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

Abstract

To provide a transition metal compound capable of producing an olefin polymer having a high molecular weight and a narrow molecular weight distribution, a polymerization catalyst containing the compound, and a method for producing the polymer using the catalyst.SOLUTION: The present invention provides a transition metal compound [A] represented by general formula [1], with a specific substituent being incorporated into a 2-indenyl ring.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a transition metal compound, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer using the olefin polymerization catalyst.

Background Art

[0002] Olefin polymers are molded by various molding methods and are used in a wide range of applications. For example, films or sheets used for packaging food products, liquids, or daily necessities are made of extruded ethylene polymers. Depending on the molding method or application, the properties required of olefin polymers vary. For example, when performing T-die molding, it is required to have processing performance such as being able to be molded stably even at high speeds (high-speed film-forming processability) and having a small neck-in.

[0003] Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branched structure, so it has a large melt tension. Therefore, it has good moldability such as a small neck-in and is used in various applications. However, there are still problems such as low mechanical strength such as tensile strength, tear strength, or impact resistance of the molded body, and poor high-speed film-forming processability in T-die molding.

[0004] On the other hand, ethylene polymers produced using Ziegler catalysts or metallocene catalysts, in contrast to LDPE, have high tensile strength, tear strength, or impact resistance due to their molecular structure, and are therefore used in applications where mechanical strength is required. However, there is a problem that the melt tension is small and the moldability is poor.

[0005] In order to solve these problems, methods (Patent Documents 1 and 2) for producing an ethylene polymer having long-chain branches in the presence of a solid catalyst component composed of two transition metal compounds and a solid carrier have been proposed. In addition, as a method for producing an ethylene-based polymer having long-chain branches in the presence of a solid catalyst component composed of a transition metal compound and a solid carrier, a method using a crosslinked bis(1-indenyl) type compound as the transition metal compound (Patent Document 3) and a method using a crosslinked cyclopentadienyl(1-indenyl) type compound (Patent Documents 4 and 5) have been reported. On the other hand, Patent Document 6 reports olefin polymerization using a transition metal compound having a 2-indenyl group as described below.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0007] By the way, it is desirable that the olefin polymerization catalyst used in production has high catalytic activity from the viewpoint of production efficiency. Further, when an olefin-based polymer typified by an ethylene-based polymer is used for applications that require high strength such as pipes, it is desired that the olefin-based polymer has a high molecular weight and a narrow molecular weight distribution. However, the techniques reported in Patent Documents 3 to 6 have problems such as room for improvement in the molecular weight and molecular weight distribution of the produced olefin-based polymer.

[0008] Therefore, an object of the present invention is to provide a transition metal compound capable of producing an olefin polymer having a high molecular weight and a narrow molecular weight distribution, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer using the olefin polymerization catalyst.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by introducing a specific substituent into the 2-indenyl ring of a silyl-bridged (2-indenyl)(2,3,4,5-tetramethylcyclopentadienyl) type complex, and have completed the present invention.

[0010] The gist of the present invention is as follows. [1] A transition metal compound [A] represented by the following general formula [1]. [Chemical formula] (In general formula [1], M is a Group 4 transition metal atom of the periodic table, n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. The anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene derivative group. When n is 2 or more, the groups represented by a plurality of Xs may be the same or different from each other, and may be bonded to each other to form a ring, Q is a Group 14 atom of the periodic table, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8is, independently of one another, a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, R 2 , R 3 , R 4 , R 5 at least one of R R 2 ~R 5 may combine with adjacent substituents to form a ring which may have a substituent, R 7 and R 8 may combine with each other to form a ring containing Q, and this ring may have a substituent.)

[0011] [2] In the general formula [1], M is a zirconium atom or a hafnium atom, X is, independently of one another, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, Q is a carbon atom or a silicon atom, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are, independently of one another, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, the transition metal compound [A] according to item [1].

[0012] [3] In the general formula [1], Q is a silicon atom, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 and R 8 wherein each of R and R is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, the transition metal compound [A] according to item [1] or [2].

[0013] [4] In the general formula [1], R 1 and R 6 are hydrogen atoms, the transition metal compound [A] according to any one of items [1] to [3].

[0014] [5] In the general formula [1], R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, the transition metal compound [A] according to any one of items [1] to [4].

