 39%.
  • the identification of di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride is the 1 H NMR spectrum And FD-MS spectra. The measurement results are shown below.
  • the mixture was cooled in an ice bath, methylmagnesium bromide / diethyl ether solution (3 M) (0.42 ml, 1.26 mmol) was added, and the mixture was heated in an oil bath at 60 ° C. for 22 hours.
  • the solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using celite. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane.
  • the desired product was obtained by drying under reduced pressure. (Yield 53 mg, 39% yield).
  • the target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
  • the reaction mixture was cooled in an ice bath, methylmagnesium bromide / diethyl ether solution (3 M) 0.80 ml (2.40 mmol) was added, and the mixture was heated to reflux for 22 hours.
  • the solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using celite.
  • the solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane and added dropwise to hexane. A part of the solvent was distilled off under reduced pressure, and the resulting precipitate was collected by filtration.
  • the desired product was obtained by drying under reduced pressure. (Yield 113 mg, 45% yield).
  • the target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
  • the target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
  • Example B1 A stainless steel autoclave with an internal volume of 2 L that has been sufficiently purged with nitrogen is charged with 1030 mL of hexane and 12 mL of ethylidene norbornene (ENB). The total pressure was adjusted to 1.6 MPa-G by supplying ethylene.
  • Example B2 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A2. ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate The same operation as in Example B1 was performed except that the volume was changed to 00003 mmol.
  • Example B3 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A3. ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate changed to 0.00032mmol Except that, the same operation as in Example B1 was performed.
  • Example B4 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.0001 mmol of di-p-tolylsilylene prepared in Example A4. Changed ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate to 0.0004 mmol Except that, the same operation as in Example B1 was performed.
  • Example B5 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared from 0.0001 mmol of diphenylsilylene ( ⁇ 5- Except that cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.0004 mmol. The same operation as in Example B1 was performed.
  • Example B6 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared by adding 0.0001 mmol of diphenylsilylene ( ⁇ 5- Except that cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.0004 mmol. The same operation as in Example B1 was performed.
  • Example B7 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A7. ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride, 0.00032 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate The same operation as in Example B1 was performed except that the change was made.
  • Example B8 Di-p-tolylsilylene ( ⁇ 5 -cyclopentadienyl) [ ⁇ 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.0001 mmol of di p-tolylsilylene prepared in Example A8 ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3, The same operation as in Example B1 was carried out except that 4-g ′] dicromenyl) zirconium dichloride and triphenylcarbenium tetrakis (pentafluorophenyl) borate were changed to 0.0004 mmol.

Abstract

[Problem] To provide: a transition metal compound which has high polymerization activity and is useful for the production of an olefin polymer that has a high molecular weight; and a method. [Solution] A transition metal compound which is represented by general formula (I) or (II). (In the formulae, each one of R1-R14 moieties represents a hydrogen atom, a hydrocarbon group or the like; at least one of R5-R12 moieties represents a substituent that is expressed as ZR (wherein Z represents an oxygen atom or the like; and R represents a hydrocarbon group or the like, which is bonded to a fluorenyl ligand via Z); A represents a divalent hydrocarbon group; Y represents a carbon atom, a silicon atom or the like; M represents a group 4 transition metal atom of the periodic table; j represents an integer of 1-4; and Q represents a halogen atom or the like.)

Description

遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer
　本発明は、新規な遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法に関する。 The present invention relates to a novel transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer.
　エチレン／プロピレン／非共役ジエン共重合体ゴム（EPDM）に代表されるエチレン／α－オレフィン系ゴムは、その分子構造の主鎖に不飽和結合を有してないため、汎用されている共役ジエン系ゴムに比べ、耐熱性、耐候性に優れることから、自動車用部品、電線用材料、建築土木資材、工業材部品、各種樹脂の改質材等の用途に幅広く使用されている。 Ethylene / α-olefin rubber represented by ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) does not have an unsaturated bond in the main chain of its molecular structure. Because it is superior in heat resistance and weather resistance compared to rubber, it is widely used in applications such as automotive parts, electric wire materials, building civil engineering materials, industrial material parts, and various resin modifiers.
　従来EPDM等のエチレン／α－オレフィン／非共役ポリエン共重合体ゴムは、一般的にチタン系触媒あるいはバナジウム系触媒と有機アルミニウム化合物の組合せからなる触媒系（いわるゆチーグラー・ナッタ触媒系）を用いて製造されてきた。この触媒系の最大の欠点はその生産性であり、重合活性が低く触媒寿命が短いが故に、0から50℃付近の低い温度での重合を余儀なくされている。このため、重合溶液の高い粘度が障害となり、重合器内のオレフィン共重合体の濃度を充分に上げることができず、生産性が著しく低いという不具合を生じている。さらには、重合活性が低いために重合終了時に共重合体中に含まれる触媒残渣の量が多く、製品要求性能を満たさない場合が多々ある。従ってこれを除去するための脱灰処理プロセスが必要となり、生産コストの面で著しく不利となっている。 Conventionally, ethylene / α-olefin / non-conjugated polyene copolymer rubbers such as EPDM generally have a catalyst system consisting of a titanium catalyst or a combination of a vanadium catalyst and an organoaluminum compound (so-called Ziegler-Natta catalyst system). Have been manufactured. The biggest drawback of this catalyst system is its productivity, and because of its low polymerization activity and short catalyst life, polymerization at low temperatures around 0 to 50 ° C. is forced. For this reason, the high viscosity of the polymerization solution becomes an obstacle, the concentration of the olefin copolymer in the polymerization vessel cannot be sufficiently increased, and there is a problem that the productivity is extremely low. Furthermore, since the polymerization activity is low, the amount of the catalyst residue contained in the copolymer at the end of the polymerization is large and often does not satisfy the required product performance. Therefore, a deashing process for removing this is required, which is a significant disadvantage in terms of production cost.
　オレフィン重合用の均一系触媒としては、いわゆるメタロセン化合物がよく知られている。1980年代以降、活発に研究が行なわれてきたメタロセン触媒系は、優れた重合活性とα－オレフィン共重合能を示し、シングルサイト触媒であるが故に分子量分布、組成分布の狭いオレフィン系共重合体の製造を可能にするものである。このメタロセン化合物を触媒として用いたα－オレフィンの重合では、メタロセン化合物の配位子のシクロペンタジエニル環に置換基を導入したり、２個のシクロペンタジエニル環を架橋させたりすることにより、重合活性、得られるα－オレフィン重合体の分子量などが大きく変化することが知られ、多くの改良研究が行われている。 So-called metallocene compounds are well known as homogeneous catalysts for olefin polymerization. The metallocene catalyst system, which has been actively researched since the 1980s, has excellent polymerization activity and α-olefin copolymerization ability, and is a single-site catalyst, so it has a narrow molecular weight distribution and composition distribution. It is possible to manufacture. In the polymerization of α-olefins using this metallocene compound as a catalyst, a substituent is introduced into the cyclopentadienyl ring of the ligand of the metallocene compound or two cyclopentadienyl rings are cross-linked. It has been known that the polymerization activity, the molecular weight of the resulting α-olefin polymer, and the like vary greatly, and many improvement studies have been conducted.
　このような研究の一環として、シクロペンタジエニル配位子およびフルオレニル配位子を有するメタロセン化合物を用いた重合結果がJ. A. Ewenによって報告されている（J. Am. Chem. Soc., 110, 6255(1988)）。さらに、このメタロセン化合物の改良として、シクロペンタジエニル配位子とフルオレニル配位子とを二価のケイ素含有置換基を介して架橋したメタロセン化合物が報告されている（例えば、特許文献１、非特許文献１，２）。 As part of such research, J. A. Ewen reported the results of polymerization using metallocene compounds with cyclopentadienyl and fluorenyl ligands (J. Am. Chem. Soc., 110, 6255 (1988)). Furthermore, as an improvement of this metallocene compound, a metallocene compound in which a cyclopentadienyl ligand and a fluorenyl ligand are bridged through a divalent silicon-containing substituent has been reported (for example, Patent Document 1, Non-Patent Document 1, Patent Documents 1 and 2).
　また、フルオレニル配位子に様々な置換基を導入し、種々のフルオレニル配位子の立体的及び電子的効果が重合結果に与える影響も報告されている（Chem. Rev., 100, 1205(2000)等）。これらの文献において、フルオレン上の置換基効果の一つとして、メトキシ基のような含ヘテロ原子電子供与性基を4または5位に有する場合は触媒活性およびポリマー分子量が向上し、2,3,6または7位に有する場合は著しく重合活性が低下することが報告されている（例えば、特許文献２、非特許文献３，４）。 In addition, the influence of the steric and electronic effects of various fluorenyl ligands on the polymerization results by introducing various substituents into the fluorenyl ligand has been reported (Chem. 205 Rev., 100, 1205 (2000 )etc). In these documents, as one of the substituent effects on fluorene, when a heteroatom-containing electron donating group such as a methoxy group is present at the 4 or 5 position, the catalytic activity and the polymer molecular weight are improved. It has been reported that the polymerization activity is remarkably lowered when it is in the 6th or 7th position (for example, Patent Document 2, Non-Patent Documents 3 and 4).
　一般に、フルオレンの4,5位は置換基の導入が困難であるため、メタロセン化合物の触媒性能、製造コスト、生産効率などを考慮すると、フルオレン上にメトキシ基を有するメタロセン化合物は商業的実用化には不利である。したがって、フルオレニル配位子を有する既存のメタロセン化合物には、置換基を導入しやすい2,3,6または7位をアルキル基で修飾したものが非常に多く、隣接する置換基同士で環構造を形成することで優れたオレフィン重合触媒の実現を目指した報告例もある（特許第4367688号等）。 In general, it is difficult to introduce substituents at positions 4 and 5 of fluorene. Therefore, considering the catalytic performance, production cost, production efficiency, etc. of metallocene compounds, metallocene compounds having a methoxy group on fluorene are suitable for commercial use. Is disadvantageous. Therefore, existing metallocene compounds having a fluorenyl ligand are very often modified with an alkyl group at the 2, 3, 6 or 7 position where a substituent can be easily introduced, and a ring structure is formed between adjacent substituents. There is also a report example aiming at realization of an excellent olefin polymerization catalyst by forming (Patent No. 4367688, etc.).
　メタロセン触媒系を用いたエチレン／α－オレフィン／非共役ポリエン共重合体の製造方法に関しても多数報告されている。 A number of reports have been made on a method for producing an ethylene / α-olefin / non-conjugated polyene copolymer using a metallocene catalyst system.
　メタロセン触媒系を用いたエチレン／α－オレフィン／非共役ポリエン共重合体の製造方法においては、無脱灰プロセスに適応可能な重合活性、高温重合に耐え得る高い分子量、モノマー回収工程に負荷のかからない非共役ポリエン共重合能、物性面において良好な低温特性を示すための高いモノマー交互共重合能等、生産面、コスト面、物性面における課題を解決するため、従来、メタロセン化合物に種々の改良が加えられてきている。 In the production method of ethylene / α-olefin / non-conjugated polyene copolymer using metallocene catalyst system, polymerization activity applicable to non-deashing process, high molecular weight capable of withstanding high temperature polymerization, and no burden on monomer recovery process In order to solve problems in production, cost, and physical properties such as non-conjugated polyene copolymerization ability and high monomer alternating copolymerization ability to show good low-temperature properties in terms of physical properties, various improvements have been made to metallocene compounds. It has been added.
　たとえば特許文献３には、特定の架橋シクロペンタジエニル-フルオレニルメタロセン化合物を含む触媒を用いたエチレン／α－オレフィン／非共役ポリエン共重合体の製造方法が開示されており、この製造方法により、良好な重合活性で、良好な非共役ポリエン共重合能で、かつ非常に高い分子量を示し、かつモノマー交互共重合性の強いエチレン／α－オレフィン／非共役ポリエン共重合体を製造することができ、さらに、重合温度をより高く設定できることが記載されている。 For example, Patent Document 3 discloses a process for producing an ethylene / α-olefin / non-conjugated polyene copolymer using a catalyst containing a specific bridged cyclopentadienyl-fluorenyl metallocene compound. To produce an ethylene / α-olefin / nonconjugated polyene copolymer with good polymerization activity, good non-conjugated polyene copolymerization ability, a very high molecular weight, and strong monomer alternating copolymerization Further, it is described that the polymerization temperature can be set higher.
特開平７－１３８２７５号公報JP 7-138275 A 特開平６－１７２４４３号公報JP-A-6-172443 国際公開第２００９／０８１７９４号International Publication No. 2009/081794
　しかしながら、従来のメタロセン触媒系を用いたオレフィン重合体（たとえば、エチレン／α－オレフィン／非共役ポリエン共重合体）の製造方法には、重合活性、および製造される共重合体の高分子量化の観点から、さらなる改良の余地があった。 However, conventional methods for producing olefin polymers (for example, ethylene / α-olefin / nonconjugated polyene copolymers) using a metallocene catalyst system involve polymerization activity and high molecular weight of the produced copolymer. From the viewpoint, there was room for further improvement.
　このような従来技術における問題点に鑑み、本発明は、高い重合活性で、分子量の高いオレフィン重合体（とりわけエチレン／α－オレフィン／非共役ポリエン共重合体）を製造する方法、ならびにこのようなオレフィン重合体の製造に有用なメタロセン化合物およびオレフィン重合用触媒を提供することを目的とする。 In view of such problems in the prior art, the present invention provides a method for producing an olefin polymer having a high polymerization activity and a high molecular weight (especially an ethylene / α-olefin / nonconjugated polyene copolymer), and such a method. It is an object of the present invention to provide a metallocene compound and an olefin polymerization catalyst useful for the production of an olefin polymer.
　本発明者らは鋭意研究したところ、特定の構造を有する架橋メタロセン化合物を含むオレフィン重合用触媒を使用したオレフィン重合体の製造方法、ならびにこのようなオレフィン重合体の製造に有用なメタロセン化合物（遷移金属化合物）およびオレフィン重合用触媒により上記課題を解決できることを見い出し、本発明を完成させた。本発明の要旨は以下のとおりである。 The present inventors have intensively studied and found that a method for producing an olefin polymer using a catalyst for olefin polymerization containing a bridged metallocene compound having a specific structure, as well as a metallocene compound (transition) useful for the production of such an olefin polymer. The present inventors have found that the above problems can be solved by a metal compound) and an olefin polymerization catalyst, and have completed the present invention. The gist of the present invention is as follows.
　［１］
　下記一般式［Ｉ］または［ＩＩ］で表される遷移金属化合物［Ａ］。 [1]
The transition metal compound [A] represented by the following general formula [I] or [II].
Figure JPOXMLDOC01-appb-C000003
 〔式［I］および［II］において、
　Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ13およびＲ14は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ1からＲ4までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、Ｒ13およびＲ14は互いに結合して環を形成していてもよく、
　Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11およびＲ12は、それぞれ独立に、水素原子、ＺＲで表される置換基（ただし、Ｚは酸素原子または硫黄原子であり、Ｒは炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｚを介してフルオレニル配位子と結合している。）、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基（ただし、ＺＲで表される置換基を除く。）、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ5からＲ12までの隣接した置換基は互いに結合して環を形成していてもよく、Ｒ5からＲ12のうち、少なくとも１つはＺＲで表される置換基であり、
　Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれ、
　Ａは芳香環を含んでいてもよい炭素原子数２～２０の二価の飽和もしくは不飽和の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、
　Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、
　ｊは１～４の整数であり、
　Ｑは、ハロゲン原子、炭素数１～２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から選ばれ、ｊが２以上の場合は、複数個あるＱは互いに同一であっても異なっていてもよい。〕
　［２］
　前記一般式［I］または［II］においてＺが酸素原子である前記［１］の遷移金属化合物［Ａ］。
Figure JPOXMLDOC01-appb-C000003
 [In the formulas [I] and [II]
R 1 , R 2 , R 3 , R 4 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group or a nitrogen-containing group. , An atom or a substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents from R 1 to R 4 may be bonded to each other to form a ring, R 13 and R 14 may be bonded to each other to form a ring.
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom or a substituent represented by ZR (where Z is an oxygen atom or a sulfur atom) R is a substituent selected from the group consisting of 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 and a halogen-containing group; A hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group (however, the substitution represented by ZR) An atom or a substituent selected from the group consisting of a halogen atom and a halogen-containing group, and adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring, among the R 5 of R 12, at least one Z In a substituent represented,
Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom;
A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A contains two or more ring structures including a ring formed with Y. You may,
M is a titanium atom, a zirconium atom or a hafnium atom,
j is an integer from 1 to 4,
Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, a plurality of Q May be the same as or different from each other. ]
[2]
The transition metal compound [A] of the above [1], wherein Z is an oxygen atom in the general formula [I] or [II].
　［３］
　前記一般式［I］または［II］においてＹがケイ素原子である前記［１］または［２］の遷移金属化合物［Ａ］。 [3]
The transition metal compound [A] of the above [1] or [2], wherein Y is a silicon atom in the general formula [I] or [II].
　［４］
　前記一般式［I］または［II］においてＭがジルコニウム原子である前記［１］～［３］のいずれの遷移金属化合物［Ａ］。 [4]
The transition metal compound [A] according to any one of [1] to [3], wherein M is a zirconium atom in the general formula [I] or [II].
　［５］
　前記［１］～［４］のいずれの遷移金属化合物［Ａ］を含有するオレフィン重合用触媒。 [5]
A catalyst for olefin polymerization containing the transition metal compound [A] of any one of [1] to [4].
　［６］
　［Ｂ］［B-1］有機金属化合物、
　　　　［B-2］有機アルミニウムオキシ化合物、および
　　　　［B-3］遷移金属化合物［Ａ］と反応してイオン対を形成する化合物
からなる群より選ばれる少なくとも１種の化合物をさらに含有する前記［５］のオレフィン重合用触媒。 [6]
[B] [B-1] organometallic compound,
[B-2] The above-mentioned [5] further containing at least one compound selected from the group consisting of an organoaluminumoxy compound, and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair. ] Olefin polymerization catalyst.
　［７］
　前記［５］または［６］のオレフィン重合用触媒の存在下でオレフィンを重合する工程［Ｐ］を含む、オレフィン重合体の製造方法。 [7]
The manufacturing method of an olefin polymer including process [P] which superposes | polymerizes an olefin in presence of the catalyst for olefin polymerization of said [5] or [6].
　［８］
　前記工程［Ｐ］がエチレンを重合する工程である前記［７］のオレフィン重合体（すなわち、エチレン系重合体）の製造方法。 [8]
The method for producing an olefin polymer (that is, an ethylene polymer) according to [7], wherein the step [P] is a step of polymerizing ethylene.
　［９］
　前記工程［Ｐ］がエチレンと非共役ポリエンとを共重合する工程である前記［８］のオレフィン重合体の製造方法。 [9]
The method for producing an olefin polymer according to [8], wherein the step [P] is a step of copolymerizing ethylene and a non-conjugated polyene.
　［１０］
　前記非共役ポリエンが下記一般式［III］で表される前記［９］のオレフィン重合体の製造方法。 [10]
The method for producing an olefin polymer according to [9], wherein the non-conjugated polyene is represented by the following general formula [III].
Figure JPOXMLDOC01-appb-C000004
 　〔式中、ｍは０から２の整数であり、
　Ｒ15、Ｒ16、Ｒ17およびＲ18は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、該炭化水素基は二重結合を有していてもよく、
　Ｒ15からＲ18までのうちの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成していてもよく、Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成していてもよく、
　以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ15からＲ18までの少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ15からＲ18までの任意の二つの置換基は互いに結合して環を形成し、該環は二重合を含んでいる。
（iii）Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成している。
（iv）Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成している。〕
　［１１］
　前記非共役ポリエンが、５－エチリデン－２－ノルボルネン（ＥＮＢ）または５－ビニル－２－ノルボルネン（ＶＮＢ）であることを特徴とする、前記［１０］のオレフィン重合体の製造方法。
Figure JPOXMLDOC01-appb-C000004
 [Wherein m is an integer from 0 to 2;
R 15 , R 16 , R 17 and R 18 are each independently selected from 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. The hydrocarbon group may have a double bond,
Any two substituents of from R 15 to R 18 may bond to each other to form a ring, the ring may contain a double bond, with a pair of R 15 and R 16, Alternatively, R 17 and R 18 may form an alkylidene group, R 15 and R 17 , or R 16 and R 18 may be bonded to each other to form a double bond,
At least one of the following requirements (i) to (iv) is satisfied.
(I) At least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds.
(Ii) Any two substituents from R 15 to R 18 are bonded to each other to form a ring, and the ring includes bipolymerization.
(Iii) R 15 and R 16 or R 17 and R 18 form an alkylidene group.
(Iv) R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond. ]
[11]
[10] The method for producing an olefin polymer according to [10], wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).
　［１２］
　前記工程［Ｐ］がエチレンと炭素数が３から２０のα－オレフィンと非共役ポリエンとを共重合する工程である前記［９］～［１１］のいずれかのオレフィン重合体の製造方法。 [12]
The method for producing an olefin polymer according to any one of [9] to [11], wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
　［１３］
　前記α－オレフィンがプロピレンである前記［１２］のオレフィン重合体の製造方法。 [13]
[12] The method for producing an olefin polymer according to [12], wherein the α-olefin is propylene.
　［１４］
　前記工程［Ｐ］の重合温度が８０℃以上である前記［８］～［１３］のオレフィン重合体の製造方法。 [14]
The method for producing an olefin polymer according to the above [8] to [13], wherein the polymerization temperature in the step [P] is 80 ° C. or higher.
　［１５］
　前記工程［Ｐ］が炭素数３～２０のα－オレフィンを重合する工程である前記［７］のオレフィン重合体の製造方法。 [15]
The method for producing an olefin polymer according to the above [7], wherein the step [P] is a step of polymerizing an α-olefin having 3 to 20 carbon atoms.
　［１６］
　前記工程［Ｐ］がエチレンと炭素数３～２０のα－オレフィンとを共重合する工程である前記［１５］のオレフィン重合体の製造方法。 [16]
The method for producing an olefin polymer according to [15], wherein the step [P] is a step of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.
　［１７］
　前記α－オレフィンがプロピレンである前記［１５］または［１６］のオレフィン重合体の製造方法。 [17]
[15] The process for producing an olefin polymer according to [16], wherein the α-olefin is propylene.
　本発明によれば、高い重合活性で、分子量の高いオレフィン重合体、とりわけエチレン／α－オレフィン／非共役ポリエン共重合体を製造することができる。 According to the present invention, an olefin polymer having a high polymerization activity and a high molecular weight, particularly an ethylene / α-olefin / non-conjugated polyene copolymer can be produced.
