WO2019188644A1 - Composé de métal de transition, catalyseur pour la polymérisation d'oléfine, et procédé de production d'un polymère d'oléfine - Google Patents

Composé de métal de transition, catalyseur pour la polymérisation d'oléfine, et procédé de production d'un polymère d'oléfine 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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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/ja
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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

La présente invention aborde le problème de la réalisation d'un composé de métal de transition qui a une activité de polymérisation élevée et qui est utile pour la production d'un polymère d'oléfine ayant un poids moléculaire élevé ; et un procédé. La solution selon l'invention porte sur un composé de métal de transition qui est représenté par la formule générale (I) ou (II). (Dans Les formules, chacune des fractions R1-R14 représente un atome d'hydrogène, un groupe hydrocarboné ou similaire ; au moins l'une des fractions R5-R12 représente un radical qui est exprimé sous la forme ZR (où Z représente un atome d'oxygène ou similaire ; et R représente un groupe hydrocarboné ou similaire, qui est lié à un ligand fluorényle par l'intermédiaire de Z) ; A représente un groupe hydrocarboné divalent ; Y représente un atome de carbone, un atome de silicium ou similaire ; M représente un atome de métal de transition du groupe 4 du tableau périodique ; j représente un nombre entier de 1 à 4 ; et Q représente un atome d'halogène ou similaire.)
PCT/JP2019/011656 2018-03-26 2019-03-20 Composé de métal de transition, catalyseur pour la polymérisation d'oléfine, et procédé de production d'un polymère d'oléfine WO2019188644A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172443A (ja) * 1992-06-22 1994-06-21 Fina Technol Inc メタロセン触媒系を用いてシンジオタクテイツクポリオレフイン類の融点および分子量を調節する方法
JPH08176222A (ja) * 1994-10-25 1996-07-09 Tosoh Corp オレフィン重合触媒およびオレフィン重合体の製造方法
WO2009081794A1 (fr) * 2007-12-21 2009-07-02 Mitsui Chemicals, Inc. Procédé de production d'un copolymère d'éthylène/alpha-oléfine/polyène non conjugué
JP2015147862A (ja) * 2014-02-06 2015-08-20 東ソー株式会社 ポリエチレン系重合体製造用触媒及びそれを用いてなるポリエチレン系重合体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172443A (ja) * 1992-06-22 1994-06-21 Fina Technol Inc メタロセン触媒系を用いてシンジオタクテイツクポリオレフイン類の融点および分子量を調節する方法
JPH08176222A (ja) * 1994-10-25 1996-07-09 Tosoh Corp オレフィン重合触媒およびオレフィン重合体の製造方法
WO2009081794A1 (fr) * 2007-12-21 2009-07-02 Mitsui Chemicals, Inc. Procédé de production d'un copolymère d'éthylène/alpha-oléfine/polyène non conjugué
JP2015147862A (ja) * 2014-02-06 2015-08-20 東ソー株式会社 ポリエチレン系重合体製造用触媒及びそれを用いてなるポリエチレン系重合体の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HELMUT G. ALT ET AL.: "Syndiospezifische Polymerisation von Propylen: 2- und 2, 7-substituierte Metallocenkomplex des typs (C13H8-nCR' 2C5H4) MCl2 (n=1, 2; R=Alkoxy, Alkyl, Aryl, Hal; R' =Me, Ph; M=Zr, Hf", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 522, 1996, pages 39 - 54, XP002247789, doi:10.1016/0022-328X(95)06045-X *
SAIKI HASEGAWA ET AL.: "High-Temperature Ethylene/a-Olefin Copolymerization with a Zirconocene catalyst: Effects of the Zirconocene Ligand and Polymerization Conditions on Copolymerization Behavior", JOURNAL OF POLYMER SCIENCE : PART A: POLYMER CHEMISTRY, vol. 38, 2000, pages 4641 - 4648, XP001037588 *

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