[0015] [6] In the general formula [1], R 3 and R 4 are bonded to each other to form a ring which may have a substituent, the transition metal compound [A] according to any one of items [1] to [5].

[0016] [7] An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of items [1] to [6].

[0017] [8] [B-1] An organometallic compound, [B-2] An organoaluminum oxy compound, and [B-3] A compound that reacts with the transition metal compound [A] to form an ion pair The olefin polymerization catalyst according to item [7], further comprising at least one compound [B] selected from the group consisting of

[0018] A process for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to item [7] or [8] of [9].

[0019]

[10] The method for producing an olefin polymer according to item [9], wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.

Advantages of the Invention

[0020] According to the transition metal compound, the olefin polymerization catalyst containing the transition metal compound, and the method for producing an olefin polymer using the olefin polymerization catalyst according to the present invention, an olefin polymer having a high molecular weight and a narrow molecular weight distribution can be produced.

Modes for Carrying Out the Invention

[0021] Hereinafter, the transition metal compound and the like according to the present invention will be described in more detail. [Transition metal compound [A]] The transition metal compound [A] according to the present invention (hereinafter, also referred to as "component (A)") is represented by the following general formula [1].

[0022]

Chemical formula

[0023] 《M, n, X》 In the general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom. n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral, preferably 1 or 2.

[0024] X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons, and the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene derivative group. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group.

[0025] When n is 2 or more, the groups represented by a plurality of Xs may be the same as or different from each other, and may be bonded to each other to form a ring. Further, when a plurality of the rings exist, the rings may be the same as or different from each other.

[0026] Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., preferably chlorine or bromine, and more preferably chlorine.

[0027] Examples of the hydrocarbon group include linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbutan-2-yl group), 4,4-dimethylpentyl group, etc.; A linear or branched alkenyl group or an unsaturated double bond-containing group such as a vinyl group, an allyl group, a propenyl group (prop-1-en-1-yl group), an iso-propenyl group (prop-1-en-2-yl group), an arylenyl group (prop-1,2-dien-1-yl group), a but-3-en-1-yl group, a crotyl group (but-2-en-1-yl group), a but-3-en-2-yl group, a methallyl group (2-methylallyl group), a buta-1,3-dienyl group, a pent-4-en-1-yl group, a pent-3-en-1-yl group, a pent-2-en-1-yl group, an iso-pentenyl group (3-methylbut-3-en-1-yl group), a 2-methylbut-3-en-1-yl group, a pent-4-en-2-yl group, a prenyl group (3-methylbut-2-en-1-yl group); A linear or branched alkynyl group or an unsaturated triple bond-containing group such as an ethynyl group, a prop-2-yn-1-yl group, a propargyl group (prop-1-yn-1-yl group); An aromatic-containing linear or branched alkyl group and an unsaturated double bond-containing group such as a benzyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, a 2,4,6-trimethylbenzyl group, a 3,5-dimethylbenzyl group, a cuminyl group (4-iso-propylbenzyl group), a 2,4,6-tri-iso-propylbenzyl group, a 4-tert-butylbenzyl group, a 3,5-di-tert-butylbenzyl group, a 1-phenylethyl group, a benzhydryl group (diphenylmethyl group); A cyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, a 2-adamantyl group; Aromatic substituents such as phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), duryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. can be mentioned. Among the hydrocarbon groups, a methyl group, iso-butyl group, neopentyl group, silyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group are preferable.

[0028] Examples of the halogen-containing group include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion. Among the halogen-containing groups, a pentafluorophenyl group is preferable.

[0029] Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, trimethylsilylmethyl group. Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.

[0030] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-iso-propylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-iso-propylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion. Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.

[0031] Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group). Among the sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) is preferable.

[0032] Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a pyrrolyl group, and a bistriflylimide group. Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferable.

[0033] Examples of the phosphorus-containing group include a hexafluorophosphate anion.

[0034] Examples of the boron-containing group include groups represented by tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, BR4 (where each R independently represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.).

[0035] Examples of the aluminum-containing group include

[0036] [Chemical formula] Groups represented by AlR4 (where each R independently represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.) that can form a four-membered ring (where M represents M in the general formula [1]) represented by

[0037] Examples of the conjugated diene derivative group include 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperylenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, etc., and metallocyclopentene group.