　本発明についてさらに詳細に説明する。 The present invention will be described in further detail.
　　　　　　　　　　　〔遷移金属化合物［Ａ］〕
　本発明に係る遷移金属化合物［Ａ］（以下「架橋メタロセン化合物［Ａ］」または「成分（Ａ）」と記載することもある。）は、下記一般式［I］または［II］で表される。 [Transition metal compound [A]]
The transition metal compound [A] according to the present invention (hereinafter sometimes referred to as “bridged metallocene compound [A]” or “component (A)”) is represented by the following general formula [I] or [II]. The
Figure JPOXMLDOC01-appb-C000005
 　《Ｒ 1 ～Ｒ 14 、Ｙ、Ａ》
　前記一般式［I］および［II］において、
　Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ13およびＲ14は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ1からＲ4までの隣接した置換基は互いに結合して環を形成していてもよく（ただし、シクロペンタジエニル基およびＲ1～Ｒ4によって形成される構造から、フルオレニル基および置換フルオレニル基は除く。）、互いに結合していなくてもよく、好ましくは互いに結合しておらず、Ｒ13およびＲ14は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、
　Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11およびＲ12は、それぞれ独立に、水素原子、ＺＲで表される置換基（ただし、Ｚは酸素原子または硫黄原子であり、Ｒは炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｚを介してフルオレニル配位子と結合している。）、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基（ただし、ＺＲで表される置換基を除く。）、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ5からＲ12までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、Ｒ5からＲ12のうち、少なくとも１つ以上はＺＲで表される置換基である。
Figure JPOXMLDOC01-appb-C000005
 << R 1 to R 14 , Y, A >>
In the general formulas [I] and [II],
R 1 , R 2 , R 3 , R 4 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group or a nitrogen-containing group. , An atom or a substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents from R 1 to R 4 may be bonded to each other to form a ring (provided that from the structure formed by the cyclopentadienyl group and R 1 ~ R 4, except fluorenyl group and substituted fluorenyl groups.), it may not be linked to each other, not preferably bonded to each other, R 13 And R 14 may be bonded to each other to form a ring, and may not be bonded to each other;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom or a substituent represented by ZR (where Z is an oxygen atom or a sulfur atom) R is a substituent selected from the group consisting of 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 and a halogen-containing group; A hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group (however, the substitution represented by ZR) An atom or a substituent selected from the group consisting of a halogen atom and a halogen-containing group, and adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring, It may not be linked to each other, from R 5 Of 12, at least one is a substituent represented by ZR.
　炭素数１～２０の炭化水素基としては、炭素数１～２０のアルキル基、炭素数３～２０の環状飽和炭化水素基、炭素数２～２０の鎖状不飽和炭化水素基、炭素数３～２０の環状不飽和炭化水素基が例示される。また、Ｒ1からＲ12までの隣接した置換基が互いに結合して環を形成する場合であれば、互いに結合して環を形成する炭素数１～２０の炭化水素基としては、炭素数１～２０のアルキレン基、炭素数６～２０のアリーレン基等が例示される。 Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, and 3 carbon atoms. Illustrative are ˜20 cyclic unsaturated hydrocarbon groups. In the case where adjacent substituents from R 1 to R 12 are bonded to each other to form a ring, the hydrocarbon group having 1 to 20 carbon atoms that are bonded to each other to form a ring includes Examples include an alkylene group having ˜20, an arylene group having 6 to 20 carbon atoms, and the like.
　炭素数１～２０のアルキル基としては、直鎖状飽和炭化水素基であるメチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デカニル基など、分岐状飽和炭化水素基であるイソプロピル基、イソブチル基、s-ブチル基、t-ブチル基、t-アミル基、ネオペンチル基、3-メチルペンチル基、1,1-ジエチルプロピル基、1,1-ジメチルブチル基、1-メチル-1-プロピルブチル基、1,1-ジプロピルブチル基、1,1-ジメチル-2-メチルプロピル基、1-メチル-1-イソプロピル-2-メチルプロピル基、シクロプロピルメチル基などが例示される。アルキル基の炭素数は好ましくは１～６である。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl groups which are linear saturated hydrocarbon groups. , N-octyl group, n-nonyl group, n-decanyl group, etc., branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3 -Methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl Group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like are exemplified. The alkyl group preferably has 1 to 6 carbon atoms.
　炭素数３～２０の環状飽和炭化水素基としては、環状飽和炭化水素基であるシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルネニル基、1-アダマンチル基、2-アダマンチル基など、環状飽和炭化水素基の水素原子が炭素数１から１７の炭化水素基で置き換えられた基である3-メチルシクロペンチル基、3-メチルシクロヘキシル基、4-メチルシクロヘキシル基、4-シクロヘキシルシクロヘキシル基、4-フェニルシクロヘキシル基などが例示される。環状飽和炭化水素基の炭素数は好ましくは５～１１である。 Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups, 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, which is a group in which a hydrogen atom of a cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms, 4 Examples include -cyclohexylcyclohexyl group and 4-phenylcyclohexyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5 to 11.
　炭素数２～２０の鎖状不飽和炭化水素基としては、アルケニル基であるエテニル基（ビニル基）、1-プロペニル基、2-プロペニル基（アリル基）、1-メチルエテニル基（イソプロペニル基）など、アルキニル基であるエチニル基、1-プロピニル基、2-プロピニル基（プロパルギル基）などが例示される。鎖状不飽和炭化水素基の炭素数は好ましくは２～４である。 Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group) which are alkenyl groups. Examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), which are alkynyl groups. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
　炭素数３～２０の環状不飽和炭化水素基としては、環状不飽和炭化水素基であるシクロペンタジエニル基、ノルボルニル基、フェニル基、ナフチル基、インデニル基、アズレニル基、フェナントリル基、アントラセニル基など、環状不飽和炭化水素基の水素原子が炭素数１から１５の炭化水素基で置き換えられた基である3-メチルフェニル基（m-トリル基）、4-メチルフェニル基（p-トリル基）、4-エチルフェニル基、4-t-ブチルフェニル基、4-シクロヘキシルフェニル基、ビフェニリル基、3,4-ジメチルフェニル基、3,5-ジメチルフェニル基、2,4,6-トリメチルフェニル基（メシチル基）など、直鎖状炭化水素基または分岐状飽和炭化水素基の水素原子が炭素数３から１９の環状飽和炭化水素基または環状不飽和炭化水素基で置き換えられた基であるベンジル基、クミル基などが例示される。環状不飽和炭化水素基の炭素数は好ましくは６～１０である。 Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, anthracenyl group and the like, which are cyclic unsaturated hydrocarbon groups 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which a hydrogen atom of a cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A group in which a hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced by a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as a mesityl group) A benzyl group and a cumyl group and the like. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6-10.
　炭素数１～２０のアルキレン基としては、メチレン基、エチレン基、ジメチルメチレン基（イソプロピリデン基）、エチルメチレン基、1-メチルエチレン基、2-メチルエチレン基、1,1-ジメチルエチレン基、1,2-ジメチルエチレン基、n-プロピレン基などが例示される。アルキレン基の炭素数は好ましくは１～６である。 Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples include 1,2-dimethylethylene group and n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.
　炭素数６～２０のアリーレン基としては、o-フェニレン基、m-フェニレン基、p-フェニレン基、4,4'-ビフェニリレン基などが例示される。アリーレン基の炭素数は好ましくは６から１２である。 Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, 4,4′-biphenylylene group and the like. The carbon number of the arylene group is preferably 6 to 12.
　アリール基としては、前述した炭素数３～２０の環状不飽和炭化水素基の例と一部重複するが、芳香族化合物から誘導された置換基であるフェニル基、1-ナフチル基、2-ナフチル基、アントラセニル基、フェナントレニル基、テトラセニル基、クリセニル基、ピレニル基、インデニル基、アズレニル基、ピロリル基、ピリジル基、フラニル基、チオフェニル基などが例示される。アリール基としては、フェニル基または2-ナフチル基が好ましい。 The aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but is a phenyl group, a 1-naphthyl group, a 2-naphthyl group which is a substituent derived from an aromatic compound. Groups, 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 are exemplified. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.
　前記芳香族化合物としては、芳香族炭化水素および複素環式芳香族化合物であるベンゼン、ナフタレン、アントラセン、フェナントレン、テトラセン、クリセン、ピレン、ピレン、インデン、アズレン、ピロール、ピリジン、フラン、チオフェンなどが例示される。 Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, etc. Is done.
　置換アリール基としては、前述した炭素数３～２０の環状不飽和炭化水素基の例と一部重複するが、前記アリール基が有する１以上の水素原子が炭素数１～２０の炭化水素基、アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基により置換されてなる基が挙げられ、具体的には3-メチルフェニル基（m-トリル基）、4-メチルフェニル基（p-トリル基）、3-エチルフェニル基、4-エチルフェニル基、3,4-ジメチルフェニル基、3,5-ジメチルフェニル基、ビフェニリル基、4-（トリメチルシリル）フェニル基、4-アミノフェニル基、4-（ジメチルアミノ）フェニル基、4-（ジエチルアミノ）フェニル基、4-モルフォリニルフェニル基、4-メトキシフェニル基、4-エトキシフェニル基、4-フェノキシフェニル基、3,4-ジメトキシフェニル基、3,5-ジメトキシフェニル基、3-メチル-4-メトキシフェニル基、3,5-ジメチル-4-メトキシフェニル基、3-（トリフルオロメチル）フェニル基、4-（トリフルオロメチル）フェニル基、3-クロロフェニル基、4-クロロフェニル基、3-フルオロフェニル基、4-フルオロフェニル基、5-メチルナフチル基、2-(6-メチル)ピリジル基などが例示される。 The substituted aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms, Examples include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group. Specifically, a 3-methylphenyl group (m-tolyl group) ), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4- (trimethylsilyl) Phenyl group, 4-aminophenyl group, 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxy Enyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3- (trifluoromethyl) phenyl group 4- (trifluoromethyl) phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2- (6-methyl) pyridyl group, etc. Illustrated.
　ケイ素含有基としては、炭素数１～２０の炭化水素基において、炭素原子がケイ素原子で置き換えられた基であるトリメチルシリル基、トリエチルシリル基、t-ブチルジメチルシリル基、トリイソプロピルシリル基等のアルキルシリル基、ジメチルフェニルシリル基、メチルジフェニルシリル基、t-ブチルジフェニルシリル基等のアリールシリル基、ペンタメチルジシラニル基、トリメチルシリルメチル基などが例示される。アルキルシリル基の炭素数は１～１０が好ましく、アリールシリル基の炭素数は６～１８が好ましい。 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, each of which is a hydrocarbon group having 1 to 20 carbon atoms in which a carbon atom is replaced with a silicon atom. Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and t-butyldiphenylsilyl group, pentamethyldisiranyl group and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.
　窒素含有基としては、アミノ基、ニトロ基、およびN-モルフォリニル基、ならびに上述した炭素数１～２０の炭化水素基またはケイ素含有基において、=CH-構造単位が窒素原子で置き換えられた基、-CH2-構造単位が炭素数１～２０の炭化水素基が結合した窒素原子で置き換えられた基、または-CH3構造単位が炭素数１～２０の炭化水素基が結合した窒素原子またはニトリル基で置き換えられた基であるジメチルアミノ基、ジエチルアミノ基、ジメチルアミノメチル基、シアノ基、ピロリジニル基、ピペリジニル基、ピリジニル基などが例示される。窒素含有基としては、ジメチルアミノ基、N-モルフォリニル基が好ましい。 Examples of the nitrogen-containing group include an amino group, a nitro group, and an N-morpholinyl group, and the above-described hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group, in which = CH-structural unit is replaced with a nitrogen atom, A group in which the —CH 2 — structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a nitrogen atom or nitrile in which a hydrocarbon group having a —CH 3 structural unit to have 1 to 20 carbon atoms is bonded Examples thereof include a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, and a pyridinyl group, which are groups replaced with a group. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.
　酸素含有基としては、水酸基、ならびに上述した炭素数１～２０の炭化水素基、ケイ素含有基または窒素含有基において、-CH2-構造単位が酸素原子またはカルボニル基で置き換えられた基、または-CH3構造単位が炭素数１～２０の炭化水素基が結合した酸素原子で置き換えられた基であるメトキシ基、エトキシ基、t-ブトキシ基、フェノキシ基、トリメチルシロキシ基、メトキシエトキシ基、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、t-ブトキシメチル基、1-ヒドロキシエチル基、1-メトキシエチル基、1-エトキシエチル基、2-ヒドロキシエチル基、2-メトキシエチル基、2-エトキシエチル基、n-2-オキサブチレン基、n-2-オキサペンチレン基、n-3-オキサペンチレン基、アルデヒド基、アセチル基、プロピオニル基、ベンゾイル基、トリメチルシリルカルボニル基、カルバモイル基、メチルアミノカルボニル基、カルボキシ基、メトキシカルボニル基、カルボキシメチル基、エトカルボキシメチル基、カルバモイルメチル基、フラニル基、ピラニル基などが例示される。酸素含有基としては、メトキシ基が好ましい。 Examples of the oxygen-containing group include a hydroxyl group, a group in which the —CH 2 — structural unit is replaced with an oxygen atom or a carbonyl group in the above-described hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group, or — A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, hydroxymethyl, which is a group in which a CH 3 structural unit is replaced by an oxygen atom bonded with a hydrocarbon group having 1 to 20 carbon atoms 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-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group And trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, pyranyl group and the like. As the oxygen-containing group, a methoxy group is preferable.
　ハロゲン原子としては、第１７族元素であるフッ素、塩素、臭素、ヨウ素などが例示される。 Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine and iodine.
　ハロゲン含有基としては、上述した炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基または酸素含有基において、水素原子がハロゲン原子によって置換された基であるトリフルオロメチル基、トリブロモメチル基、ペンタフルオロエチル基、ペンタフルオロフェニル基などが例示される。 Examples of the halogen-containing group include a trifluoromethyl group, a tribromo group in which a hydrogen atom is substituted with a halogen atom in the above-described hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, nitrogen-containing group or oxygen-containing group. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.
　ＺＲで表される置換基は、一部が上述した酸素含有基と重複している。 The substituent represented by ZR partially overlaps the oxygen-containing group described above.
　ＺＲで表される置換基において、Ｚは酸素原子または硫黄原子であり、好ましくは酸素原子である。 In the substituent represented by ZR, Z is an oxygen atom or a sulfur atom, preferably an oxygen atom.
　Ｒは炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｒの中のＺと結合する原子は炭素原子またはケイ素原子である。これらの例としては、Ｒ1～Ｒ4、Ｒ13、Ｒ14として例示したものが挙げられ、好ましくはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、シクロヘキシル基、シクロへプチル基等の炭素数１～２０のアルキル基、またはフェニル基や2-ナフチル基等のアリール基、m-トリル基、p-トリル基等の置換アリール基、トリメチルシリル基、トリエチルシリル基、t-ブチルジメチルシリル基、トリイソプロピルシリル基等のアルキルシリル基であり、より好ましくはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、等の炭素数１～２０のアルキル基であり、さらに好ましくはメチル基である。 R is a substituent selected from the group consisting of 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 and a halogen-containing group; The atom bonded to is a carbon atom or a silicon atom. Examples thereof include those exemplified as R 1 to R 4 , R 13 and R 14 , preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert An alkyl group having 1 to 20 carbon atoms such as -butyl group, cyclohexyl group and cycloheptyl group, or an aryl group such as phenyl group and 2-naphthyl group, a substituted aryl group such as m-tolyl group and p-tolyl group, Alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Alkyl group having 1 to 20 carbon atoms such as tert-butyl group, more preferably methyl group.
　ＺＲで表される置換基は、Ｚを介してフルオレニル配位子と結合している。 The substituent represented by ZR is bonded to the fluorenyl ligand through Z.
　一般式［I］および［II］において、Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれ、好ましくは炭素原子またはケイ素原子であり、より好ましくはケイ素原子である。 In the general formulas [I] and [II], Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.
　一般式［II］において、Ａは芳香環を含んでいてもよい炭素原子数２～２０の二価の飽和もしくは不飽和の炭化水素基であり、ＡはＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。炭素原子数２～２０の二価の飽和もしくは不飽和の炭化水素基としては、Ｒ1～Ｒ14として例示したものが挙げられる。 In the general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A includes two rings including a ring formed with Y. The above ring structure may be included. Examples of the divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms include those exemplified as R 1 to R 14 .
　シクロペンタジエニル基：
　上記一般式［I］、［II］における置換基Ｒ1からＲ4を有するシクロペンタジエニル基としては、Ｒ1からＲ4が水素原子である無置換シクロペンタジエニル基、３－ｔ－ブチルシクロペンタジエニル基、３－メチルシクロペンタジエニル基、３－トリメチルシリルシクロペンタジエニル基、３－フェニルシクロペンタジエニル基、３－アダマンチルシクロペンタジエニル基、３－アミルシクロペンタジエニル基、３－シクロヘキシルシクロペンタジエニル基などの３位１置換シクロペンタジエニル基、３－ｔ－ブチル－５－メチルシクロペンタジエニル基、３－ｔ－ブチル－５－エチルシクロペンタジエニル基、３－フェニル－５－メチルシクロペンタジエニル基、３，５－ジ－ｔ－ブチルシクロペンタジエニル基、３，５－ジメチルシクロペンタジエニル基、３－フェニル－５－メチルシクロペンタジエニル基、３－トリメチルシリル－５－メチルシクロペンタジエニル基などの３，５位２置換シクロペンタジエニル基などが挙げることができるがこの限りではない。架橋メタロセン化合物の合成のし易さ、製造コスト及び非共役ポリエンの共重合能の観点から、無置換（Ｒ1～Ｒ4が水素原子）であるシクロペンタジエニル基が好ましい。 Cyclopentadienyl group:
The cyclopentadienyl group having substituents R 1 to R 4 in the above general formulas [I] and [II] is an unsubstituted cyclopentadienyl group in which R 1 to R 4 are hydrogen atoms, 3-t- Butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group Group, 3-position cyclopentadienyl group such as 3-cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl Group, 3-phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclo Examples thereof include a 3,5-disubstituted cyclopentadienyl group such as an tantadienyl group, a 3-phenyl-5-methylcyclopentadienyl group, and a 3-trimethylsilyl-5-methylcyclopentadienyl group. is not. From the viewpoint of ease of synthesis of the bridged metallocene compound, production cost, and copolymerization ability of the nonconjugated polyene, a cyclopentadienyl group which is unsubstituted (R 1 to R 4 are hydrogen atoms) is preferable.
　置換フルオレニル基：
　上記一般式［I］、［II］において、Ｒ5からＲ12のうち、少なくとも１つ以上はＺＲで表される置換基である。 Substituted fluorenyl group:
In the general formulas [I] and [II], at least one of R 5 to R 12 is a substituent represented by ZR.
　Ｒ5からＲ12のうち、好ましくはＲ6およびＲ11の少なくとも一方がＺＲであり、より好ましくはＲ6およびＲ11の両方がＺＲである。 Among R 5 to R 12 , preferably at least one of R 6 and R 11 is ZR, more preferably both R 6 and R 11 are ZR.
　Ｒ5、Ｒ8、Ｒ9およびＲ12は、架橋メタロセン化合物の合成のし易さの観点からは、好ましくは水素原子である。 R 5 , R 8 , R 9 and R 12 are preferably hydrogen atoms from the viewpoint of easy synthesis of the bridged metallocene compound.
　Ｒ7およびＲ10としては、ＺＲではない場合には、合成のし易さの観点からは、水素原子または炭素数１～２０の炭化水素基が好ましく、より高い重合活性を実現する観点からは、水素原子が特に好ましい。この炭素数１～２０の炭化水素基としては、Ｒ1～Ｒ14の炭素数１～２０の炭化水素基として例示したものが挙げられ、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、tert-ブチル基等のアルキル基が好ましく、tert-ブチル基がより好ましい。 R 7 and R 10 , when not ZR, are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of ease of synthesis, and from the viewpoint of realizing higher polymerization activity. A hydrogen atom is particularly preferable. Examples of the hydrocarbon group having 1 to 20 carbon atoms include those exemplified as the hydrocarbon group having 1 to 20 carbon atoms of R 1 to R 14 , such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Alkyl groups such as n-butyl group and tert-butyl group are preferred, and tert-butyl group is more preferred.
　架橋部：
　上記一般式［I］においてＲ13およびＲ14は互いに同一であっても異なってもよい。Ｒ13およびＲ14としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、フェニル基、ｍ－トリル基、ｐ－トリル基、４－ｔ－ブチルフェニル基、ｐ－クロロフェニル基、４－ビフェニル基、２－ナフチル基、キシリル基、ベンジル基、ｍ－トリフルオロメチルフェニル基が、高分子量のエチレン／α－オレフィン／非共役ポリエン共重合体を生成させることから、好ましい。 Cross-linking part:
In the general formula [I], R 13 and R 14 may be the same or different from each other. R 13 and R 14 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, m- A tolyl group, p-tolyl group, 4-t-butylphenyl group, p-chlorophenyl group, 4-biphenyl group, 2-naphthyl group, xylyl group, benzyl group, m-trifluoromethylphenyl group is a high molecular weight ethylene. This is preferable because a / α-olefin / non-conjugated polyene copolymer is produced.
　上記一般式［II］において、Ａは芳香環を含んでいてもよい炭素原子数２～２０の二価の飽和もしくは不飽和の炭化水素基であり、ＹはこのＡと結合し、例えば、下記式［IIa］で表されるシクロヘキシリデン基などのシクロアルキリデン基、下記式［IIb］で表されるシクロテトラメチレンシリレン基（１－シラシクロペンチリデン基）などのシクロメチレンシリレン基を構成する。 In the above general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and Y is bonded to this A. For example, A cycloalkylidene group such as a cyclohexylidene group represented by the formula [IIa] and a cyclomethylenesilylene group such as a cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by the following formula [IIb] .
Figure JPOXMLDOC01-appb-C000006
 （式［IIa］及び［IIb］において、●は、上記一般式［II］における（置換）シクロペンタジエニル基および置換フルオレニル基との結合点を表す。）
　また、ＡはＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000006
 (In formulas [IIa] and [IIb], ● represents the point of attachment to the (substituted) cyclopentadienyl group and substituted fluorenyl group in the above general formula [II].)
A may include two or more ring structures including a ring formed with Y.
　上記［IIa］で表されるシクロヘキシリデン基以外に具体的には、シクロプロピリデン基、シクロブチリデン基、シクロペンチリデン基、シクロヘプチリデン基、シクロオクチリデン基、ビシクロ[３．３．１]ノニリデン基、ノルボルニリデン基、アダマンチリデン基、テトラヒドロナフチリデン基、ジヒドロインダニリデン基などを挙げることができる。 Specifically, in addition to the cyclohexylidene group represented by the above [IIa], a cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cycloheptylidene group, cyclooctylidene group, bicyclo [3.3 .1] Nonylidene group, norbornylidene group, adamantylidene group, tetrahydronaphthylidene group, dihydroindanilidene group and the like.
　上記［IIb］で表されるシクロテトラメチレンシリレン基（１－シラシクロペンチリデン基）以外に具体的には、シクロジメチレンシリレン基、シクロトリメチレンシリレン基、シクロペンタメチレンシリレン基、シクロヘキサメチレンシリレン基、シクロヘプタメチレンシリレン基などを挙げることができる。 In addition to the cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by [IIb] above, specifically, cyclodimethylenesilylene group, cyclotrimethylenesilylene group, cyclopentamethylenesilylene group, cyclohexamethylene Examples thereof include a silylene group and a cycloheptamethylenesilylene group.
　《Ｍ、ｊ、Ｑ》
　一般式［I］および［II］において、Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、好ましくはジルコニウム原子またはハフニウム原子であり、より好ましくはジルコニウム原子である。 << M, j, Q >>
In the general formulas [I] and [II], M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.
　ｊは１～４の整数であり、好ましくは２である。 J is an integer of 1 to 4, preferably 2.
　Ｑは、ハロゲン原子、炭素数１～２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から選ばれ、ｊが２以上の場合は、複数個あるＱは互いに同一であっても異なっていてもよい。 Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, a plurality of Q May be the same as or different from each other.
　ハロゲン原子および炭素数１～２０の炭化水素基の詳細は、上述のとおりである。Ｑがハロゲン原子である場合は、塩素原子が好ましい。Ｑが炭素数１～２０の炭化水素基である場合は、該炭化水素基の炭素数は１から７であることが好ましい。 Details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.
　アニオン配位子としては、メトキシ基、t-ブトキシ基、フェノキシ基などのアルコキシ基、アセテート、ベンゾエートなどのカルボキシレート基、メシレート、トシレートなどのスルホネート基などを例示することができる。 Examples of 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.
　孤立電子対で配位可能な中性配位子としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニルメチルホスフィンなどの有機リン化合物、テトラヒドロフラン、ジエチルエーテル、ジオキサン、1,2-ジメトキシエタンなどのエーテル化合物などを例示することができる。 Neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc. An ether compound etc. can be illustrated.
　（前記遷移金属化合物［Ａ］の好ましい態様）
　前記遷移金属化合物［Ａ］の好ましい態様としては、たとえば、ジメチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジメチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジエチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジエチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-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-n－プロピルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジ-n-プロピルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジイソプロピルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジイソプロピルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-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-n－ブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジ-n－ブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジイソブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジイソブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-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-tert－ブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジ-tert－ブチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジシクロペンチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジシクロペンチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジシクロヘキシルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジシクロヘキシルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジシクロへプチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジシクロへプチルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、ジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-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-m-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジ-m-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-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-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、1-シラシクロペンチリデンシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド、1-シラシクロペンチリデンシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリドが挙げられる。さらに、ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド、ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチル、ジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド、ジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチル、ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジ-t-ブチル-4-メトキシフルオレニル)]ジルコニウムジクロリド、およびジp-トリルシリレン(η5-シクロペンタジエニル)(η5-4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)ジルコニウムジクロリドも挙げられる。 (Preferred embodiment of the transition metal compound [A])
Preferable embodiments of the transition metal compound [A] include, for example, dimethylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, dimethylsilylene (η 5- Cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diethylsilylene (η 5 -cyclopentadienyl) [η 5- (2 , 7-Dimethoxyfluorenyl)] zirconium dichloride, diethylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride Di-n-propylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-n-propylsilylene (η 5 -cyclopentadienyl) [ η 5 - (2,7- dimethoxy-3,6-di -tert- butyl fluorenylidenephenyl )] Zirconium dichloride, diisopropyl silylene (eta 5 - cyclopentadienyl) [η 5 - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, diisopropyl silylene (eta 5 - cyclopentadienyl) [η 5 - ( 2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, di-n-butylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorene) Nyl)] zirconium dichloride, di-n-butylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diisobutyl Silylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, diisobutylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy- 3,6-di-tert-butylfluorenyl)] zirconium Dichloride, di -tert- butylsilylene (eta 5 - cyclopentadienyl) [η 5 - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, di -tert- butylsilylene (eta 5 - cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, dicyclopentylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy Fluorenyl)] zirconium dichloride, dicyclopentylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, dicyclohexylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, dicyclohexylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3 , 6-Di-tert-butylfluorenyl)] zirconi Mujikurorido, Puchirushiriren dicyclohexyl (eta 5 - cyclopentadienyl) [η 5 - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, dicyclohexyl Puchirushiriren (eta 5 - cyclopentadienyl) [η 5 - (2 , 7-Dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride Diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, di-m-tolylsilylene (η 5- Cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-m-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3 , 6-Di-tert-butylfluorenyl)] zirconium dichloride, di -p-Tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5 -(2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, 1-silacyclopentylidenesilylene (η 5 -cyclopentadienyl) [η 5- (2,7- Dimethoxyfluorenyl)] zirconium dichloride, 1-silacyclopentylidenesilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Zirconium dichloride is mentioned. Further, di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, di-p-tolylsilylene (η 5 -Cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7- Dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride, and di-p-tolylsilylene (η 5 -Cyclopentadienyl) (η 5 -4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,4 -g '] dicromenyl) zirconium dichloride.
　《遷移金属化合物［Ａ］の製造方法》
　本発明に係る遷移金属化合物［Ａ］は、たとえば国際公開第０１／２７１２４号の第８４～９２頁に記載された製造方法を、式（１２）で表される化合物として、式（１２）の中のＲ5～Ｒ12が本発明における上述した式［I］または［II］で定義されるＲ5～Ｒ12とそれぞれ一致する化合物を用いて実施することにより、製造することができる。 << Production Method of Transition Metal Compound [A] >>
The transition metal compound [A] according to the present invention can be produced by, for example, using the production method described on pages 84 to 92 of WO 01/27124 as a compound represented by formula (12). R 5 ~ R 12 in is by carried out using compounds conforming respectively R 5 ~ R 12 as defined in formula [I] or [II] described above in the present invention, can be produced.
　　　　　　　　　　　〔オレフィン重合用触媒〕
　本発明に係るオレフィン重合用触媒は、本発明の遷移金属化合物［Ａ］を含んでいる。 [Olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention contains the transition metal compound [A] of the present invention.
　本発明のオレフィン重合用触媒は、好ましくは、
［Ｂ］［B-1］有機金属化合物、［B-2］有機アルミニウムオキシ化合物、および［B-3］遷移金属化合物［Ａ］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ばれる少なくとも１種の化合物（以下「化合物［Ｂ］」ともいう。）
をさらに含有する。 The olefin polymerization catalyst of the present invention is preferably
[B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] transition metal compounds [A] to form ion pairs. At least one compound (hereinafter also referred to as “compound [B]”)
Is further contained.
　本発明のオレフィン重合用触媒は、必要に応じて、好ましくは、
（Ｃ）担体
をさらに含有する。 The olefin polymerization catalyst of the present invention is preferably, if necessary,
(C) It further contains a carrier.
　本発明のオレフィン重合用触媒は、必要に応じて、
（Ｄ）有機化合物成分
をさらに含有してもよい。 The olefin polymerization catalyst of the present invention, if necessary,
(D) An organic compound component may be further contained.
　なお、本発明に係るオレフィン重合用触媒は、後述するオレフィン（エチレン、炭素数３～２０のα－オレフィンなど）の重合に使用することができる。 The olefin polymerization catalyst according to the present invention can be used for polymerization of olefin (ethylene, α-olefin having 3 to 20 carbon atoms, etc.) described later.
　以下、遷移金属化合物［Ａ］以外の各成分について具体的に説明する。 Hereinafter, each component other than the transition metal compound [A] will be specifically described.
　（化合物［Ｂ］）
　化合物［Ｂ］（以下「成分（Ｂ）」と記載することもある。）は、
　［B-1］有機金属化合物（以下「成分（B-1）」ともいう。）、好ましくは下記一般式（B-1a）で表される有機アルミニウム化合物［B-1a］、下記一般式（B-1b）で表される第１族金属とアルミニウムとの錯アルキル化物［B-1b］、または下記一般式（B-1c）で表される第２族または第１２族金属のジアルキル化合物［B-1c］、
　　　Ｒa mＡｌ（ＯＲb)n Ｈp Ｘq … （B-1a）
〔一般式（B-1a）中、Ｒa およびＲb は、炭素原子数が１～１５の炭化水素基を示し、互いに同一でも異なっていてもよく、Ｘはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３の数であり、かつｍ＋ｎ＋ｐ＋ｑ＝３である。〕
　　　Ｍa ＡｌＲa 4  … （B-1b）
〔一般式（B-1b）中、Ｍa はＬｉ、ＮａまたはＫを示し、Ｒa は炭素原子数が１～１５（好ましくは１～４）の炭化水素基を示す。〕
　　　Ｒa rＭbＲb s  Ｘt … （B-1c）
〔一般式（B-1c）中、Ｒa およびＲb は、炭素原子数が１～１５の炭化水素基を示し、互いに同一でも異なっていてもよく、Ｍb は、Ｍｇ、ＺｎおよびＣｄから選ばれ、Ｘはハロゲン原子を示し、rは０＜r≦２、ｓは０≦ｓ≦１、ｔは０≦ｔ≦１であり、かつｒ＋ｓ＋ｔ＝２である。〕、
　［B-2］有機アルミニウムオキシ化合物（以下「成分（B-2）」ともいう。）、および
　［B-3］遷移金属化合物［Ａ］と反応してイオン対を形成する化合物（以下「成分（B-3）」ともいう。）
からなる群から選ばれる少なくとも１種の化合物である。 (Compound [B])
Compound [B] (hereinafter sometimes referred to as “component (B)”)
[B-1] Organometallic compound (hereinafter also referred to as “component (B-1)”), preferably an organoaluminum compound [B-1a] represented by the following general formula (B-1a), B-1b) complex alkylated product of group 1 metal and aluminum [B-1b], or dialkyl compound of group 2 or group 12 metal represented by the following general formula (B-1c) [ B-1c],
R a m Al (OR b ) n H p X q (B-1a)
[In the general formula (B-1a), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m represents 0 <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M a AlR a 4 (B-1b)
[In the general formula (B-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms. ]
R a r M b R b s   X t (B-1c)
[In the general formula (B-1c), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other, and M b is selected from Mg, Zn and Cd. X is a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ],
[B-2] an organoaluminum oxy compound (hereinafter also referred to as “component (B-2)”), and [B-3] a compound that forms an ion pair by reacting with the transition metal compound [A] (hereinafter referred to as “component”). (B-3) ".)
At least one compound selected from the group consisting of:
　《有機金属化合物［B-1］》
　有機アルミニウム化合物［B-1a］としては、
　トリメチルアルミニウム、トリエチルアルミニウム、トリ-n-ブチルアルミニウム、トリ-n-ヘキシルアルミニウム、トリ-n-オクチルアルミニウムなどのトリ-n-アルキルアルミニウム、
　トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリsec-ブチルアルミニウム、トリ-t-ブチルアルミニウム、トリ-2-メチルブチルアルミニウム、トリ-3-メチルヘキシルアルミニウム、トリ-2-エチルヘキシルアルミニウムなどのトリ分岐状アルキルアルミニウム、
　トリシクロヘキシルアルミニウム、トリシクロオクチルアルミニウムなどのトリシクロアルキルアルミニウム、
　トリフェニルアルミニウム、トリ（4-メチルフェニル）アルミニウムなどのトリアリールアルミニウム、
　ジエチルアルミニウムハイドライド、ジイソプロピルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどのジアルキルアルミニウムハイドライド、
　一般式(i-C4H9)xAly(C5H10)z（式中、x、y、zは正の数であり、z≦2xである。）で表されるイソプレニルアルミニウムなどのアルケニルアルミニウム、
　イソブチルアルミニウムメトキシド、イソブチルアルミニウムエトキシドなどのアルキルアルミニウムアルコキシド、
　ジメチルアルミニウムメトキシド、ジエチルアルミニウムエトキシド、ジブチルアルミニウムブトキシドなどのジアルキルアルミニウムアルコキシド、
　エチルアルミニウムセスキエトキシド、ブチルアルミニウムセスキブトキシドなどのアルキルアルミニウムセスキアルコキシド、
　一般式Ｒa 2.5Ａｌ(ＯＲb)0.5などで表される平均組成を有する部分的にアルコキシ化されたアルキルアルミニウム、
　ジエチルアルミニウムフェノキシド、ジエチルアルミニウム(2,6-ジ-t-ブチル-4-メチルフェノキシド)などのアルキルアルミニウムアリーロキシド、
　ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジブチルアルミニウムクロリド、ジエチルアルミニウムブロミド、ジイソブチルアルミニウムクロリドなどのジアルキルアルミニウムハライド、
　エチルアルミニウムセスキクロリド、ブチルアルミニウムセスキクロリド、エチルアルミニウムセスキブロミドなどのアルキルアルミニウムセスキハライド、
　エチルアルミニウムジクロリドなどのアルキルアルミニウムジハライドなどの部分的にハロゲン化されたアルキルアルミニウム、
　エチルアルミニウムジヒドリド、プロピルアルミニウムジヒドリドなどのアルキルアルミニウムジヒドリドおよびその他の部分的に水素化されたアルキルアルミニウム、
　エチルアルミニウムエトキシクロリド、ブチルアルミニウムブトキシクロリド、エチルアルミニウムエトキシブロミドなどの部分的にアルコキシ化およびハロゲン化されたアルキルアルミニウム
などを例示することができる。また、上記一般式Ｒa mＡｌ(ＯＲb)nＨpＸqで表される化合物に類似する化合物も使用することができ、例えば窒素原子を介して2以上のアルミニウム化合物が結合した有機アルミニウム化合物を挙げることができる。このような化合物として具体的には、(C2H5)2AlN(C2H5)Al(C2H5)2などを挙げることができる。 << Organic metal compound [B-1] >>
As organoaluminum compound [B-1a],
Tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,
Tri-branched alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri-t-butyl aluminum, tri-2-methylbutyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum ,
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum,
Triarylaluminum such as triphenylaluminum, tri (4-methylphenyl) aluminum,
Dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride,
Such as isoprenylaluminum represented by the general formula (iC 4 H 9 ) x Al y (C 5 H 10 ) z (wherein x, y, z are positive numbers and z ≦ 2x) Alkenyl aluminum,
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide,
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide,
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide,
A partially alkoxylated alkylaluminum having an average composition represented by the general formula R a 2.5 Al (OR b ) 0.5, etc.
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride,
Alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride and other partially hydrogenated alkyl aluminums,
Examples thereof include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide. A compound similar to the compound represented by the general formula R a m Al (OR b ) n H p X q can also be used. For example, organoaluminum in which two or more aluminum compounds are bonded via a nitrogen atom. A compound can be mentioned. Specific examples of such a compound include (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 .
　第１族金属とアルミニウムとの錯アルキル化物［B-1b］としては、例えば、ＬｉＡｌ（Ｃ2Ｈ5）4、ＬｉＡｌ（Ｃ7Ｈ15）4が挙げられる。 Examples of the complex alkylated product [B-1b] of Group 1 metal and aluminum include LiAl (C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
　第２族または第１２族金属のジアルキル化合物［B-1c］としては、例えば、ジメチルマグネシウム、ジエチルマグネシウム、ジｎ－ブチルマグネシウム、エチルｎ－ブチルマグネシウム、ジフェニルマグネシウム、ジメチル亜鉛、ジエチル亜鉛、ジｎ－ブチル亜鉛、ジフェニル亜鉛が挙げられる。 Examples of the group 2 or group 12 metal dialkyl compound [B-1c] include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, and din. -Butyl zinc and diphenyl zinc are mentioned.
　これらの中では、前記有機アルミニウム化合物［B-1a］が好ましい。 Of these, the organoaluminum compound [B-1a] is preferred.
　有機金属化合物［B-1］は１種単独で用いてもよく、２種以上を併用してもよい。 The organometallic compound [B-1] may be used alone or in combination of two or more.
　《有機アルミニウムオキシ化合物［B-2］》
　有機アルミニウムオキシ化合物［B-2］としては、例えば、従来公知のアルミノキサンであってもよく、特開平２－７８６８７号公報に例示されているようなベンゼンに対して不溶性または難溶性の有機アルミニウムオキシ化合物であってもよい。従来公知のアルミノキサンは、例えば、下記（１）～（４）の方法によって製造することができ、通常、炭化水素溶媒の溶液として得られる。 << Organic aluminum oxy compound [B-2] >>
The organoaluminum oxy compound [B-2] may be, for example, a conventionally known aluminoxane, which is insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. It may be a compound. The conventionally known aluminoxane can be produced, for example, by the following methods (1) to (4), and is usually obtained as a solution in a hydrocarbon solvent.
　（１）吸着水を含有する化合物または結晶水を含有する塩類、例えば、塩化マグネシウム水和物、硫酸銅水和物、硫酸アルミニウム水和物、硫酸ニッケル水和物、塩化第１セリウム水和物等の炭化水素媒体懸濁液に、トリアルキルアルミニウム等の有機アルミニウム化合物を添加して、吸着水または結晶水と有機アルミニウム化合物とを反応させる方法。 (1) A compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension such as
　（２）ベンゼン、トルエン、ジエチルエーテル、テトラヒドロフラン等の媒体中で、トリアルキルアルミニウム等の有機アルミニウム化合物に、直接水、氷または水蒸気を作用させる方法。 (2) A method in which water, ice or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.
　（３）デカン、ベンゼン、トルエン等の媒体中で、トリアルキルアルミニウム等の有機アルミニウム化合物に、ジメチルスズオキシド、ジブチルスズオキシド等の有機スズ酸化物を反応させる方法。 (3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.
　（４）トリアルキルアルミニウム等の有機アルミニウムと、３級アルコール、ケトン、およびカルボン酸等の炭素－酸素結合を持つ有機化合物とを反応させて生成する化合物を、熱分解反応等の非加水分解的転化をする方法。 (4) Non-hydrolyzable compounds such as thermal decomposition reactions are produced by reacting organic aluminum such as trialkylaluminum with organic compounds having carbon-oxygen bonds such as tertiary alcohols, ketones and carboxylic acids. How to convert.
　なお、上記アルミノキサンは、少量の有機金属成分を含有してもよい。また、回収された上記アルミノキサンの溶液から溶媒または未反応有機アルミニウム化合物を蒸留して除去した後、溶媒に再溶解またはアルミノキサンの貧溶媒に懸濁させてもよい。 The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in a solvent or suspended in a poor aluminoxane solvent.
　アルミノキサンを調製する際に用いられる有機アルミニウム化合物としては、具体的には、有機アルミニウム化合物［B-1a］として例示したものと同一の有機アルミニウム化合物が挙げられる。これらの中でも、トリアルキルアルミニウム、トリシクロアルキルアルミニウムが好ましく、トリメチルアルミニウムが特に好ましい。 Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound [B-1a]. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
　その他、有機アルミニウムオキシ化合物［B-2］としては、例えば、修飾メチルアルミノキサンが挙げられる。修飾メチルアルミノキサンとは、トリメチルアルミニウムとトリメチルアルミニウム以外のアルキルアルミニウムとを用いて調製されるアルミノキサンである。このような化合物は、一般にＭＭＡＯと呼ばれている。ＭＭＡＯは、米国特許第４９６０８７８号明細書および米国特許第５０４１５８４号明細書で挙げられている方法で調製することができる。また、東ソー・ファインケム（株）社等からもトリメチルアルミニウムとトリイソブチルアルミニウムとを用いて調製された、Ｒがイソブチル基であるアルミノキサンが、ＭＭＡＯやＴＭＡＯといった名称で商業生産されている。 Other examples of the organoaluminum oxy compound [B-2] include modified methylaluminoxane. Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. In addition, aluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and the like, in which R is an isobutyl group, are commercially produced under the names MMAO and TMAO.
　このようなＭＭＡＯは、各種溶媒への溶解性および保存安定性を改良したアルミノキサンであり、具体的には上記のようなベンゼンに対して不溶性または難溶性のものとは違い、脂肪族炭化水素や脂環族炭化水素に溶解するという特徴を持つ。 Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike MMAO, which is insoluble or hardly soluble in benzene, aliphatic hydrocarbons and It has the feature of being soluble in alicyclic hydrocarbons.
　さらに、有機アルミニウムオキシ化合物［B-2］としては、例えば、ホウ素原子を含む有機アルミニウムオキシ化合物や、国際公開第２００５／０６６１９１号、国際公開第２００７／１３１０１０号に例示されているようなハロゲンを含むアルミノキサン、国際公開第２００３／０８２８７９号に例示されているようなイオン性アルミノキサンを挙げることもできる。 Furthermore, as the organoaluminum oxy compound [B-2], for example, an organoaluminum oxy compound containing a boron atom, or a halogen as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010. Examples of the aluminoxane include ionic aluminoxane as exemplified in International Publication No. WO2003 / 082879.
　有機アルミニウムオキシ化合物［B-2］は１種単独で用いてもよく、２種以上を併用してもよい。 The organoaluminum oxy compound [B-2] may be used alone or in combination of two or more.
　《遷移金属化合物［Ａ］と反応してイオン対を形成する化合物［B-3］》
　遷移金属化合物［Ａ］と反応してイオン対を形成する化合物［B-3］（以下「イオン性化合物［B-3］」ともいう。）としては、例えば、特表平１－５０１９５０号公報、特表平１－５０２０３６号公報、特開平３－１７９００５号公報、特開平３－１７９００６号公報、特開平３－２０７７０３号公報、特開平３－２０７７０４号公報、米国特許第５３２１１０６号明細書等に記載されたルイス酸、イオン性化合物、ボラン化合物およびカルボラン化合物が挙げられる。さらに、ヘテロポリ化合物およびイソポリ化合物も挙げることができる。 << Compound [B-3] which reacts with transition metal compound [A] to form an ion pair >>
As compound [B-3] (hereinafter also referred to as “ionic compound [B-3]”) that reacts with transition metal compound [A] to form an ion pair, for example, JP-A-1-501950 JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
　イオン性化合物［B-3］としては、一般式（B-3a）で表される化合物が好ましい。 As the ionic compound [B-3], a compound represented by the general formula (B-3a) is preferable.
Figure JPOXMLDOC01-appb-C000007
 　式（B-3a）中、Ｒe+としては、例えば、Ｈ+、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが挙げられる。Ｒf～Ｒiはそれぞれ独立に有機基、好ましくはアリール基である。
Figure JPOXMLDOC01-appb-C000007
 In the formula (B-3a), examples of R e + include H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R f to R i are each independently an organic group, preferably an aryl group.
　カルベニウムカチオンとしては、例えば、トリフェニルカルベニウムカチオン、トリス（メチルフェニル）カルベニウムカチオン、トリス（ジメチルフェニル）カルベニウムカチオン等の三置換カルベニウムカチオンが挙げられる。 Examples of the carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.
　アンモニウムカチオンとしては、例えば、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、トリ（ｎ－プロピル）アンモニウムカチオン、トリイソプロピルアンモニウムカチオン、トリ（ｎ－ブチル）アンモニウムカチオン、トリイソブチルアンモニウムカチオン等のトリアルキルアンモニウムカチオン；Ｎ，Ｎ－ジメチルアニリニウムカチオン、Ｎ，Ｎ－ジエチルアニリニウムカチオン、Ｎ，Ｎ－２，４，６－ペンタメチルアニリニウムカチオン等のＮ，Ｎ－ジアルキルアニリニウムカチオン；ジイソプロピルアンモニウムカチオン、ジシクロヘキシルアンモニウムカチオン等のジアルキルアンモニウムカチオンが挙げられる。 Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; N N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation And dialkyl ammonium cations.
　ホスホニウムカチオンとしては、例えば、トリフェニルホスホニウムカチオン、トリス（メチルフェニル）ホスホニウムカチオン、トリス（ジメチルフェニル）ホスホニウムカチオン等のトリアリールホスホニウムカチオンが挙げられる。 Examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tris (methylphenyl) phosphonium cation, and a tris (dimethylphenyl) phosphonium cation.
　Ｒe+としては、例えば、カルベニウムカチオン、アンモニウムカチオンが好ましく、特にトリフェニルカルベニウムカチオン、Ｎ，Ｎ－ジメチルアニリニウムカチオン、Ｎ，Ｎ－ジエチルアニリニウムカチオンが好ましい。 As R e + , for example, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.
　カルベニウム塩としては、例えば、トリフェニルカルベニウムテトラフェニルボレート、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルカルベニウムテトラキス（３，５－ジトリフルオロメチルフェニル）ボレート、トリス（４－メチルフェニル）カルベニウムテトラキス（ペンタフルオロフェニル）ボレート、トリス（３，５－ジメチルフェニル）カルベニウムテトラキス（ペンタフルオロフェニル）ボレートが挙げられる。 Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl). ) Carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.
　アンモニウム塩としては、例えば、トリアルキル置換アンモニウム塩、Ｎ，Ｎ－ジアルキルアニリニウム塩、ジアルキルアンモニウム塩が挙げられる。 Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.
　トリアルキル置換アンモニウム塩としては、例えば、トリエチルアンモニウムテトラフェニルボレート、トリプロピルアンモニウムテトラフェニルボレート、トリ（ｎ－ブチル）アンモニウムテトラフェニルボレート、トリメチルアンモニウムテトラキス（ｐ－トリル）ボレート、トリメチルアンモニウムテトラキス（ｏ－トリル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリプロピルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリプロピルアンモニウムテトラキス（２，４－ジメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（３，５－ジメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（４－トリフルオロメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（３，５－ジトリフルオロメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（ｏ－トリル）ボレート、ジオクタデシルメチルアンモニウムテトラフェニルボレート、ジオクタデシルメチルアンモニウムテトラキス（ｐ－トリル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（ｏ－トリル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（２，４－ジメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（３，５－ジメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（４－トリフルオロメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（３，５－ジトリフルオロメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムが挙げられる。 Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o- Tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis ( o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, Dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate DOO, dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate include dioctadecyl methyl ammonium.
　Ｎ，Ｎ－ジアルキルアニリニウム塩としては、例えば、Ｎ，Ｎ－ジメチルアニリニウムテトラフェニルボレート、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、Ｎ，Ｎ－ジメチルアニリニウムテトラキス（３，５－ジトリフルオロメチルフェニル）ボレート、Ｎ，Ｎ－ジエチルアニリニウムテトラフェニルボレート、Ｎ，Ｎ－ジエ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、Ｎ，Ｎ－ジエチルアニリニウムテトラキス（３，５－ジトリフルオロメチルフェニル）ボレート、Ｎ，Ｎ－２，４，６－ペンタメチルアニリニウムテトラフェニルボレート、Ｎ，Ｎ－２，４，６－ペンタ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）ボレートが挙げられる。 Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenyl borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoro) Methylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.
　ジアルキルアンモニウム塩としては、例えば、ジ（１－プロピル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジシクロヘキシルアンモニウムテトラフェニルボレートが挙げられる。 Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
　イオン性化合物［B-3］としては、その他、特開２００４－５１６７６号公報に開示されているイオン性化合物も制限無く使用が可能である。 As the ionic compound [B-3], other ionic compounds disclosed in JP-A-2004-51676 can be used without limitation.
　イオン性化合物［B-3］は１種単独で用いてもよく、２種以上を併用してもよい。 The ionic compound [B-3] may be used alone or in combination of two or more.
　〈担体［Ｃ］〉
　担体［Ｃ］としては、例えば、無機または有機の化合物であって、顆粒状ないしは微粒子状の固体が挙げられる。後述する本発明のオレフィン重合体の製造方法において、遷移金属化合物［Ａ］は、好ましくは担体［Ｃ］に担持された形態で用いられる。 <Carrier [C]>
Examples of the carrier [C] include inorganic or organic compounds, and granular or fine particle solids. In the method for producing an olefin polymer of the present invention described later, the transition metal compound [A] is preferably used in a form supported on a carrier [C].
　《無機化合物》
　担体［Ｃ］における無機化合物としては、多孔質酸化物、無機塩化物、粘土、粘土鉱物またはイオン交換性層状化合物が好ましい。 <Inorganic compounds>
The inorganic compound in the carrier [C] is preferably a porous oxide, inorganic chloride, clay, clay mineral or ion-exchangeable layered compound.
　多孔質酸化物としては、例えば、SiO2、Al2O3、MgO、ZrO2、TiO2、B2O3、CaO、ZnO、BaO、ThO2等の酸化物、またはこれらを含む複合物もしくは混合物を使用することができる。例えば、天然または合成ゼオライト、SiO2－MgO、SiO2－Al2O3、SiO2－TiO2、SiO2－V2O5、SiO2－Cr2O3、SiO2－TiO2－MgOを使用することができる。これらの中でも、SiO2および／またはAl2O3を主成分として含有する多孔質酸化物が好ましい。 Examples of the porous oxide include oxides such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, and ThO 2 , or composites containing these, Mixtures can be used. For example, natural or synthetic zeolite, SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 , SiO 2 —TiO 2 —MgO Can be used. Among these, a porous oxide containing SiO 2 and / or Al 2 O 3 as a main component is preferable.
　多孔質酸化物は、種類および製法によりその性状は異なる。本発明に好ましく用いられる担体は、粒径が好ましくは１～３００μｍ、より好ましくは３～１００μｍであり；比表面積が好ましくは５０～１３００ｍ2／g、より好ましくは２００～１２００ｍ2／ｇであり；細孔容積が好ましくは０．３～３．０ｃｍ3／ｇ、より好ましくは０．５～２．０ｃｍ3／ｇである。このような担体は、必要に応じて１００～１０００℃、好ましくは１５０～７００℃で乾燥および／または焼成して使用される。粒子形状については特に制限はないが、特に好ましくは球状である。 The properties of porous oxides vary depending on the type and production method. The carrier preferably used in the present invention has a particle size of preferably 1 to 300 μm, more preferably 3 to 100 μm; a specific surface area of preferably 50 to 1300 m 2 / g, more preferably 200 to 1200 m 2 / g. The pore volume is preferably 0.3 to 3.0 cm 3 / g, more preferably 0.5 to 2.0 cm 3 / g. Such a carrier is used after being dried and / or calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. The particle shape is not particularly limited, but is particularly preferably spherical.
　無機塩化物としては、例えば、MgCl2、MgBr2、MnCl2、MnBr2が用いられる。無機塩化物は、そのまま用いてもよいし、ボールミル、振動ミルにより粉砕した後に用いてもよい。また、アルコール等の溶媒に無機塩化物を溶解させた後、析出剤によって微粒子状に析出させたものを用いることもできる。 As the inorganic chloride, for example, MgCl 2 , MgBr 2 , MnCl 2 , and MnBr 2 are used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvent, such as alcohol, what was made to precipitate into a fine particle form with a depositing agent can also be used.
　粘土は、通常粘土鉱物を主成分として構成される。イオン交換性層状化合物は、イオン結合等によって構成される面が互いに弱い結合力で平行に積み重なった結晶構造を有する化合物であり、含有されるイオンが交換可能である。大部分の粘土鉱物はイオン交換性層状化合物である。また、これらの粘土、粘土鉱物、イオン交換性層状化合物としては、天然産のものに限らず、人工合成物を使用することもできる。また、粘土、粘土鉱物またはイオン交換性層状化合物としては、粘土、粘土鉱物、または六方最密パッキング型、アンチモン型、CdCl2型、CdI2型等の層状の結晶構造を有するイオン結晶性化合物を例示することができる。 Clay is usually composed mainly of clay minerals. An ion-exchange layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Also, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, or ion crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl 2 type, CdI 2 type, etc. It can be illustrated.
　粘土、粘土鉱物としては、例えば、カオリン、ベントナイト、木節粘土、ガイロメ粘土、アロフェン、ヒシンゲル石、パイロフィライト、ウンモ群、モンモリロナイト群、バーミキュライト、リョクデイ石群、パリゴルスカイト、カオリナイト、ナクライト、ディッカイト、ハロイサイト、ペクトライト、テニオライトが挙げられる。 Examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, pectolite, teniolite.
　イオン交換性層状化合物としては、例えば、α－Zr（HAsO4）2・H2O、α－Zr（HPO4）2、α－Zr（KPO4）2・3H2O、α－Ti（HPO4）2、α－Ti（HAsO4）2・H2O、α－Sn（HPO4）2・H2O、γ－Zr（HPO4）2、γ－Ti（HPO4）2、γ－Ti（NH4PO4）2・H2O等の多価金属の結晶性酸性塩が挙げられる。 Examples of the ion-exchangeable layered compound include α-Zr (HAsO 4 ) 2 · H 2 O, α-Zr (HPO 4 ) 2 , α-Zr (KPO 4 ) 2 · 3H 2 O, α-Ti (HPO 4 ) 2 , α-Ti (HAsO 4 ) 2 · H 2 O, α-Sn (HPO 4 ) 2 · H 2 O, γ-Zr (HPO 4 ) 2 , γ-Ti (HPO 4 ) 2 , γ- Examples include crystalline acidic salts of polyvalent metals such as Ti (NH 4 PO 4 ) 2 .H 2 O.
　粘土、粘土鉱物には、化学処理を施すことも好ましい。化学処理としては、表面に付着している不純物を除去する表面処理、粘土の結晶構造に影響を与える処理等、何れも使用できる。化学処理としては、具体的には、酸処理、アルカリ処理、塩類処理、有機物処理等が挙げられる。 It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like.
　イオン交換性層状化合物は、イオン交換性を利用し、層間の交換性イオンを別の大きな嵩高いイオンと交換することにより、層間が拡大した状態の層状化合物であってもよい。このような嵩高いイオンは、層状構造を支える支柱的な役割を担っており、通常、ピラーと呼ばれる。また、このように層状化合物の層間に別の物質を導入することをインターカレーションという。 The ion-exchangeable layered compound may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation.
　インターカレーションするゲスト化合物としては、例えば、TiCl4、ZrCl4等の陽イオン性無機化合物、Ti（OR）4、Zr（OR）4、PO（OR）3、B（OR）3等の金属アルコキシド（Rは炭化水素基等）、[Al13O4（OH）24]7+、[Zr4（OH）14]2+、[Fe3O（OCOCH3）6]+等の金属水酸化物イオンが挙げられる。これらの化合物は１種単独で用いてもよく、２種以上を併用してもよい。また、これらの化合物をインターカレーションする際に、Si（OR）4、Al（OR）3、Ge（OR）4等の金属アルコキシド（Rは炭化水素基等）などを加水分解して得た重合物、SiO2等のコロイド状無機化合物などを共存させることもできる。 Examples of the guest compounds to be intercalated include, for example, TiCl 4, ZrCl 4 cationic inorganic compounds such as, Ti (OR) 4, Zr (OR) 4, PO (OR) 3, B (OR) 3 or the like of metal Metal hydroxide such as alkoxide (R is hydrocarbon group, etc.), [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ] 2+ , [Fe 3 O (OCOCH 3 ) 6 ] + Examples include physical ions. These compounds may be used individually by 1 type, and may use 2 or more types together. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) 4 , Al (OR) 3 , Ge (OR) 4 (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO 2, and the like can also coexist.
　ピラーとしては、例えば、上記金属水酸化物イオンを層間にインターカレーションした後に加熱脱水することにより生成する酸化物が挙げられる。 Examples of the pillar include an oxide generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
　担体［Ｃ］の中でも、SiO2および／またはAl2O3を主成分として含有する多孔質酸化物が好ましい。また、粘土または粘土鉱物も好ましく、特に好ましいものはモンモリロナイト、バーミキュライト、ペクトライト、テニオライトおよび合成雲母である。 Among the supports [C], a porous oxide containing SiO 2 and / or Al 2 O 3 as a main component is preferable. Also preferred are clays or clay minerals, particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
　《有機化合物》
　担体［Ｃ］における有機化合物としては、例えば、粒径が５～３００μｍの範囲にある顆粒状ないしは微粒子状固体が挙げられる。具体的には、エチレン、プロピレン、１－ブテン、４－メチル－１－ペンテン等の炭素数２～１４のα－オレフィンを主成分として生成される（共）重合体、ビニルシクロヘキサン、スチレンを主成分として生成される（共）重合体、およびそれらの変成体を例示することができる。 《Organic compound》
Examples of the organic compound in the carrier [C] include a granular or fine particle solid having a particle size in the range of 5 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, vinylcyclohexane and styrene are mainly used. The (co) polymer produced | generated as a component, and those modifications can be illustrated.
　〈有機化合物成分［Ｄ］〉
　本発明において、有機化合物成分［Ｄ］は、必要に応じて、重合性能および生成ポリマーの物性を向上させる目的で使用される。有機化合物［Ｄ］としては、例えば、アルコール類、フェノール性化合物、カルボン酸、リン化合物、アミド、ポリエーテルおよびスルホン酸塩等が挙げられる。 <Organic compound component [D]>
In the present invention, the organic compound component [D] is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound [D] include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.
　〈各成分の使用法および添加順序〉
　オレフィン重合の際には、各成分の使用法、添加順序は任意に選ばれるが、以下のような方法が例示される。以下では、遷移金属化合物［Ａ］、化合物［Ｂ］、担体［Ｃ］および有機化合物成分［Ｄ］を、それぞれ「成分（Ａ）～（Ｄ）」ともいう。
（１）成分（Ａ）を単独で重合器に添加する方法。
（２）成分（Ａ）および成分（Ｂ）を任意の順序で重合器に添加する方法。
（３）成分（Ａ）を成分（Ｃ）に担持した触媒成分と、
　　　成分（Ｂ）とを任意の順序で重合器に添加する方法。
（４）成分（Ｂ）を成分（Ｃ）に担持した触媒成分と、
　　　成分（Ａ）とを任意の順序で重合器に添加する方法。
（５）成分（Ａ）と成分（Ｂ）とを成分（Ｃ）に担持した触媒成分を
　　　重合器に添加する方法。 <Usage and order of addition of each component>
In the case of olefin polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound [A], the compound [B], the carrier [C], and the organic compound component [D] are also referred to as “components (A) to (D)”, respectively.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) a catalyst component having component (A) supported on component (C);
A method of adding the component (B) to the polymerization vessel in an arbitrary order.
(4) a catalyst component carrying component (B) on component (C);
A method of adding the component (A) to the polymerization vessel in an arbitrary order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization vessel.
　上記（２）～（５）の各方法においては、各触媒成分の少なくとも２種は予め接触されていてもよい。成分（Ｂ）が担持されている上記（４）、（５）の各方法においては、必要に応じて担持されていない成分（Ｂ）を、任意の順序で添加してもよい。この場合、成分（Ｂ）は、同一でも異なっていてもよい。また、成分（Ｃ）に成分（Ａ）が担持された固体触媒成分、成分（Ｃ）に成分（Ａ）および成分（Ｂ）が担持された固体触媒成分は、オレフィンが予備重合されていてもよく、予備重合された固体触媒成分上に、さらに触媒成分が担持されていてもよい。 In each of the above methods (2) to (5), at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which the component (B) is supported, the component (B) that is not supported may be added in any order as necessary. In this case, the component (B) may be the same or different. Further, the solid catalyst component in which the component (C) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In addition, a catalyst component may be further supported on the prepolymerized solid catalyst component.
　　　　　　　　　〔オレフィン重合体の製造方法〕
　本発明のオレフィン重合体の製造方法は、上述のオレフィン重合用触媒の存在下でオレフィン（エチレン、炭素数３以上２０以下のα－オレフィンなど）を重合する工程［Ｐ］を有することを特徴としている。ここで「重合」とは、単独重合および共重合の総称である。また「オレフィン重合用触媒の存在下でオレフィンを重合する」とは、上記（１）～（５）の各方法のように任意の方法でオレフィン重合用触媒の各成分を重合器に添加して前記オレフィンを重合する態様を包含する。 [Olefin polymer production method]
The method for producing an olefin polymer of the present invention comprises a step [P] of polymerizing an olefin (ethylene, α-olefin having 3 to 20 carbon atoms, etc.) in the presence of the above-mentioned catalyst for olefin polymerization. Yes. Here, “polymerization” is a general term for homopolymerization and copolymerization. The term “polymerize olefin in the presence of an olefin polymerization catalyst” means that each component of the olefin polymerization catalyst is added to the polymerization vessel by any method as in the above methods (1) to (5). The aspect which superposes | polymerizes the said olefin is included.
　本発明では、重合は、溶液重合、懸濁重合等の液相重合法または気相重合法のいずれにおいても実施できる。液相重合法において用いられる不活性炭化水素媒体としては、例えば、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；エチレンクロリド、クロルベンゼン、ジクロロメタン等のハロゲン化炭化水素が挙げられる。不活性炭化水素媒体は１種単独で用いてもよく、２種以上を混合して用いてもよい。また、重合に供給されうる液化オレフィン自身を溶媒として用いる、いわゆるバルク重合法を用いることもできる。 In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.
　オレフィン重合用触媒を用いてオレフィンの重合を行うに際して、オレフィン重合用触媒を構成し得る各成分の使用量は以下のとおりである。また、オレフィン重合用触媒において、各成分の含有量を以下のとおりに調節することができる。 When the olefin polymerization is performed using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. In the olefin polymerization catalyst, the content of each component can be adjusted as follows.
　成分（Ａ）は、反応容積１リットル当り、通常１×１０-10～１×１０-2モル、好ましくは１×１０-8～１×１０-3モルとなるような量で用いられる。 Component (A) is generally used in an amount of 1 × 10 −10 to 1 × 10 −2 mol, preferably 1 × 10 −8 to 1 × 10 −3 mol per liter of reaction volume.
　成分（B-1）は、成分（B-1）と成分（Ａ）中の全遷移金属原子（Ｍ）とのモル比〔（B-1）/Ｍ〕が通常１～５０，０００、好ましくは１０～２０，０００、特に好ましくは５０～１０，０００となるような量で用いることができる。 Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of usually 1 to 50,000, preferably Can be used in an amount of 10 to 20,000, particularly preferably 50 to 10,000.
　成分（B-2）は、成分（B-2）中のアルミニウム原子と成分（Ａ）中の全遷移金属原子（Ｍ）とのモル比〔Ａｌ/Ｍ〕が通常１０～５，０００、好ましくは２０～２，０００となるような量で用いることができる。 Component (B-2) has a molar ratio [Al / M] of aluminum atoms in component (B-2) to all transition metal atoms (M) in component (A) of usually 10 to 5,000, preferably Can be used in an amount of 20 to 2,000.
　成分（B-3）は、成分（B-3）と成分（Ａ）中の全遷移金属原子（Ｍ）とのモル比〔（B-3）/Ｍ〕が通常１～１０００、好ましくは１～２００となるような量で用いることができる。 Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) of usually 1 to 1000, preferably 1 It can be used in an amount of 200.
　成分（Ｃ）を用いる場合は、成分（Ａ）と成分（Ｃ）との重量比〔（Ａ）/（Ｃ）〕が好ましくは０．０００１～１、より好ましくは０．０００５～０．５、さらに好ましくは０．００１～０．１となるような量で用いることができる。 When component (C) is used, the weight ratio of component (A) to component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5. More preferably, it can be used in an amount of 0.001 to 0.1.
　成分（Ｄ）を用いる場合は、
　成分（Ｂ）が成分（B-1）の場合には、モル比〔（Ｄ）/（B-1）〕が通常０．０１～１０、好ましくは０．１～５となるような量で、
　成分（Ｂ）が成分（B-2）の場合には、モル比〔（Ｄ）/（B-2）〕が通常０．００５～２、好ましくは０．０１～１となるような量で、
　成分（Ｂ）が成分（B-3）の場合は、モル比〔（Ｄ）/（B-3）〕が通常０．０１～１０、好ましくは０．１～５となるような量で用いることができる。 When using component (D),
When component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. ,
When component (B) is component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. ,
When component (B) is component (B-3), it is used in such an amount that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. be able to.
　本発明の製造方法において、重合温度は、通常－５０～＋２００℃、好ましくは０～２００℃、より好ましくは８０～２００℃であり、重合圧力は、通常常圧～１０ＭＰａゲージ圧、好ましくは常圧～５ＭＰａゲージ圧である。重合反応は、回分式、半連続式、連続式のいずれの方法においても行うことができる。さらに重合を反応条件の異なる二段以上に分けて行うこともできる。得られるオレフィン重合体の分子量は、重合系に水素等を存在させるか、重合温度を変化させるか、または成分（Ｂ）の使用量により調節することができる。 In the production method of the present invention, the polymerization temperature is usually −50 to + 200 ° C., preferably 0 to 200 ° C., more preferably 80 to 200 ° C., and the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure. Pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen or the like to exist in the polymerization system, changing the polymerization temperature, or using the component (B).
　特に水素は、触媒の重合活性を向上させる効果や、重合体の分子量を増加または低下させる効果が得られることがあり、好ましい添加物であるといえる。系内に水素を添加する場合、その量はオレフィン１モルあたり０．００００１～１００ＮＬ程度が適当である。系内の水素濃度は、水素の供給量を調整する以外にも、水素を生成または消費する反応を系内で行う方法や、膜を利用して水素を分離する方法、水素を含む一部のガスを系外に放出することによっても調整することができる。 In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.
　本発明の製造方法で得られたオレフィン重合体（たとえば、エチレン／α－オレフィン／非共役ポリエン共重合体）に対しては、オレフィン重合体を上記方法で合成した後に、必要に応じて公知の触媒失活処理工程、触媒残渣除去工程、乾燥工程等の後処理工程を行ってよい。 For the olefin polymer obtained by the production method of the present invention (for example, ethylene / α-olefin / non-conjugated polyene copolymer), after synthesizing the olefin polymer by the above-mentioned method, it is known as necessary. You may perform post-processing processes, such as a catalyst deactivation processing process, a catalyst residue removal process, and a drying process.
　〈オレフィン〉
　本発明の製造方法の一つの態様において、重合反応に供給されるオレフィンは、炭素数３～２０のα－オレフィンである。 <Olefin>
In one embodiment of the production method of the present invention, the olefin supplied to the polymerization reaction is an α-olefin having 3 to 20 carbon atoms.
　この態様においては、エチレンを単独重合してもよく、エチレンと非共役ジエンとを共重合してもよく、エチレンと炭素数３以上２０以下のα－オレフィンと非共役ジエンとを共重合してもよい。 In this embodiment, ethylene may be homopolymerized, ethylene may be copolymerized with a nonconjugated diene, or ethylene may be copolymerized with an α-olefin having 3 to 20 carbon atoms and a nonconjugated diene. Also good.
　また、本発明の製造方法の他の態様において、重合反応に供給されるオレフィンは、炭素数３～２０のα－オレフィンである。 In another embodiment of the production method of the present invention, the olefin supplied to the polymerization reaction is an α-olefin having 3 to 20 carbon atoms.
　この態様においては、エチレンと炭素数３以上２０以下のα－オレフィンとを共重合してもよく、炭素数３以上２０以下のα－オレフィンと非共役ジエンとを共重合してもよく、エチレンと炭素数３以上２０以下のα－オレフィンと非共役ジエンとを共重合してもよい。 In this embodiment, ethylene and an α-olefin having 3 to 20 carbon atoms may be copolymerized, or an α-olefin having 3 to 20 carbon atoms and a non-conjugated diene may be copolymerized. And an α-olefin having 3 to 20 carbon atoms and a non-conjugated diene may be copolymerized.
　本発明の製造方法によれば、高い重合活性で、分子量の高いオレフィン重合体、とりわけエチレン／α－オレフィン／非共役ポリエン共重合体を製造することができる。 According to the production method of the present invention, an olefin polymer having a high polymerization activity and a high molecular weight, particularly an ethylene / α-olefin / non-conjugated polyene copolymer can be produced.
　前記α－オレフィンとしては、炭素数３～１０のα－オレフィンが特に好ましい。 The α-olefin is particularly preferably an α-olefin having 3 to 10 carbon atoms.
　本発明で用いられる炭素数３以上のα－オレフィンとしては、プロピレン、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン、ビニルシクロヘキサンなどの炭素数３から２０の直鎖状または分岐状のα－オレフィンを例示することができる。α－オレフィンとしては、炭素数３～１０のα－オレフィン、例えば炭素数３から１０の直鎖状または分岐状のα－オレフィンが好ましく、プロピレン、1-ブテン、1-ヘキセンおよび1-オクテンがより好ましく、プロピレンがさらに好ましい。これらのα－オレフィンは１種単独で、または２種以上組み合わせて用いることができる。またその選択については、生成する共重合体の特性上最も望ましいものとなるように選ぶことが可能である。例えば、本発明で得られるエチレン系重合体または当共重合体を含む混合物を加硫処理した際の物性が望ましいものとなるようにα－オレフィンの種類を選択することができる。 Examples of the α-olefin having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc., linear or branched α having 3 to 20 carbon atoms -Olefin can be exemplified. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, for example, a linear or branched α-olefin having 3 to 10 carbon atoms, and propylene, 1-butene, 1-hexene and 1-octene are preferred. More preferably, propylene is more preferable. These α-olefins can be used alone or in combination of two or more. The selection can be made so as to be the most desirable in terms of the properties of the copolymer to be produced. For example, the type of α-olefin can be selected so that the physical properties when the ethylene polymer obtained in the present invention or a mixture containing the copolymer is vulcanized are desirable.
　前記非共役ポリエンとしては、非共役不飽和結合を２個以上有する化合物が制限なく使用できるが、例えば後述の非共役環状ポリエン、非共役鎖状ポリエンなどが挙げられ、１種単独で、あるいは２種以上を組み合わせて用いることが可能である。 As the non-conjugated polyene, a compound having two or more non-conjugated unsaturated bonds can be used without limitation, and examples thereof include a non-conjugated cyclic polyene and a non-conjugated chain polyene described later, and one kind alone or two It is possible to use a combination of more than one species.
　［非共役環状ポリエン］
　非共役環状ポリエンとして具体的には、例えば下記一般式［III］で表される化合物が挙げられる。 [Non-conjugated cyclic polyene]
Specific examples of the non-conjugated cyclic polyene include compounds represented by the following general formula [III].
Figure JPOXMLDOC01-appb-C000008
 　式［III］において、ｍは０から２の整数であり、
　Ｒ15、Ｒ16、Ｒ17およびＲ18は水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
　Ｒ15からＲ18までの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成していてもよく、Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成していてもよく、
　以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ15からＲ18の少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ18からＲ18までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる。
（iii）Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成している。
（iv）Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成している。
Figure JPOXMLDOC01-appb-C000008
 In the formula [III], m is an integer from 0 to 2,
R 15 , R 16 , R 17 and R 18 are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups or substituents Each may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R 15 to R 18 may be bonded to each other to form a ring, and the ring may contain a double bond, and R 15 and R 16 may be combined with each other, or R 17 and R 18 may form an alkylidene group, R 15 and R 17 or R 16 and R 18 may be bonded to each other to form a double bond,
At least one of the following requirements (i) to (iv) is satisfied.
(I) At least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds.
(Ii) Any two substituents from R 18 to R 18 are bonded to each other to form a ring, and the ring contains a double bond.
(Iii) R 15 and R 16 or R 17 and R 18 form an alkylidene group.
(Iv) R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond.
　上記一般式［III］において、Ｒ15、Ｒ16、Ｒ17およびＲ18として挙げた、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基の具体例としては、上記一般式［I］および［II］の説明の中で挙げられたこれらの原子および置換基の具体例が挙げられる。 In the above general formula [III], the hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups mentioned as R 15 , R 16 , R 17 and R 18 Specific examples of the group include specific examples of these atoms and substituents mentioned in the description of the general formulas [I] and [II].
　上記一般式［III］において、Ｒ15、Ｒ16、Ｒ17およびＲ18のいずれか一つ以上が、二重結合を一つ以上有する炭化水素基である場合、該炭化水素基としてはエテニル基（ビニル基）、1-プロペニル基、2-プロペニル基（アリル基）、1-メチルエテニル基（イソプロペニル基）、1-ブテニル基、2-ブテニル基、3-ブテニル基、1,4-ヘキサジエニル基などが例示される。例えばＲ15がエテニル基（ビニル基）の場合、上記一般式［III］の化合物は下記一般式［III-I］で表すことができる。 In the general formula [III], when any one or more of R 15 , R 16 , R 17 and R 18 is a hydrocarbon group having one or more double bonds, the hydrocarbon group is an ethenyl group. (Vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,4-hexadienyl group Etc. are exemplified. For example, when R 15 is an ethenyl group (vinyl group), the compound of the general formula [III] can be represented by the following general formula [III-I].
Figure JPOXMLDOC01-appb-C000009
 　式［III-I］において、ｍは０から２の整数であり、
　Ｒ16、Ｒ17およびＲ18は水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
　Ｒ16からＲ18の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ17とＲ18とでアルキリデン基を形成していてもよく、Ｒ16とＲ18とが互いに結合して二重結合を形成していてもよい。
Figure JPOXMLDOC01-appb-C000009
 In the formula [III-I], m is an integer of 0 to 2,
R 16 , R 17 and R 18 are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from a halogen atom and a halogen-containing group; Each may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R 16 to R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 form an alkylidene group. R 16 and R 18 may be bonded to each other to form a double bond.
　上記一般式［III］において、Ｒ15からＲ18までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる場合、上記一般式［III］の化合物は、例えば下記一般式［III-II］または［III-III］で表すことができる。 In the general formula [III], when any two substituents from R 15 to R 18 are bonded to each other to form a ring and the ring contains a double bond, the general formula [III] The compound can be represented, for example, by the following general formula [III-II] or [III-III].
Figure JPOXMLDOC01-appb-C000010
 　式［III-II］および［III-III］において、ｍは０から２の整数であり、
　Ｒ16、Ｒ17およびＲ18は水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
　Ｒ16からＲ18の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ17とＲ18とでアルキリデン基を形成していてもよく、Ｒ16とＲ18とが互いに結合して二重結合を形成していてもよい。
Figure JPOXMLDOC01-appb-C000010
 In the formulas [III-II] and [III-III], m is an integer of 0 to 2,
R 16 , R 17 and R 18 are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, an atom or a substituent selected from a halogen atom and a halogen-containing group; Each may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R 16 to R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 form an alkylidene group. R 16 and R 18 may be bonded to each other to form a double bond.
　上記一般式［III］において、Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成している場合、該アルキリデン基は通常炭素数１から２０のアルキリデン基であり、具体的な例としてはメチレン基（ＣＨ2＝）、エチリデン基（ＣＨ3ＣＨ＝）、プロピリデン基（ＣＨ3ＣＨ2ＣＨ＝）およびイソプロピリデン基（(ＣＨ3)2Ｃ＝）などが挙げられる。例えば、Ｒ15とＲ16とでエチリデン基を形成している場合、上記一般式［III］の化合物は下記一般式［III-IV］で表すことができる。 In the above general formula [III], when R 15 and R 16 or R 17 and R 18 form an alkylidene group, the alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms. Specific examples include a methylene group (CH 2 =), an ethylidene group (CH 3 CH =), a propylidene group (CH 3 CH 2 CH =), an isopropylidene group ((CH 3 ) 2 C =), and the like. For example, when R 15 and R 16 form an ethylidene group, the compound of the general formula [III] can be represented by the following general formula [III-IV].
Figure JPOXMLDOC01-appb-C000011
 　式［III-IV］において、ｍは０から２の整数であり、
　Ｒ17およびＲ18は水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
　Ｒ17とＲ18とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ17とＲ18とでアルキリデン基を形成していてもよい。
Figure JPOXMLDOC01-appb-C000011
 In the formula [III-IV], m is an integer of 0 to 2,
R 17 and R 18 are each 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, or a halogen-containing group, or a substituent. They may be different, and the hydrocarbon group may have a double bond,
R 17 and R 18 may be bonded to each other to form a ring, the ring may contain a double bond, and R 17 and R 18 may form an alkylidene group.
　上記一般式［III］において、Ｒ15とＲ17とが、またはＲ16とＲ8とが互いに結合して二重結合を形成している場合、上記一般式［III］の化合物は、例えば下記一般式［III-V］で表すことができる。 In the general formula [III], when R 15 and R 17 or R 16 and R 8 are bonded to each other to form a double bond, the compound of the general formula [III] is, for example, It can be represented by the general formula [III-V].
Figure JPOXMLDOC01-appb-C000012
 　式［III-V］において、ｍは０から２の整数であり、
　Ｒ16およびＲ18は水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
　Ｒ16とＲ18とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000012
 In the formula [III-V], m is an integer of 0 to 2,
R 16 and R 18 are substituents selected from 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, and they are the same or different. The hydrocarbon group may have a double bond,
R 16 and R 18 may be bonded to each other to form a ring, and the ring may contain a double bond.
　上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ15からＲ18の少なくとも一つが二重結合を一つ以上有する炭化水素基である化合物として、例えば５－ビニル－２－ノルボルネン（ＶＮＢ）および下記の化合物などが例示される。これらのうち、５－ビニル－２－ノルボルネン（ＶＮＢ）が好ましい。 Among the non-conjugated cyclic polyenes represented by the above general formula [III], as a compound in which at least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds, for example, 5-vinyl-2-norbornene (VNB) and the following compounds are exemplified. Of these, 5-vinyl-2-norbornene (VNB) is preferred.
Figure JPOXMLDOC01-appb-C000013
 　上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ15からＲ18までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる化合物として、例えばジシクロペンタジエン（ＤＣＰＤ）、ジメチルジシクロペンタジエンおよび下記の化合物などが例示される。これらのうち、ジシクロペンタジエン（ＤＣＰＤ）が好ましい。
Figure JPOXMLDOC01-appb-C000013
 Of the non-conjugated cyclic polyene represented by the general formula [III], any two substituents from R 15 to R 18 are bonded to each other to form a ring, and the ring contains a double bond. Examples of the compound include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds. Of these, dicyclopentadiene (DCPD) is preferred.
Figure JPOXMLDOC01-appb-C000014
 　上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成している化合物として、５－メチレン－２－ノルボルネン、５－エチリデン－２－ノルボルネン（ＥＮＢ）、５－イソプロピリデン－２－ノルボルネンおよび下記の化合物などが例示される。これらのうち、５－エチリデン－２－ノルボルネン（ＥＮＢ）が好ましい。
Figure JPOXMLDOC01-appb-C000014
 Among the non-conjugated cyclic polyenes represented by the above general formula [III], as compounds in which an alkylidene group is formed by R 15 and R 16 or R 17 and R 18 , 5-methylene-2-norbornene , 5-ethylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene and the following compounds. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.
Figure JPOXMLDOC01-appb-C000015
 　上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成している化合物としては、下記のものが好ましい。
Figure JPOXMLDOC01-appb-C000015
 Of the non-conjugated cyclic polyenes represented by the above general formula [III], R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond. Are preferred.
Figure JPOXMLDOC01-appb-C000016
 　上記一般式［III］で表される非共役環状ポリエンとしては、ｍが０の非共役環状ポリエンが好ましく、特に上記一般式［III］においてｍが０のアルキリデン基置換非共役環状ポリエン、上記一般式［III］においてｍが０の二重結合含有環置換非共役環状ポリエン、ｍが０の二重結合含有炭化水素基置換非共役環状ポリエンが好ましい。具体的には、５－エチリデン－２－ノルボルネン（ＥＮＢ）、ジシクロペンタジエン（ＤＣＰＤ）、５－ビニル－２－ノルボルネン（ＶＮＢ）がより好ましい。このうち５－エチリデン－２－ノルボルネン（ＥＮＢ）または５－ビニル－２－ノルボルネン（ＶＮＢ）が特に好ましい。
Figure JPOXMLDOC01-appb-C000016
 As the non-conjugated cyclic polyene represented by the general formula [III], a non-conjugated cyclic polyene having m = 0 is preferable, and in particular, an alkylidene group-substituted non-conjugated cyclic polyene in which m is 0 in the general formula [III], In formula [III], a double bond-containing ring-substituted nonconjugated cyclic polyene in which m is 0 and a double bond-containing hydrocarbon group-substituted nonconjugated cyclic polyene in which m is 0 are preferred. Specifically, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are more preferable. Of these, 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB) is particularly preferred.
　［非共役鎖状ポリエン］
　非共役鎖状ポリエンとして具体的には、例えば、１，４－ヘキサジエン、１，５－ヘプタジエン、１，６－オクタジエン、１，７－ノナジエン、１，８－デカジエン、１，１２－テトラデカジエン、３－メチル－１，４－ヘキサジエン、４－メチル－１，４－ヘキサジエン、５－メチル－１，４－ヘキサジエン、４－エチル－１，４－ヘキサジエン、３，３－ジメチル－１，４－ヘキサジエン、５－メチル－１，４－ヘプタジエン、５－エチル－１，４－ヘプタジエン、５－メチル－１，５－ヘプタジエン、６－メチル－１，５－ヘプタジエン、５－エチル－１，５－ヘプタジエン、４－メチル－１，４－オクタジエン、５－メチル－１，４－オクタジエン、４－エチル－１，４－オクタジエン、５－エチル－１，４－オクタジエン、５－メチル－１，５－オクタジエン、６－メチル－１，５－オクタジエン、５－エチル－１，５－オクタジエン、６－エチル－１，５－オクタジエン、６－メチル－１，６－オクタジエン、７－メチル－１，６－オクタジエン、６－エチル－１，６－オクタジエン、６－プロピル－１，６－オクタジエン、６－ブチル－１，６－オクタジエン、７－メチル－１，６－オクタジエン、６，７－ジメチル－１，６－オクタジエン、４－メチル－１，４－ノナジエン、５－メチル－１，４－ノナジエン、４－エチル－１，４－ノナジエン、５－エチル－１，４－ノナジエン、５－メチル－１，５－ノナジエン、６－メチル－１，５－ノナジエン、５－エチル－１，５－ノナジエン、６－エチル－１，５－ノナジエン、６－メチル－１，６－ノナジエン、７－メチル－１，６－ノナジエン、６－エチル－１，６－ノナジエン、７－エチル－１，６－ノナジエン、７－メチル－１，７－ノナジエン、８－メチル－１，７－ノナジエン、７－エチル－１，７－ノナジエン、６，７－ジメチル－１，６－ノナジエン、５－メチル－１，４－デカジエン、５－エチル－１，４－デカジエン、５－メチル－１，５－デカジエン、６－メチル－１，５－デカジエン、５－エチル－１，５－デカジエン、６－エチル－１，５－デカジエン、６－メチル－１，６－デカジエン、６－エチル－１，６－デカジエン、７－メチル－１，６－デカジエン、７－エチル－１，６－デカジエン、７－メチル－１，７－デカジエン、８－メチル－１，７－デカジエン、７－エチル－１，７－デカジエン、８－エチル－１，７－デカジエン、８－メチル－１，８－デカジエン、９－メチル－１，８－デカジエン、８－エチル－１，８－デカジエン、６－メチル－１，６－ウンデカジエン、９－メチル－１，８－ウンデカジエンなどが挙げられる。 [Non-conjugated chain polyene]
Specific examples of the non-conjugated chain polyene include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, and 1,12-tetradecadiene. 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4 -Hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5 -Heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl 1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7- Methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6, 7-dimethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7 Methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7- Ethyl-1,7-nonadiene, 6,7-dimethyl-1,6-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-deca Diene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8- Examples include undecadiene.
　他の非共役鎖状ポリエンとしては、例えば１，７－オクタジエン、１，９－デカジエン等のα，ω－ジエン等が挙げられる
　また、他の非共役鎖状ポリエンとしては、例えば下記一般式［IV-I］で表される非共役トリエンまたはテトラエンが挙げられる。 Examples of other non-conjugated chain polyenes include α, ω-dienes such as 1,7-octadiene and 1,9-decadiene. Examples of other non-conjugated chain polyenes include the following general formula [ Non-conjugated triene or tetraene represented by IV-I].
Figure JPOXMLDOC01-appb-C000017
 　式［IV-I］において、ｐおよびrは、０または１（ただしｐとrとは同時に０ではない）、
　qは０～５の整数（ただしｐとrの両方が１の場合qは０ではない）、
　sは１～６の整数、
　Ｒ19、Ｒ20、Ｒ21、Ｒ22、Ｒ23、Ｒ24およびＲ25はそれぞれ独立して水素原子または炭素数１～３のアルキル基、
　Ｒ26は炭素数１～３のアルキル基、
　Ｒ27は水素原子、炭素数１～３のアルキル基または－(ＣＨ2)n－ＣＲ28＝Ｃ(Ｒ29)Ｒ30で表される基（ここでｎは１～５の整数、Ｒ28およびＲ29はそれぞれ独立して水素原子または炭素数１～３のアルキル基、Ｒ30は炭素数１～３のアルキル基である）
である。ただしｐとrの両方が１の場合、Ｒ27は水素原子または炭素数１～３のアルキル基である。
Figure JPOXMLDOC01-appb-C000017
 In the formula [IV-I], p and r are 0 or 1 (p and r are not 0 at the same time),
q is an integer from 0 to 5 (but q is not 0 when both p and r are 1),
s is an integer from 1 to 6,
R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R 26 is an alkyl group having 1 to 3 carbon atoms,
R 27 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group represented by — (CH 2 ) n —CR 28 ═C (R 29 ) R 30 (where n is an integer of 1 to 5, R 28 And R 29 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 30 is an alkyl group having 1 to 3 carbon atoms)
It is. However, when both p and r are 1, R 27 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
　上記一般式［IV-I］で示される非共役トリエンまたはテトラエンの中でも下記一般式［IV-II］で示される非共役トリエンが好ましい。 Among the non-conjugated trienes or tetraenes represented by the above general formula [IV-I], non-conjugated trienes represented by the following general formula [IV-II] are preferable.
Figure JPOXMLDOC01-appb-C000018
 　式［IV-II］において、Ｒ21、Ｒ22、Ｒ25、Ｒ26およびＲ27はそれぞれ独立して水素原子、メチル基またはエチル基である。ただし、Ｒ26とＲ27とが同時に水素原子になることはない。
Figure JPOXMLDOC01-appb-C000018
 In the formula [IV-II], R 21 , R 22 , R 25 , R 26 and R 27 are each independently a hydrogen atom, a methyl group or an ethyl group. However, R 26 and R 27 are not hydrogen atoms at the same time.
　なお、上記一般式［IV-II］で示される非共役トリエンは、上記一般式［IV-I］で示される非共役トリエンまたはテトラエンにおいてpが０、qが０、rが１、sが２、Ｒ23およびＲ24が水素原子である非共役トリエンである。さらに上記一般式［IV-II］で示される非共役トリエンの中でも、Ｒ25およびＲ27がどちらもメチル基である化合物が好ましい。 The non-conjugated triene represented by the general formula [IV-II] is a non-conjugated triene or tetraene represented by the general formula [IV-I], wherein p is 0, q is 0, r is 1, and s is 2 , R 23 and R 24 are hydrogen atoms. Furthermore, among the non-conjugated trienes represented by the above general formula [IV-II], compounds in which R 25 and R 27 are both methyl groups are preferred.
　上記一般式［IV-I］で表される非共役トリエンまたはテトラエンとしては、具体的には下記化合物などが挙げられる（ただし、上記一般式［IV-II］に含まれる化合物は除く）。 Specific examples of the non-conjugated triene or tetraene represented by the general formula [IV-I] include the following compounds (excluding compounds included in the general formula [IV-II]).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 　上記一般式［IV-II］で表される非共役トリエンとしては、具体的には下記化合物などが挙げられる。
Figure JPOXMLDOC01-appb-C000021
 Specific examples of the non-conjugated triene represented by the above general formula [IV-II] include the following compounds.
Figure JPOXMLDOC01-appb-C000022
 　上記一般式［IV-I］で表される非共役トリエンまたはテトラエンは公知の方法で製造することができ、その方法は例えば本出願人による特開平９－２３５３２７号公報、特開２００１－１１４８３７号公報などに詳細に記載されている。
Figure JPOXMLDOC01-appb-C000022
 The non-conjugated triene or tetraene represented by the above general formula [IV-I] can be produced by a known method. For example, Japanese Patent Application Laid-Open Nos. 9-235327 and 2001-114837 by the present applicant. It is described in detail in publications and the like.
　工程［Ｐ］において共重合を行う場合、各モノマーの供給量は、製造しようとするオレフィン重合体の組成に応じて適宜設定される。 When copolymerization is performed in step [P], the supply amount of each monomer is appropriately set according to the composition of the olefin polymer to be produced.
　以下、本発明の製造方法により製造されるオレフィン重合体がエチレン／α－オレフィン／非共役ポリエン共重合体である場合について説明する。 Hereinafter, the case where the olefin polymer produced by the production method of the present invention is an ethylene / α-olefin / non-conjugated polyene copolymer will be described.
　本発明の製造方法により製造されるエチレン／α－オレフィン／非共役ポリエン共重合体は、（i）エチレンから誘導される構造単位（エチレン単位）と、（ii）炭素数３以上のα－オレフィンから誘導される構造単位（α－オレフィン単位）とを、モル比［（i）/(ii)］で表して通常99/1～1/99の範囲で含有するが、特に制限はない。 The ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention comprises (i) a structural unit derived from ethylene (ethylene unit) and (ii) an α-olefin having 3 or more carbon atoms. The structural unit (α-olefin unit) derived from is usually contained in the range of 99/1 to 1/99 in terms of molar ratio [(i) / (ii)], but is not particularly limited.
　本発明の製造方法により製造されるエチレン／α－オレフィン／非共役ポリエン共重合体のエチレンに由来する構造単位の含有量は、通常50 mol%以上である。 The content of structural units derived from ethylene in the ethylene / α-olefin / nonconjugated polyene copolymer produced by the production method of the present invention is usually 50 mol% or more.
　また本発明の製造方法により製造されるエチレン／α－オレフィン／非共役ポリエン共重合体の非共役ポリエン化合物に由来する構造単位は、特に制限はないが、全構造単位中、通常0.1～49 mol%、好ましくは0.2～8 mol%、さらに好ましくは0.3～5 mol%の割合の範囲にある。 The structural unit derived from the non-conjugated polyene compound of the ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention is not particularly limited, but is usually 0.1 to 49 mol in all the structural units. %, Preferably 0.2 to 8 mol%, more preferably 0.3 to 5 mol%.
　本発明の製造方法により製造される、エチレン／α－オレフィン／非共役ポリエン共重合体の135℃デカリン中で測定した極限粘度［η］は、好ましくは2 dl/g以上、より好ましくは4 dl/g以上であり、その上限はたとえば20 dl/gであってもよい。 The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention, measured in decalin at 135 ° C., is preferably 2 dl / g or more, more preferably 4 dl / g and the upper limit may be, for example, 20 dl / g.
　以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
　架橋メタロセン化合物およびその前駆体の構造は、1H NMRスペクトル（270 MHz、日本電子GSH-270）、FD-質量（以下FD-MS）スペクトル（日本電子SX-102A）等を測定し、決定した。 The structure of the bridged metallocene compound and its precursor was determined by measuring 1 H NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (hereinafter FD-MS) spectrum (JEOL SX-102A), etc. .
　エチレン／α－オレフィン／非共役ポリエン共重合体の物性／性状は以下の方法で測定した。 The physical properties / properties of the ethylene / α-olefin / non-conjugated polyene copolymer were measured by the following methods.
　［エチレン含有量、プロピレン含有量、5-エチリデン-2-ノルボルネン（ENB）含有量］
　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、パルス幅4.7μ秒（45°パルス）測定条件下（100 MHz、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、パルス幅5.0μ秒（45°パルス）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、算出した。 [Ethylene content, propylene content, 5-ethylidene-2-norbornene (ENB) content]
o-Dichlorobenzene / benzene-d 6 (4/1 [vol / vol%]) as the measurement solvent, measurement temperature 120 ° C, spectrum width 250ppm, pulse repetition time 5.5 seconds, pulse width 4.7μs (45 ° pulse) Measurement conditions (100 MHz, JEOL ECX400P) or measurement temperature 120 ° C, spectral width 250 ppm, pulse repetition time 5.5 seconds, pulse width 5.0 μs (45 ° pulse) Measurement conditions (125 MHz, Bruker BioSpin AVANCEIIIcryo -500), the 13 C NMR spectrum was measured and calculated.
　［極限粘度（［η］）］
　デカリン溶媒を用いて、135℃で測定した。重合体約20 mgをデカリン15 mlに溶解し、135℃のオイルバス中で比粘度ηspを測定した。このデカリン溶液にデカリン溶媒を5 ml追加して希釈後、同様にして比粘度ηspを測定した。この希釈操作をさらに２回繰り返し、濃度（C）を0に外挿した時のηsp/Cの値を極限粘度として採用した。
　　　［η］＝ｌｉｍ(ηsp/C)  (C→0) [Intrinsic viscosity ([η])]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the polymer was dissolved in 15 ml of decalin, and the specific viscosity η sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution and diluting, the specific viscosity η sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η sp / C when the concentration (C) was extrapolated to 0 was adopted as the limiting viscosity.
[Η] = lim (η sp / C) (C → 0)
　＜遷移金属化合物の製造＞
　［実施例Ａ１］
　（i）ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシフルオレニル)シランの合成
　三方コックおよび磁気攪拌子を備えた100 mL三口フラスコを充分に窒素置換した後、2,7-ジメトキシフルオレン1.13 g(5.0 mmol)を入れ、ジエチルエーテル80 mLを加えた。ドライアイス/メタノール浴で冷却しながら1.55 Mのn-ブチルリチウム(5.3 mmol)/ヘキサン溶液3.4 mLを徐々に加えた後、窒素雰囲気下室温で6時間攪拌してスラリーを得た。このスラリーに対してドライアイス/メタノール浴で冷却しながらジ-p-トリルジクロロシラン1.3 mL(5.5 mmol)を徐々に添加した。室温まで徐々に昇温した後、窒素雰囲気下室温で20時間攪拌し、スラリーを得た。このスラリーをヘキサンで洗浄することにより黄土色固体1.41ｇを得た。続いて、三方コックおよび磁気攪拌子を備えた200 mL二口フラスコを充分に窒素置換した後、得られた黄土色固体1.41 g(3.0 mmol)を入れ、テトラヒドロフラン40 mLを加えた。1,3-ジメチル-2-イミダゾリジノン(DMI)0.36 mLを加えた後、ドライアイス/メタノール浴で冷却しながら2.0 Mのシクロペンタジエニルナトリウム(3.3 mmol)/テトラヒドロフラン溶液1.65 mLを徐々に添加した。室温まで徐々に昇温した後、窒素雰囲気下室温で24時間攪拌し、スラリーを得た。これに塩化アンモニウム水溶液50 mLと酢酸エチル30 mLを加え、200 mL分液漏斗を用いて水層を除き、有機層を得た。この有機層を飽和食塩水50 mLで洗い、無水硫酸マグネシウムで乾燥した後、濾過して硫酸マグネシウムを除き、濾液の溶媒を留去して淡橙色固体を得た。この淡橙色固体をメタノールで洗い、淡黄色固体としてジ-p-トリルシクロペンタジエニル(2,7-ジメトキシフルオレニル)シランを得た(387 mg(0.773 mmol, 15%))。ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシフルオレニル)シランのFD-MSスペクトルの測定値を下に示す。
　FD-MS: m/z = 500.2 (M+) <Production of transition metal compound>
[Example A1]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane A 100 mL three-necked flask equipped with a three-way cock and a magnetic stirrer was thoroughly purged with nitrogen, and then 2,7- Dimethoxyfluorene 1.13 g (5.0 mmol) was added, and diethyl ether 80 mL was added. While cooling in a dry ice / methanol bath, 3.4 mL of a 1.55 M n-butyllithium (5.3 mmol) / hexane solution was gradually added, and then stirred at room temperature for 6 hours under a nitrogen atmosphere to obtain a slurry. To this slurry, 1.3 mL (5.5 mmol) of di-p-tolyldichlorosilane was gradually added while cooling in a dry ice / methanol bath. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The slurry was washed with hexane to obtain 1.41 g of an ocherous solid. Subsequently, a 200 mL two-necked flask equipped with a three-way cock and a magnetic stirrer was sufficiently purged with nitrogen, and then 1.41 g (3.0 mmol) of the obtained ocherous solid was added, and 40 mL of tetrahydrofuran was added. After adding 0.36 mL of 1,3-dimethyl-2-imidazolidinone (DMI), gradually cool 1.65 mL of 2.0 M cyclopentadienyl sodium (3.3 mmol) / tetrahydrofuran solution while cooling in a dry ice / methanol bath. Added. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere to obtain a slurry. To this was added 50 mL of an aqueous ammonium chloride solution and 30 mL of ethyl acetate, and the aqueous layer was removed using a 200 mL separatory funnel to obtain an organic layer. The organic layer was washed with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and the filtrate was evaporated to give a pale orange solid. This pale orange solid was washed with methanol to obtain di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane as a pale yellow solid (387 mg (0.773 mmol, 15%)). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane are shown below.
FD-MS: m / z = 500.2 (M + )
　（ii）ジ-p-トリルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドの合成
　磁気攪拌子を備えた100 mLシュレンクを充分に窒素置換した後、ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシフルオレニル)シラン351 mg(0.70 mmol)を入れ、トルエン20 mLとテトラヒドロフラン 0.114 mL(1.4 mmol)を加えた。氷/食塩浴で冷やしながら、1.55 Mのn-ブチルリチウム(1.4 mmol)/ヘキサン溶液0.91 mLを徐々に加えた後、窒素雰囲気下室温で1時間攪拌した。その後オイルバスを用いて40度で4時間加熱撹拌してスラリーを得た。減圧下で溶媒を留去して得られた固体をヘキサンで洗浄し、黄色固体を得た。磁気攪拌子を備えた100 mLシュレンクに得られた黄色固体を入れ、ジエチルエーテル20 mLを加えた。メタノール/ドライアイス浴で冷やしながら四塩化ジルコニウム163 mg(0.70 mmol)を加えた後、室温まで徐々に昇温し、窒素雰囲気下室温で20時間攪拌してスラリーを得た。減圧下で溶媒を留去して得られた固体をトルエンで抽出し、このトルエン溶液から約-20度で再結晶することにより、黄色固体としてジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを得た。収量は30 mg(0.65 mmol)、収率は6.5%であった。ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドの同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 (Ii) Synthesis of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride After substitution, 351 mg (0.70 mmol) of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane was added, and 20 mL of toluene and 0.114 mL (1.4 mmol) of tetrahydrofuran were added. While cooling in an ice / salt bath, 0.91 mL of a 1.55 M n-butyllithium (1.4 mmol) / hexane solution was gradually added, followed by stirring at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the mixture was heated and stirred at 40 ° C. for 4 hours using an oil bath to obtain a slurry. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane to obtain a yellow solid. The obtained yellow solid was put into a 100 mL Schlenk equipped with a magnetic stirring bar, and 20 mL of diethyl ether was added. After adding 163 mg (0.70 mmol) of zirconium tetrachloride while cooling in a methanol / dry ice bath, the temperature was gradually raised to room temperature and stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The solid obtained by distilling off the solvent under reduced pressure was extracted with toluene, and recrystallized from this toluene solution at about −20 ° C. to give di-p-tolylsilylene (η 5 -cyclopentadiene as a yellow solid. Enyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was obtained. The yield was 30 mg (0.65 mmol), and the yield was 6.5%. The identification of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was performed by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
2.42 (s, 6H), 3.30 (s, 6H), 5.98 (t, 2H, J = 2 Hz), 6.08 (d, 2H, J = 2 Hz), 6.75 (t, 2H, J = 2 Hz), 7.21 (dd, 2H, J = 8, 1 Hz), 7.38 (d, 4H, J = 7 Hz), 7.85 (d, 2H, J = 9 Hz ), 8.05 (d, 4H, J = 8 Hz) 
　FD-MS: m/z = 658.0 (M+) 1 H NMR (270 MHz, CDCl 3 )
2.42 (s, 6H), 3.30 (s, 6H), 5.98 (t, 2H, J = 2 Hz), 6.08 (d, 2H, J = 2 Hz), 6.75 (t, 2H, J = 2 Hz), 7.21 (dd, 2H, J = 8, 1 Hz), 7.38 (d, 4H, J = 7 Hz), 7.85 (d, 2H, J = 9 Hz), 8.05 (d, 4H, J = 8 Hz)
FD-MS: m / z = 658.0 (M + )
　［実施例Ａ２］
　（i）ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)シランの合成
　三方コックおよび磁気攪拌子を備えた100 mL三口フラスコを充分に窒素置換した後、2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレン711 mg(2.1 mmol)を入れ、ジエチルエーテル30 mLを加えた。氷浴で冷却しながら1.55 Mのn-ブチルリチウム(2.2 mmol)/ヘキサン溶液1.4 mLを徐々に加えた後、窒素雰囲気下室温で23時間攪拌してスラリーを得た。このスラリーに対してドライアイス/メタノール浴で冷却しながらジ-p-トリルジクロロシラン0.55 mL(2.3 mmol)を徐々に添加した。室温まで徐々に昇温した後、窒素雰囲気下室温で17時間攪拌し、スラリーを得た。このスラリーをヘキサンで洗浄することにより白色固体550 mgを得た。続いて、三方コックおよび磁気攪拌子を備えた200 mL二口フラスコを充分に窒素置換した後、得られた白色固体550 mg(0.94 mmol)を入れ、テトラヒドロフラン30 mLを加えた。1,3-ジメチル-2-イミダゾリジノン(DMI)0.20 mLを加えた後、ドライアイス/メタノール浴で冷却しながら2.0 Mのシクロペンタジエニルナトリウム(1.89 mmol)/テトラヒドロフラン溶液0.94 mLを徐々に添加した。室温まで徐々に昇温した後、窒素雰囲気下室温で20時間攪拌し、スラリーを得た。これに塩化アンモニウム水溶液50 mLと酢酸エチル20 mLを加え、200 mL分液漏斗を用いて水層を除き、有機層を得た。この有機層を飽和食塩水50 mLで洗い、無水硫酸マグネシウムで乾燥した後、濾過して硫酸マグネシウムを除き、濾液の溶媒を留去して黄色固体を得た。この黄色固体をシリカゲルカラムクロマトグラフィーにより精製し(ヘキサン:酢酸エチル=50:1)、減圧下溶媒を留去することで淡橙色固体としてジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)シランを得た(306 mg(0.50 mmol, 24%))。ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)シランのFD-MSスペクトルの測定値を下に示す。
　FD-MS: m/z = 612.4 (M+) [Example A2]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane A 100 mL three-necked flask equipped with a three-way cock and a magnetic stirring bar Then, 711 mg (2.1 mmol) of 2,7-dimethoxy-3,6-di-tert-butylfluorene was added, and 30 mL of diethyl ether was added. A 1.55 M n-butyllithium (2.2 mmol) / hexane solution (1.4 mL) was gradually added while cooling in an ice bath, and the mixture was stirred at room temperature for 23 hours under a nitrogen atmosphere to obtain a slurry. To this slurry, 0.55 mL (2.3 mmol) of di-p-tolyldichlorosilane was gradually added while cooling with a dry ice / methanol bath. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 17 hours under a nitrogen atmosphere to obtain a slurry. This slurry was washed with hexane to obtain 550 mg of a white solid. Subsequently, a 200 mL two-necked flask equipped with a three-way cock and a magnetic stirrer was sufficiently purged with nitrogen, and then the obtained white solid 550 mg (0.94 mmol) was added, and tetrahydrofuran 30 mL was added. After adding 0.20 mL of 1,3-dimethyl-2-imidazolidinone (DMI), gradually cool 0.94 mL of 2.0 M cyclopentadienyl sodium (1.89 mmol) / tetrahydrofuran solution while cooling in a dry ice / methanol bath. Added. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. To this was added 50 mL of an aqueous ammonium chloride solution and 20 mL of ethyl acetate, and the aqueous layer was removed using a 200 mL separatory funnel to obtain an organic layer. This organic layer was washed with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and the solvent of the filtrate was distilled off to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1), and the solvent was distilled off under reduced pressure to obtain di-p-tolylcyclopentadienyl (2,7-dimethoxy) as a pale orange solid. -3,6-di-tert-butylfluorenyl) silane was obtained (306 mg (0.50 mmol, 24%)). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane are shown below.
FD-MS: m / z = 612.4 (M + )
　（ii）ジ-p-トリルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリドの合成
　磁気攪拌子を備えた100 mLシュレンクを充分に窒素置換した後、ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)シラン306 mg(0.50 mmol)を入れ、ジエチルエーテル40 mlを加えた。ドライアイス/メタノール浴で冷やしながら、1.55 Mのn-ブチルリチウム(1.02 mmol)/ヘキサン溶液0.66 mLを徐々に加えた後、窒素雰囲気下室温で23時間攪拌してスラリーを得た。メタノール/ドライアイス浴で冷やしながら四塩化ジルコニウム116 mg(0.50 mmol)を加えた後、室温まで徐々に昇温し、窒素雰囲気下室温で20時間攪拌してスラリーを得た。減圧下で溶媒を留去して得られた固体をヘキサンで洗浄し、残渣をトルエンで抽出した。トルエン溶液のトルエンを減圧下留去することにより、淡橙色固体としてジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリドを得た。収量は151 mg(0.30 mmol)、収率は39%であった。ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリドの同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 (Ii) Synthesis of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride After fully replacing nitrogen with a 100 mL Schlenk with di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane 306 mg (0.50 mmol) And 40 ml of diethyl ether was added. While cooling in a dry ice / methanol bath, 0.65 mL of a 1.55 M n-butyllithium (1.02 mmol) / hexane solution was gradually added, followed by stirring at room temperature for 23 hours under a nitrogen atmosphere to obtain a slurry. After adding 116 mg (0.50 mmol) of zirconium tetrachloride while cooling in a methanol / dry ice bath, the temperature was gradually raised to room temperature and stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane, and the residue was extracted with toluene. Toluene in the toluene solution was distilled off under reduced pressure to obtain di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert -Butylfluorenyl)] zirconium dichloride was obtained. The yield was 151 mg (0.30 mmol), and the yield was 39%. The identification of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride is the 1 H NMR spectrum And FD-MS spectra. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
1.44 (s, 18H), 2.41 (s, 6H), 3.24 (s, 6H), 5.83 (t, 2H, J = 2 Hz), 6.02 (s, 2H), 6.70 (t, 2H, J = 2 Hz), 7.38 (d, 4H, J = 8 Hz), 7.83 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
　FD-MS: m/z = 770.1 (M+) 1 H NMR (270 MHz, CDCl 3 )
1.44 (s, 18H), 2.41 (s, 6H), 3.24 (s, 6H), 5.83 (t, 2H, J = 2 Hz), 6.02 (s, 2H), 6.70 (t, 2H, J = 2 Hz ), 7.38 (d, 4H, J = 8 Hz), 7.83 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
FD-MS: m / z = 770.1 (M + )
　［実施例Ａ３］
　（i）ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シランの合成
　窒素雰囲気下、100 ml二口フラスコに2,7-ジメトキシ-3,6-ジメチルフルオレン 756 mg (2.97 mmol)および脱水シクロペンチルメチルエーテル 50 mlを添加した。-78℃に冷却しながらn-ブチルリチウム/ヘキサン溶液 (1.55 M) 2.01 ml (3.12 mmol）を徐々に添加し、室温で18時間攪拌した。ジ-p-トリルジクロロシラン802 mg (3.27 mmol)を添加した後、22時間半撹拌した。窒素ボックス内に持ち込み溶媒を減圧留去した後、ヘキサンで洗浄した。得られた固体を減圧下で乾燥し白色固体957 mgを得た。 [Example A3]
(I) Synthesis of di-p- tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane In a 100 ml two-necked flask under nitrogen atmosphere -756 mg (2.97 mmol) dimethylfluorene and 50 ml dehydrated cyclopentyl methyl ether were added. While cooling to -78 ° C, 2.01 ml (3.12 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred at room temperature for 18 hours. After adding 802 mg (3.27 mmol) of di-p-tolyldichlorosilane, the mixture was stirred for 22 and a half hours. It was brought into a nitrogen box and the solvent was distilled off under reduced pressure, followed by washing with hexane. The obtained solid was dried under reduced pressure to obtain 957 mg of a white solid.
　続いて窒素雰囲気下、100 ml三口フラスコに先の反応で得られた白色固体 957 mg 、THF 50mlを添加した。-78℃に冷却し、1,3-ジメチル-2-イミダゾリジノン（DMI）0.415 ml (3.85 mmol）、2.0 Mのシクロペンタジエニルナトリウム(3.84 mmol）テトラヒドロフラン溶液1.92 mlを添加し、徐々に室温に戻しながらで23時間攪拌した。氷浴下、塩化アンモニウム水溶液を加えて反応を停止させた後、酢酸エチルで抽出し、有機相を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥し濃縮乾固した。得られた固体をメタノールで洗浄し、減圧下で乾燥して粗生成物（淡橙色粉末）を得た。シリカゲルクロマトグラフィー（展開溶媒ヘキサン→ヘキサン:酢酸エチル=50:1）により精製し、目的物（白色粉末）を得た(収量449 mg、2段階収率　29%）。ジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シランのFD-MSスペクトルの測定値を下に示す。
　FD-MS: m/z =528.3(M+) Subsequently, 957 mg of the white solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml three-necked flask under a nitrogen atmosphere. Cool to -78 ° C, add 1.15 ml of 1,3-dimethyl-2-imidazolidinone (DMI) 0.415 ml (3.85 mmol), 2.0 M cyclopentadienyl sodium (3.84 mmol) in tetrahydrofuran and slowly The mixture was stirred for 23 hours while returning to room temperature. The reaction was stopped by adding an aqueous ammonium chloride solution in an ice bath, followed by extraction with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and concentrated to dryness. The obtained solid was washed with methanol and dried under reduced pressure to obtain a crude product (light orange powder). Purification by silica gel chromatography (developing solvent hexane → hexane: ethyl acetate = 50: 1) gave the desired product (white powder) (yield 449 mg, 2-step yield 29%). The measured value of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane is shown below.
FD-MS: m / z = 528.3 (M + )
　（ii）ジ-p-トリルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリドの合成
　窒素雰囲気下、100 mlシュレンク管にジ-p-トリルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シラン449 mg (0.850 mmol)、ジエチルエーテル40 mlを添加した。-78℃に冷却し、n-ブチルリチウム/ヘキサン溶液 (1.55 M) 1.12 ml (1.74 mmol）を添加した後、徐々に室温に戻しながら23時間撹拌した。-78℃に冷却し四塩化ジルコニウム198 mg （0.850 mmol）を添加し、室温まで徐々に昇温しながら23時間攪拌した。減圧下で溶媒を留去し、ヘキサンで洗浄後、セライトを使用してトルエン、ジクロロメタンで抽出した。減圧下で溶媒を留去して目的物を得た(収量471 mg、収率80%）。ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリドの同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 (Ii) Synthesis of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride 100 ml Schlenk under nitrogen atmosphere Di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane (449 mg, 0.850 mmol) and diethyl ether (40 ml) were added to the tube. After cooling to −78 ° C. and adding 1.12 ml (1.74 mmol) of n-butyllithium / hexane solution (1.55 M), the mixture was stirred for 23 hours while gradually returning to room temperature. After cooling to -78 ° C, 198 mg (0.850 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually warming to room temperature. The solvent was distilled off under reduced pressure, washed with hexane, and extracted with toluene and dichloromethane using Celite. The solvent was distilled off under reduced pressure to obtain the desired product (yield 471 mg, yield 80%). The identification of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride was confirmed by 1 H NMR spectrum and FD-MS Performed in the spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
2.38(s, 6H), 2.41(s, 6H), 3.25(s, 6H), 5.84 (t, 2H, J = 2 Hz), 5.99 (s, 2H), 6.69 (t, 2H, J = 2 Hz), 7.37 (d, 4H, J = 8 Hz, 4H), 7.73 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
　FD-MS: m/z =686.1(M+) 1 H NMR (270 MHz, CDCl 3 )
2.38 (s, 6H), 2.41 (s, 6H), 3.25 (s, 6H), 5.84 (t, 2H, J = 2 Hz), 5.99 (s, 2H), 6.69 (t, 2H, J = 2 Hz ), 7.37 (d, 4H, J = 8 Hz, 4H), 7.73 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
FD-MS: m / z = 686.1 (M + )
　［実施例Ａ４］
　（iii）ジ-p-トリルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチルの合成
　窒素雰囲気下、100 mlシュレンクフラスコに、実施例Ａ３で製造されたジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド 147 mg (0.21 mmol)、t-ブチルメチルエーテル50 ml、トルエン25 mlを添加した。氷浴で冷却し、メチルマグネシウムブロマイド/ジエチルエーテル溶液 (3 M) 0.42 ml (1.26 mmol）を添加し、22時間60℃のオイルバスで加熱した。減圧下で溶媒を留去し、セライトを用いてトルエンで抽出した。減圧下で溶媒を留去した後、セライトを用いてメチルシクロヘキサンで抽出した。減圧下で溶媒を留去して得られた固体をヘキサンで洗浄した。減圧下で乾燥して目的物を得た。(収量53 mg、収率39%）。目的物の同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 [Example A4]
(Iii) Synthesis of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl 100 ml Schlenk under nitrogen atmosphere Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride prepared in Example A3 147 mg was added to the flask. (0.21 mmol), 50 ml of t-butyl methyl ether and 25 ml of toluene were added. The mixture was cooled in an ice bath, methylmagnesium bromide / diethyl ether solution (3 M) (0.42 ml, 1.26 mmol) was added, and the mixture was heated in an oil bath at 60 ° C. for 22 hours. The solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using celite. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane. The desired product was obtained by drying under reduced pressure. (Yield 53 mg, 39% yield). The target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
-1.57(s, 6H), 2.36(s, 6H), 2.37(s, 6H), 3.21(s, 6H), 5.69 (t, 2H, J = 2 Hz), 5.90 (s, 2H), 6.62 (t, 2H, J = 2 Hz),7.30 (d, 4H, J = 8 Hz), 7.77 (s, 2H), 8.02 (d, 2H, J = 8 Hz)
　FD-MS: m/z = 646.2 (M+) 1 H NMR (270 MHz, CDCl 3 )
-1.57 (s, 6H), 2.36 (s, 6H), 2.37 (s, 6H), 3.21 (s, 6H), 5.69 (t, 2H, J = 2 Hz), 5.90 (s, 2H), 6.62 ( t, 2H, J = 2 Hz), 7.30 (d, 4H, J = 8 Hz), 7.77 (s, 2H), 8.02 (d, 2H, J = 8 Hz)
FD-MS: m / z = 646.2 (M + )
　［実施例Ａ５］
　（i）ジフェニルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シランの合成
　窒素雰囲気下、100 mlシュレンクフラスコに2,7-ジメトキシ-3,6-ジメチルフルオレン 1037 mg (4.08 mmol)および脱水シクロペンチルメチルエーテル 60 mlを添加した。-78℃に冷却しながらn-ブチルリチウム/ヘキサン溶液 (1.55 M) 2.80 ml (4.34 mmol）を徐々に添加し、室温で17時間攪拌した。ジフェニルジクロロシラン0.94　ml (4.47 mmol)を添加した後、23時間撹拌した。窒素ボックス内に持ち込み溶媒を減圧留去した後、ペンタンで洗浄した。得られた固体を減圧下で乾燥しオレンジ固体990 mgを得た。
続いて、窒素雰囲気下、100 mlシュレンクフラスコに先の反応で得られたオレンジ色固体 990 mg 、THF 50mlを添加した。-78℃に冷却し、1,3-ジメチル-2-イミダゾリジノン（DMI）0.46 ml (4.26 mmol）、2.0 Mのシクロペンタジエニルナトリウムテトラヒドロフラン溶液 2.10 ml (4.20 mmol）を添加し、徐々に室温に戻しながら21時間攪拌した。氷浴下、飽和塩化アンモニウム水溶液を加えて反応を停止し、ジエチルエーテルで抽出した。有機相を水、飽和食塩水で洗浄した。硫酸マグネシウムで乾燥後、濃縮乾固した。得られた固体をシリカゲルクロマトグラフィー（展開溶媒ヘキサン→ヘキサン:酢酸エチル=20:1）により精製し、目的物を得た(収量709 mg、2段階収率　35%）。ジフェニルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シランの同定は、FD-MSスペクトルで行った。以下にその測定結果を示す。
　FD-MS: m/z = 500.2 (M+) [Example A5]
(I) Synthesis of diphenylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane In a 100 ml Schlenk flask under nitrogen atmosphere, 2,7-dimethoxy-3,6-dimethylfluorene 1037 mg (4.08 mmol) and 60 ml of dehydrated cyclopentyl methyl ether were added. While cooling to -78 ° C, 2.80 ml (4.34 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred at room temperature for 17 hours. After adding 0.94 ml (4.47 mmol) of diphenyldichlorosilane, the mixture was stirred for 23 hours. It was brought into a nitrogen box and the solvent was distilled off under reduced pressure, followed by washing with pentane. The obtained solid was dried under reduced pressure to obtain 990 mg of an orange solid.
Subsequently, 990 mg of the orange solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml Schlenk flask under a nitrogen atmosphere. Cool to -78 ° C, add 0.43 ml (4.26 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI), 2.10 ml (4.20 mmol) of 2.0 M cyclopentadienyl sodium tetrahydrofuran, and gradually The mixture was stirred for 21 hours while returning to room temperature. The reaction was stopped by adding saturated aqueous ammonium chloride solution in an ice bath, and extracted with diethyl ether. The organic phase was washed with water and saturated brine. After drying with magnesium sulfate, it was concentrated to dryness. The obtained solid was purified by silica gel chromatography (developing solvent hexane → hexane: ethyl acetate = 20: 1) to obtain the desired product (yield 709 mg, 2-step yield 35%). Identification of diphenylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane was performed by FD-MS spectrum. The measurement results are shown below.
FD-MS: m / z = 500.2 (M + )
　（ii）ジフェニルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリドの合成
　窒素雰囲気下、100 mlシュレンクフラスコにジフェニルシクロペンタジエニル(2,7-ジメトキシ-3,6-ジメチルフルオレニル)シラン702 mg (1.40 mmol)、ジエチルエーテル55 mlを添加した。-78℃に冷却し、n-ブチルリチウム/ヘキサン溶液 (1.55 M) 1.85 ml (2.87 mmol）を徐々に添加し後、徐々に室温に戻しながら23時間撹拌した。-78℃に冷却し四塩化ジルコニウム323 mg （1.39 mmol）を添加し、室温まで徐々に昇温しながら23時間攪拌した。減圧下で溶媒を留去し、セライトを用いてジクロロメタンで抽出した。減圧下で溶媒を留去して、少量のジクロロメタンに溶解し、ヘキサン中に滴下した。得られた沈殿をろ過により回収して減圧下で乾燥した。得られた固体をペンタンで洗浄した後、減圧下で乾燥して目的物を得た(収量506 mg、収率55%）。目的物の同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 (Ii) Synthesis of diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride In a 100 ml Schlenk flask under nitrogen atmosphere 702 mg (1.40 mmol) of pentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane and 55 ml of diethyl ether were added. The mixture was cooled to -78 ° C, 1.85 ml (2.87 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred for 23 hours while gradually returning to room temperature. After cooling to -78 ° C, 323 mg (1.39 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually warming to room temperature. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using celite. The solvent was distilled off under reduced pressure, dissolved in a small amount of dichloromethane, and dropped into hexane. The resulting precipitate was collected by filtration and dried under reduced pressure. The obtained solid was washed with pentane and then dried under reduced pressure to obtain the desired product (yield 506 mg, yield 55%). The target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
2.38(s, 6H), 3.23(s, 6H), 5.86 (t, 2H, J = 2 Hz), 5.96 (s, 2H), 6.71 (t, 2H, J = 2 Hz), 7.55-7.57 (m, 6H), 7.73 (s, 2H), 8.18-8.22 (m, 4H)
　FD-MS: m/z = 658.0 (M+) 1 H NMR (270 MHz, CDCl 3 )
2.38 (s, 6H), 3.23 (s, 6H), 5.86 (t, 2H, J = 2 Hz), 5.96 (s, 2H), 6.71 (t, 2H, J = 2 Hz), 7.55-7.57 (m , 6H), 7.73 (s, 2H), 8.18-8.22 (m, 4H)
FD-MS: m / z = 658.0 (M + )
　［実施例Ａ６］
　（iii）ジフェニルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチルの合成
　窒素雰囲気下、100 mlシュレンクフラスコに、実施例Ａ５で製造されたジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド 264 mg (0.40 mmol)、t-ブチルメチルエーテル30 mlを添加した。氷浴で冷却し、メチルマグネシウムブロマイド/ジエチルエーテル溶液 (3 M) 0.80 ml (2.40 mmol）を添加し、22時間加熱還流した。減圧下で溶媒を留去し、セライトを用いてトルエンで抽出した。減圧下で溶媒を留去した後、セライトを用いてメチルシクロヘキサンで抽出した。減圧下で溶媒を留去して得られた固体を少量のジククロメタンに溶解させヘキサン中に滴下した。溶媒を一部減圧留去して生じた沈殿をろ過によって回収した。減圧下で乾燥して目的物を得た。(収量113 mg、収率45%）。目的物の同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 [Example A6]
(Iii) Synthesis of diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl Conducted in a 100 ml Schlenk flask under nitrogen atmosphere Diphenylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride prepared in Example A5 264 mg (0.40 mmol), t-butyl 30 ml of methyl ether was added. The reaction mixture was cooled in an ice bath, methylmagnesium bromide / diethyl ether solution (3 M) 0.80 ml (2.40 mmol) was added, and the mixture was heated to reflux for 22 hours. The solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using celite. The solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane and added dropwise to hexane. A part of the solvent was distilled off under reduced pressure, and the resulting precipitate was collected by filtration. The desired product was obtained by drying under reduced pressure. (Yield 113 mg, 45% yield). The target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3)
-1.56(s, 6H), 2.35(s, 6H), 3.20(s, 6H), 5.71 (t, 2H, J = 2 Hz), 5.87 (s, 2H), 6.64 (t, 2H, J = 2 Hz), 7.47-7.51 (m, 6H), 7.78 (s, 2H), 8.13-8.17 (m, 4H)
　FD-MS: m/z = 618.1 (M+) 1 H NMR (270 MHz, CDCl 3 )
-1.56 (s, 6H), 2.35 (s, 6H), 3.20 (s, 6H), 5.71 (t, 2H, J = 2 Hz), 5.87 (s, 2H), 6.64 (t, 2H, J = 2 Hz), 7.47-7.51 (m, 6H), 7.78 (s, 2H), 8.13-8.17 (m, 4H)
FD-MS: m / z = 618.1 (M + )
　［実施例Ａ７］
　（i）ジ-p-トリルシクロペンタジエニル(2,7-ジ-t-ブチル-4-メトキシフルオレニル)シランの合成
　窒素雰囲気下、100 ml二口フラスコに2,7-ジ-t-ブチル-4-メトキシフルオレン 771 mg (2.50 mmol)および脱水シクロペンチルメチルエーテル 50 mlを添加した。-78℃に冷却しながらn-ブチルリチウム/ヘキサン溶液 (1.55 M) 1.69 ml (2.63 mmol）を徐々に添加し、室温で18時間攪拌した。ジ-p-トリルジクロロシラン0.655 ml (2.75 mmol)を添加した後、22時間半撹拌した。窒素ボックス内に持ち込み溶媒を減圧留去した後、ヘキサンで洗浄した。得られた固体を減圧下で乾燥し白色固体1.20 gを得た。 [Example A7]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane In a 100 ml two-necked flask under nitrogen atmosphere, 2,7-di-t -Butyl-4-methoxyfluorene 771 mg (2.50 mmol) and dehydrated cyclopentyl methyl ether 50 ml were added. While cooling to -78 ° C, 1.69 ml (2.63 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred at room temperature for 18 hours. After adding 0.655 ml (2.75 mmol) of di-p-tolyldichlorosilane, the mixture was stirred for 22 and a half hours. It was brought into a nitrogen box and the solvent was distilled off under reduced pressure, followed by washing with hexane. The obtained solid was dried under reduced pressure to obtain 1.20 g of a white solid.
　続いて窒素雰囲気下、100 ml三口フラスコに先の反応で得られた白色固体 1.20 g 、THF 50mlを添加した。-78℃に冷却し、1,3-ジメチル-2-イミダゾリジノン（DMI）0.467 ml (4.34 mmol）、2.0 Mのシクロペンタジエニルナトリウム(4.34 mmol）テトラヒドロフラン溶液2.17 mlを添加し、徐々に室温に戻しながらで23時間攪拌した。氷浴下、塩化アンモニウム水溶液を加えて反応を停止させた後、酢酸エチルで抽出し、有機相を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥し濃縮乾固した。得られた固体ヘキサンで洗浄し、目的物（白色粉末）を得た(収量625 mg、2段階収率　43%）。ジ-p-トリルシクロペンタジエニル(2,7-ジ-t-ブチル-4-メトキシフルオレニル)シランのFD-MSスペクトルの測定値を下に示す。
　FD-MS: m/z =582.3(M+) Subsequently, 1.20 g of the white solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml three-necked flask under a nitrogen atmosphere. Cool to -78 ° C, add 1.67 ml (4.34 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI), 2.17 ml of 2.0 M sodium cyclopentadienyl (4.34 mmol) in tetrahydrofuran and slowly The mixture was stirred for 23 hours while returning to room temperature. The reaction was stopped by adding an aqueous ammonium chloride solution in an ice bath, followed by extraction with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and concentrated to dryness. The resultant was washed with solid hexane to obtain the desired product (white powder) (yield 625 mg, two-stage yield 43%). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane are shown below.
FD-MS: m / z = 582.3 (M + )
　（ii）ジ-p-トリルシリレン(η 5 -シクロペンタジエニル)[η 5 -(2,7-ジ-t-ブチル-4-メトキシフルオレニル)]ジルコニウムジクロリドの合成
　窒素雰囲気下、100 mlシュレンク管にジ-p-トリルシクロペンタジエニル(2,7-ジ-t-ブチル-4-メトキシフルオレニル)シラン350 mg (0.60 mmol)、ジエチルエーテル40 mlを添加した。-78℃に冷却し、n-ブチルリチウム/ヘキサン溶液 (1.55 M) 1.12 ml (1.74 mmol）を添加した後、徐々に室温に戻しながら20時間撹拌した。-78℃に冷却し四塩化ジルコニウム140 mg （0.60 mmol）を添加し、室温まで徐々に昇温しながら23時間攪拌した。減圧下で溶媒を留去し、ヘキサンで洗浄後、セライトを使用してトルエン、ジクロロメタンで抽出した。減圧下で溶媒を留去して目的物を得た(収量321 mg、収率72%）。ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジ-t-ブチル-4-メトキシフルオレニル)]ジルコニウムジクロリドの同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 (Ii) Synthesis of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride Di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane 350 mg (0.60 mmol) and diethyl ether 40 ml were added to a ml Schlenk tube. After cooling to -78 ° C. and adding 1.12 ml (1.74 mmol) of n-butyllithium / hexane solution (1.55 M), the mixture was stirred for 20 hours while gradually returning to room temperature. The mixture was cooled to -78 ° C, 140 mg (0.60 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually warming to room temperature. The solvent was distilled off under reduced pressure, washed with hexane, and extracted with toluene and dichloromethane using Celite. The solvent was distilled off under reduced pressure to obtain the desired product (yield 321 mg, yield 72%). The identification of di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride was confirmed by 1 H NMR spectrum and FD -MS spectra were used. The measurement results are shown below.
　FD-MS: m/z =740.2(M+)
　1H NMR (270 MHz, CDCl3)
1.01(s, 18H), 2.42(s, 6H), 4.01(s, 3H), 5.79-5.84(m, 2H), 6.30(d, 1H, J=1 Hz), 6.65-6.71(m, 3H), 6.89(d, 1H, J=1 Hz), 7.37(d, 4H, J=7 Hz), 7.61(dd, 1H, J=9, 2 Hz), 8.02-8.07(m, 4H), 8.27(d, J=9 Hz, 1H) FD-MS: m / z = 740.2 (M + )
1 H NMR (270 MHz, CDCl 3 )
1.01 (s, 18H), 2.42 (s, 6H), 4.01 (s, 3H), 5.79-5.84 (m, 2H), 6.30 (d, 1H, J = 1 Hz), 6.65-6.71 (m, 3H) , 6.89 (d, 1H, J = 1 Hz), 7.37 (d, 4H, J = 7 Hz), 7.61 (dd, 1H, J = 9, 2 Hz), 8.02-8.07 (m, 4H), 8.27 ( d, J = 9 Hz, 1H)
　［実施例Ａ８］
　（i）ジp-トリルシクロペンタジエニル(4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)シランの合成
　窒素雰囲気下、100 mlシュレンクフラスコに4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメン503 mg (1.42 mmol)および脱水tert-ブチルメチルエーテル 20 mlを添加した。0℃に氷浴下でn-ブチルリチウム/ヘキサン溶液 (1.57 M) 1.00 ml (1.57 mmol）を徐々に添加し、70℃オイルバスで5.5時間加熱攪拌した。-78℃でジp-トリルジクロロシラン480 mg (1.71 mmol)を添加した後、徐々に室温に戻しながら17時間撹拌した。窒素ボックス内に持ち込み溶媒を減圧留去した後、ペンタンで洗浄した。得られた固体を減圧下で乾燥しオフホワイト色固体688 mgを得た。 [Example A8]
(I) Di-p-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3, 4-g '] dicromenyl) silane synthesis In a 100 ml Schlenk flask under nitrogen atmosphere 4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2 , 1-g: 3,4-g ′] dicromene 503 mg (1.42 mmol) and dehydrated tert-butyl methyl ether 20 ml were added. 1.00 ml (1.57 mmol) of n-butyllithium / hexane solution (1.57 M) was gradually added at 0 ° C. in an ice bath, and the mixture was heated and stirred in a 70 ° C. oil bath for 5.5 hours. After adding 480 mg (1.71 mmol) of di-p-tolyldichlorosilane at −78 ° C., the mixture was stirred for 17 hours while gradually returning to room temperature. It was brought into a nitrogen box and the solvent was distilled off under reduced pressure, followed by washing with pentane. The obtained solid was dried under reduced pressure to obtain 688 mg of an off-white solid.
　続いて、窒素雰囲気下、先の反応で得られたオフホワイト色固体を100 mlシュレンクフラスコ中でテトラヒドロフラン20mlに溶かし、1,3-ジメチル-2-イミダゾリジノン（DMI）0.15 ml (1.39 mmol）を添加した。-78℃に冷却して2.0 Mのシクロペンタジエニルナトリウムテトラヒドロフラン溶液 0.66 ml (1.32 mmol）を添加し、徐々に室温に戻しながら17時間攪拌した。80℃オイルバスで6時間加熱した後、-30℃で1,3-ジメチル-2-イミダゾリジノン（DMI）0.15 ml (1.39 mmol）および2.0 Mのシクロペンタジエニルナトリウムテトラヒドロフラン溶液 0.66 ml (1.32 mmol）を追加し、徐々に室温に戻しながら16時間攪拌した。飽和塩化アンモニウム水溶液に注いで反応を停止し、ヘキサンで抽出した。有機相を水、飽和食塩水で洗浄した。硫酸マグネシウムで乾燥後、濃縮乾固した。得られた固体をメタノールで洗浄し、目的物を得た(収量425 mg、2段階収率 49%）。ジp-トリルシクロペンタジエニル(4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)シランの同定は、FD-MSスペクトルで行った。以下にその測定結果を示す。
　FD-MS: m/z = 608.4 (M+) Subsequently, the off-white solid obtained in the previous reaction was dissolved in 20 ml of tetrahydrofuran in a 100 ml Schlenk flask under a nitrogen atmosphere, and 0.15 ml (1.39 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) was obtained. Was added. After cooling to −78 ° C., 0.66 ml (1.32 mmol) of 2.0 M cyclopentadienyl sodium tetrahydrofuran solution was added, and the mixture was stirred for 17 hours while gradually returning to room temperature. After heating in an oil bath at 80 ° C for 6 hours, 0.13 ml (1.39 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) and 0.66 ml of 2.0 M cyclopentadienyl sodium tetrahydrofuran solution at -30 ° C (1.32 mmol) was added, and the mixture was stirred for 16 hours while gradually returning to room temperature. The reaction was stopped by pouring into a saturated aqueous ammonium chloride solution, and the mixture was extracted with hexane. The organic phase was washed with water and saturated brine. After drying with magnesium sulfate, it was concentrated to dryness. The obtained solid was washed with methanol to obtain the desired product (yield 425 mg, 2-step yield 49%). Di-p-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,4-g '] Dichromenyl) silane was identified by FD-MS spectrum. The measurement results are shown below.
FD-MS: m / z = 608.4 (M + )
　（ii）ジp-トリルシリレン(η 5 -シクロペンタジエニル)(η 5 -4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)ジルコニウムジクロリドの合成
　窒素雰囲気下、100 mlシュレンクフラスコにジp-トリルシクロペンタジエニル(4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)シラン425 mg (0.698 mmol)、ジエチルエーテル20 mlを添加した。-78℃に冷却し、n-ブチルリチウム/ヘキサン溶液 (1.57 M) 0.92 ml (1.44 mmol）を徐々に添加した後、徐々に室温に戻しながら18時間撹拌した。-78℃に冷却し四塩化ジルコニウム150 mg （0.644 mmol）を添加し、室温まで徐々に昇温しながら23時間攪拌した。減圧下で溶媒を留去し、残渣のジクロロメタン抽出液をセライトで濾過した。濾液を減圧下で濃縮し他の地、少量のヘキサンおよびペンタンで各3回洗浄し、減圧下で乾燥して目的物を得た(収量300 mg、収率51%）。 (Ii) di p- Torirushiriren (eta 5 - cyclopentadienyl) (η 5 -4,4,7,7- tetramethyl -3,4,7,8,9,12- hexahydro -2H- cyclopenta - Synthesis of [2,1-g: 3,4-g '] dichromyl) zirconium dichloride In a 100 ml Schlenk flask under nitrogen atmosphere, di-p-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3 , 4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,4-g ′] dicromenyl) silane 425 mg (0.698 mmol) and diethyl ether 20 ml were added. After cooling to −78 ° C., 0.92 ml (1.44 mmol) of n-butyllithium / hexane solution (1.57 M) was gradually added, and the mixture was stirred for 18 hours while gradually returning to room temperature. It cooled to -78 degreeC, 150 mg (0.644 mmol) of zirconium tetrachloride was added, and it stirred for 23 hours, heating up gradually to room temperature. The solvent was distilled off under reduced pressure, and the dichloromethane extract of the residue was filtered through celite. The filtrate was concentrated under reduced pressure, washed three times each with other sites, a small amount of hexane and pentane, and dried under reduced pressure to obtain the desired product (yield 300 mg, yield 51%).
　目的物の同定は、1H NMRスペクトルおよびFD-MSスペクトルで行った。以下にその測定結果を示す。 The target product was identified by 1 H NMR spectrum and FD-MS spectrum. The measurement results are shown below.
　1H NMR (270 MHz, CDCl3):
1.45 (s, 6H), 1.52 (s, 6H), 1.81-1.84 (m, 4H), 2.40 (s, 6H), 4.11-4.16 (m, 4H), 5.87 (t, 2H, J = 2.3 Hz), 6.13 (s, 2H), 6.67-6.69 (t, 2H, J = 2.3 Hz), 7.31 (d, 4H, J = 7.6 Hz), 7.91 (s, 2H), 7.93 (d, 4H, J = 7.6 Hz)
　FD-MS: m/z = 766.2 (M+) 1 H NMR (270 MHz, CDCl 3 ):
1.45 (s, 6H), 1.52 (s, 6H), 1.81-1.84 (m, 4H), 2.40 (s, 6H), 4.11-4.16 (m, 4H), 5.87 (t, 2H, J = 2.3 Hz) , 6.13 (s, 2H), 6.67-6.69 (t, 2H, J = 2.3 Hz), 7.31 (d, 4H, J = 7.6 Hz), 7.91 (s, 2H), 7.93 (d, 4H, J = 7.6 Hz)
FD-MS: m / z = 766.2 (M + )
　実施例Ａ１～Ａ８で製造された遷移金属化合物の構造式を以下に示す。
Figure JPOXMLDOC01-appb-C000023
 　＜エチレン／プロピレン／ＥＮＢ共重合体の製造＞
　［実施例Ｂ１］
　充分に窒素置換した内容積２Ｌのステンレス製オートクレーブにヘキサン１０３０ｍL、エチリデンノルボルネン（ＥＮＢ）１２ｍＬを装入し、系内の温度を９４℃に昇温した後、プロピレンを分圧で０．９０ＭＰａ分装入し、エチレンを供給することにより全圧を１．６ＭＰａ－Ｇとした。次に、トリイソブチルアルミニウム０．３ｍｍｏｌ、実施例Ａ１で製造したジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド０．０００１２ｍｍｏｌおよびトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート０．０００４８ｍｍｏｌを窒素で圧入し、攪拌回転数を２５０ｒｐｍにすることにより重合を開始した。その後、エチレンのみを連続的に供給することにより全圧を１．６ＭＰａ－Ｇに保ち、９５℃で１５分間重合を行った。少量のエタノールを系内に添加することにより重合を停止した後、未反応のエチレンをパージした。得られたポリマー溶液を、大過剰のメタノール／アセトン混合溶液中に投入することにより、ポリマーを析出させた。ポリマーをろ過により回収し、１２０℃の減圧下で一晩乾燥した。 The structural formulas of the transition metal compounds produced in Examples A1 to A8 are shown below.
Figure JPOXMLDOC01-appb-C000023
 <Production of ethylene / propylene / ENB copolymer>
[Example B1]
A stainless steel autoclave with an internal volume of 2 L that has been sufficiently purged with nitrogen is charged with 1030 mL of hexane and 12 mL of ethylidene norbornene (ENB). The total pressure was adjusted to 1.6 MPa-G by supplying ethylene. Next, 0.3 mmol of triisobutylaluminum, di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride prepared in Example A1 Polymerization was initiated by injecting 0,012 mmol and 0.00048 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 250 rpm. Thereafter, only ethylene was continuously supplied to keep the total pressure at 1.6 MPa-G, and polymerization was carried out at 95 ° C. for 15 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol / acetone mixed solution to precipitate a polymer. The polymer was collected by filtration and dried overnight at 120 ° C. under reduced pressure.
　その結果、エチレン含量８０．７ｍｏｌ％、ＥＮＢ含量１．５mol％、極限粘度［η］４．３ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が１１．２ｇ得られた。重合活性は３７４．３ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 11.2 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.7 mol%, an ENB content of 1.5 mol%, and an intrinsic viscosity [η] of 4.3 dl / g was obtained. The polymerization activity was 374.3 kg / mmol-Zr / h.
　［実施例Ｂ２］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ２で製造した０．００００８ｍｍｏｌのジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジ-tert-ブチルフルオレニル)]ジルコニウムジクロリド、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート０．０００３２ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B2]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A2. (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate The same operation as in Example B1 was performed except that the volume was changed to 00003 mmol.
　その結果、エチレン含量８０．８ｍｏｌ％、ＥＮＢ含量１．８mol％、極限粘度［η］４．４４ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が４．４９ｇ得られた。重合活性は２２４．５ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 4.49 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.8 mol%, an ENB content of 1.8 mol%, and an intrinsic viscosity [η] of 4.44 dl / g was obtained. The polymerization activity was 224.5 kg / mmol-Zr / h.
　［実施例Ｂ３］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ３で製造した０．００００８ｍｍｏｌのジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００３２ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B3]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A3. (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate changed to 0.00032mmol Except that, the same operation as in Example B1 was performed.
　その結果、エチレン含量８２．９ｍｏｌ％、ＥＮＢ含量１．８mol％、極限粘度［η］５．５９ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が１０．１ｇ得られた。重合活性は５０２．５ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 10.1 g of an ethylene / propylene / ENB copolymer having an ethylene content of 82.9 mol%, an ENB content of 1.8 mol%, and an intrinsic viscosity [η] of 5.59 dl / g was obtained. The polymerization activity was 502.5 kg / mmol-Zr / h.
　［実施例Ｂ４］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ４で製造した０．０００１ｍｍｏｌのジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチル、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００４ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B4]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.0001 mmol of di-p-tolylsilylene prepared in Example A4. Changed (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate to 0.0004 mmol Except that, the same operation as in Example B1 was performed.
　その結果、エチレン含量８４．３ｍｏｌ％、ＥＮＢ含量１．９mol％、極限粘度［η］５．６３ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が２．２１ｇ得られた。重合活性は８８．４ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 2.21 g of an ethylene / propylene / ENB copolymer having an ethylene content of 84.3 mol%, an ENB content of 1.9 mol%, and an intrinsic viscosity [η] of 5.63 dl / g was obtained. The polymerization activity was 88.4 kg / mmol-Zr / h.
　［実施例Ｂ５］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ５で製造した０．０００１ｍｍｏｌのジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジクロリド、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００４ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B5]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared from 0.0001 mmol of diphenylsilylene (η 5- Except that cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.0004 mmol. The same operation as in Example B1 was performed.
　その結果、エチレン含量８３．４ｍｏｌ％、ＥＮＢ含量１．９mol％、極限粘度［η］５．０８ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が８．０６ｇ得られた。重合活性は３２２．４ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 8.06 g of an ethylene / propylene / ENB copolymer having an ethylene content of 83.4 mol%, an ENB content of 1.9 mol%, and an intrinsic viscosity [η] of 5.08 dl / g was obtained. The polymerization activity was 322.4 kg / mmol-Zr / h.
　［実施例Ｂ６］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ６で製造した０．０００１ｍｍｏｌのジフェニルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシ-3,6-ジメチルフルオレニル)]ジルコニウムジメチル、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００４ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B6]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared by adding 0.0001 mmol of diphenylsilylene (η 5- Except that cyclopentadienyl) [η 5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate was changed to 0.0004 mmol. The same operation as in Example B1 was performed.
　その結果、エチレン含量８２．２ｍｏｌ％、ＥＮＢ含量２．０mol％、極限粘度［η］５．２１ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が７．９７ｇ得られた。重合活性は３１８．８ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 7.97 g of an ethylene / propylene / ENB copolymer having an ethylene content of 82.2 mol%, an ENB content of 2.0 mol%, and an intrinsic viscosity [η] of 5.21 dl / g was obtained. The polymerization activity was 318.8 kg / mmol-Zr / h.
　［実施例Ｂ７］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ７で製造した０．００００８ｍｍｏｌのジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジ-t-ブチル-4-メトキシフルオレニル)]ジルコニウムジクロリド、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００３２ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B7]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.00008 mmol of di-p-tolylsilylene prepared in Example A7. (η 5 -cyclopentadienyl) [η 5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride, 0.00032 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate The same operation as in Example B1 was performed except that the change was made.
　その結果、エチレン含量７３．７ｍｏｌ％、ＥＮＢ含量１．９mol％、極限粘度［η］３．０６ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が２．８４ｇ得られた。重合活性は１４２．０ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 2.84 g of an ethylene / propylene / ENB copolymer having an ethylene content of 73.7 mol%, an ENB content of 1.9 mol%, and an intrinsic viscosity [η] of 3.06 dl / g was obtained. The polymerization activity was 142.0 kg / mmol-Zr / h.
　［実施例Ｂ８］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、実施例Ａ８で製造した０．０００１ｍｍｏｌのジp-トリルシリレン(η5-シクロペンタジエニル)(η5-4,4,7,7-テトラメチル-3,4,7,8,9,12-ヘキサヒドロ-2H-シクロペンタ-[2,1-g:3,4-g']ジクロメニル)ジルコニウムジクロリド、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００４ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Example B8]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in 0.0001 mmol of di p-tolylsilylene prepared in Example A8 ( η 5 -cyclopentadienyl) (η 5 -4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3, The same operation as in Example B1 was carried out except that 4-g ′] dicromenyl) zirconium dichloride and triphenylcarbenium tetrakis (pentafluorophenyl) borate were changed to 0.0004 mmol.
　その結果、エチレン含量７９．５ｍｏｌ％、ＥＮＢ含量２．３mol％、極限粘度［η］６．３０ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が６．４６ｇ得られた。重合活性は１２９．２ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 6.46 g of an ethylene / propylene / ENB copolymer having an ethylene content of 79.5 mol%, an ENB content of 2.3 mol%, and an intrinsic viscosity [η] of 6.30 dl / g was obtained. The polymerization activity was 129.2 kg / mmol-Zr / h.
　［比較例Ｂ１］
　ジ-p-トリルシリレン(η5-シクロペンタジエニル)[η5-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリドを、０．０００１ｍｍｏｌのジフェニルシリレン(η5-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、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートを０．０００４ｍｍｏｌに変更したこと以外は実施例Ｂ１と同様の操作を行った。 [Comparative Example B1]
Di-p-tolylsilylene (η 5 -cyclopentadienyl) [η 5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was added to 0.0001 mmol of diphenylsilylene (η 5 -cyclopentadienyl) ( The same operation as in Example B1 was carried out except that (η 5 -fluorenyl) zirconium dichloride and triphenylcarbenium tetrakis (pentafluorophenyl) borate were changed to 0.0004 mmol.
　その結果、エチレン含量７５．０ｍｏｌ％、ＥＮＢ含量２．０mol％、極限粘度［η］２．６３ｄｌ／ｇのエチレン／プロピレン／ＥＮＢ共重合体が９．４９ｇ得られた。重合活性は３７９．６ｋｇ／ｍｍｏｌ－Ｚｒ／ｈであった。 As a result, 9.49 g of an ethylene / propylene / ENB copolymer having an ethylene content of 75.0 mol%, an ENB content of 2.0 mol%, and an intrinsic viscosity [η] of 2.63 dl / g was obtained. The polymerization activity was 379.6 kg / mmol-Zr / h.

Claims (17)

  1. 　下記一般式［Ｉ］または［ＩＩ］で表される遷移金属化合物［Ａ］。
    Figure JPOXMLDOC01-appb-C000001
     〔式［I］および［II］において、
    　Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ13およびＲ14は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ1からＲ4までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、Ｒ13およびＲ14は互いに結合して環を形成していてもよく、
    　Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11およびＲ12は、それぞれ独立に、水素原子、ＺＲで表される置換基（ただし、Ｚは酸素原子または硫黄原子であり、Ｒは炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｚを介してフルオレニル配位子と結合している。）、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基（ただし、ＺＲで表される置換基を除く。）、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ5からＲ12までの隣接した置換基は互いに結合して環を形成していてもよく、Ｒ5からＲ12のうち、少なくとも１つはＺＲで表される置換基であり、
    　Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれ、
    　Ａは芳香環を含んでいてもよい炭素原子数２～２０の二価の飽和もしくは不飽和の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、
    　Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、
    　ｊは１～４の整数であり、
    　Ｑは、ハロゲン原子、炭素数１～２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から選ばれ、ｊが２以上の場合は、複数個あるＱは互いに同一であっても異なっていてもよい。〕     The transition metal compound [A] represented by the following general formula [I] or [II].
    Figure JPOXMLDOC01-appb-C000001
     [In the formulas [I] and [II]
    R 1 , R 2 , R 3 , R 4 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group or a nitrogen-containing group. , An atom or a substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents from R 1 to R 4 may be bonded to each other to form a ring, R 13 and R 14 may be bonded to each other to form a ring.
    R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom or a substituent represented by ZR (where Z is an oxygen atom or a sulfur atom) R is a substituent selected from the group consisting of 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 and a halogen-containing group; A hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, and an oxygen-containing group (however, the substitution represented by ZR) An atom or a substituent selected from the group consisting of a halogen atom and a halogen-containing group, and adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring, among the R 5 of R 12, at least one Z In a substituent represented,
    Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom;
    A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A contains two or more ring structures including a ring formed with Y. You may,
    M is a titanium atom, a zirconium atom or a hafnium atom,
    j is an integer from 1 to 4,
    Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, a plurality of Q May be the same as or different from each other. ]
  2. 　前記一般式［I］または［II］においてＺが酸素原子である請求項１に記載の遷移金属化合物［Ａ］。 The transition metal compound [A] according to claim 1, wherein Z is an oxygen atom in the general formula [I] or [II].
  3. 　前記一般式［I］または［II］においてＹがケイ素原子である請求項１または２に記載の遷移金属化合物［Ａ］。 The transition metal compound [A] according to claim 1 or 2, wherein Y in the general formula [I] or [II] is a silicon atom.
  4. 　前記一般式［I］または［II］においてＭがジルコニウム原子である請求項１～３のいずれか一項に記載の遷移金属化合物［Ａ］。 The transition metal compound [A] according to any one of claims 1 to 3, wherein M in the general formula [I] or [II] is a zirconium atom.
  5. 　請求項１～４のいずれか一項に記載の遷移金属化合物［Ａ］を含有するオレフィン重合用触媒。 An olefin polymerization catalyst containing the transition metal compound [A] according to any one of claims 1 to 4.
  6. 　［Ｂ］［B-1］有機金属化合物、
    　　　　［B-2］有機アルミニウムオキシ化合物、および
    　　　　［B-3］遷移金属化合物［Ａ］と反応してイオン対を形成する化合物
    からなる群より選ばれる少なくとも１種の化合物をさらに含有する請求項５に記載のオレフィン重合用触媒。     [B] [B-1] organometallic compound,
    [B-2] further containing at least one compound selected from the group consisting of an organoaluminum oxy compound and a compound that forms an ion pair by reacting with [B-3] a transition metal compound [A]. The catalyst for olefin polymerization described in 1.
  7. 　請求項５または６に記載のオレフィン重合用触媒の存在下でオレフィンを重合する工程［Ｐ］を含むオレフィン重合体の製造方法。 A method for producing an olefin polymer, comprising a step [P] of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 5 or 6.
  8. 　前記工程［Ｐ］がエチレンを重合する工程である請求項７に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 7, wherein the step [P] is a step of polymerizing ethylene.
  9. 　前記工程［Ｐ］がエチレンと非共役ポリエンとを共重合する工程である請求項８に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 8, wherein the step [P] is a step of copolymerizing ethylene and a non-conjugated polyene.
  10. 　前記非共役ポリエンが下記一般式［III］で表される請求項９に記載のオレフィン重合体の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     　〔式中、ｍは０から２の整数であり、
    　Ｒ15、Ｒ16、Ｒ17およびＲ18は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、該炭化水素基は二重結合を有していてもよく、
    　Ｒ15からＲ18までのうちの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成していてもよく、Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成していてもよく、
    　以下の（i）から（iv）の要件の少なくとも一つが満たされる。
    （i）Ｒ15からＲ18までの少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
    （ii）Ｒ15からＲ18までの任意の二つの置換基は互いに結合して環を形成し、該環は二重合を含んでいる。
    （iii）Ｒ15とＲ16とで、またはＲ17とＲ18とでアルキリデン基を形成している。
    （iv）Ｒ15とＲ17とが、またはＲ16とＲ18とが互いに結合して二重結合を形成している。〕     The method for producing an olefin polymer according to claim 9, wherein the non-conjugated polyene is represented by the following general formula [III].
    Figure JPOXMLDOC01-appb-C000002
     [Wherein m is an integer from 0 to 2;
    R 15 , R 16 , R 17 and R 18 are each independently selected from 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. The hydrocarbon group may have a double bond,
    Any two substituents of from R 15 to R 18 may bond to each other to form a ring, the ring may contain a double bond, with a pair of R 15 and R 16, Alternatively, R 17 and R 18 may form an alkylidene group, R 15 and R 17 , or R 16 and R 18 may be bonded to each other to form a double bond,
    At least one of the following requirements (i) to (iv) is satisfied.
    (I) At least one of R 15 to R 18 is a hydrocarbon group having one or more double bonds.
    (Ii) Any two substituents from R 15 to R 18 are bonded to each other to form a ring, and the ring includes bipolymerization.
    (Iii) R 15 and R 16 or R 17 and R 18 form an alkylidene group.
    (Iv) R 15 and R 17 or R 16 and R 18 are bonded to each other to form a double bond. ]
  11. 　前記非共役ポリエンが、５－エチリデン－２－ノルボルネン（ＥＮＢ）または５－ビニル－２－ノルボルネン（ＶＮＢ）であることを特徴とする、請求項１０に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 10, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).
  12. 　前記工程［Ｐ］がエチレンと炭素数が３から２０のα－オレフィンと非共役ポリエンとを共重合する工程である請求項９～１１のいずれか１項に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to any one of claims 9 to 11, wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
  13. 　前記α－オレフィンがプロピレンである請求項１２に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 12, wherein the α-olefin is propylene.
  14. 　前記工程［Ｐ］の重合温度が８０℃以上である請求項８～１３のいずれか１項に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to any one of claims 8 to 13, wherein the polymerization temperature in the step [P] is 80 ° C or higher.
  15. 　前記工程［Ｐ］が炭素数３～２０のα－オレフィンを重合する工程である請求項７に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 7, wherein the step [P] is a step of polymerizing an α-olefin having 3 to 20 carbon atoms.
  16. 　前記工程［Ｐ］がエチレンと炭素数３～２０のα－オレフィンとを共重合する工程である請求項１５に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 15, wherein the step [P] is a step of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.
  17. 　前記α－オレフィンがプロピレンである請求項１５または１６に記載のオレフィン重合体の製造方法。 The method for producing an olefin polymer according to claim 15 or 16, wherein the α-olefin is propylene.
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