[0038] Examples of the neutral ligand capable of coordinating with the lone pair of electrons include ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, amines such as triethylamine, diethylamine, heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, thiophene, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine.

[0039] 《Q》 In the general formula [1], Q is an atom of Group 14 of the periodic table, such as a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

[0040] 《R 1 ~R 8 》 In the general formula [1], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and at least one of R 2 , R 3 , R 4 , R 5 is a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. At least one of R 2 , R 3 , R 4 , R 5 is a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. By using the transition metal compound [A], the molecular weight of the olefin polymer produced increases and the molecular weight distribution becomes narrower.

[0041] The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms excluding aromatic hydrocarbon groups or an aromatic hydrocarbon group having 6 to 40 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes substituents having an aromatic structure such as an arylalkyl group.

[0042] Examples of the hydrocarbon group having 1 to 40 carbon atoms include A linear or branched alkyl group having 1 to 40 carbon atoms, such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbutan-2-yl group, hexan-3-yl group, 2-methylpentan-3-yl group, heptan-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group; A vinyl group, an allyl group, a propenyl group, an iso-propenyl group, an arylenyl group, a but-3-en-1-yl group, a crotyl group, a but-3-en-2-yl group, a methallyl group, a buta-1,3-dienyl group, a penta-4-en-1-yl group, a penta-3-en-1-yl group, a penta-2-en-1-yl group, an iso-pentenyl group, a 2-methylbut-3-en-1-yl group, a penta-4-en-2-yl group, a prenyl group, a 2-methyl-but-2-en-1-yl group, a penta-3-en-2-yl group, a 2-methyl-but-3-en-2-yl group, a penta-1-en-3-yl group, a penta-2,4-dien-1-yl group, a penta-1,3-dien-1-yl group, a penta-1,4-dien-3-yl group, an iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), a penta-2,4-dien-2-yl group, a hexa-5-en-1-yl group, a hexa-4-en-1-yl group, a hexa-3-en-1-yl group, a hexa-2-en-1-yl group, a 4-methyl-penta-4-en-1-yl group, a 3-methyl-penta-4-en-1-yl group, a 2-methyl-penta-4-en-1-yl group, a hexa-5-en-2-yl group, a 4-methyl-penta-3-en-1-yl group, a 3-methyl-penta-3-en-1-yl group, a 2,3-dimethyl-but-2-en-1-yl group, a 2-methylpenta-4-en-2-yl group, a 3-ethylpenta-1-en-3-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-but-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, etc., a linear or branched alkenyl group or an unsaturated double bond-containing group having 2 to 40 carbon atoms; An ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-1-yn-1-yl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a pent-1-yn-1-yl group, a pent-2-yn-1-yl group, a pent-3-yn-1-yl group, a pent-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a pent-3-yn-2-yl group, a 2-methyl-but-3-yn-1-yl group, a pent-4-yn-2-yl group, a hex-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a 2-methyl-pent-3-yn-2-yl group, a 2,2-dimethyl-but-3-yn-1-yl group, a hex-4-yn-1-yl group, a hex-5-yn-1-yl group, or the like, a linear or branched alkynyl group or an unsaturated triple bond-containing group having 2 to 40 carbon atoms; benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl)diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzindenyl)propan-2-yl group, (1-benzindenyl)diphenylmethyl group, 2-(1-benzindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, 2-(1-azulenyl)ethyl group, etc., aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienenyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Aromatic substituents having 6 to 40 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, duryl group, 2,6 - di - iso - propylphenyl group, 2,4,6 - tri - iso - propylphenyl group, 4 - tert - butylphenyl group, 3,5 - di - tert - butylphenyl group, allylphenyl group, (but - 3 - en - 1 - yl)phenyl group, (but - 2 - en - 1 - yl)phenyl group, methallylphenyl group, prenylphenyl group, 4 - adamantylphenyl group, 3,5 - di - adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. are exemplified.

[0043] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1 - propyl group, 1 - butyl group, 1 - pentyl group, 1 - hexyl group, 1 - heptyl group, 1 - octyl group, iso - propyl group, sec - butyl group, tert - butyl group, iso - butyl group, iso - pentyl group, neopentyl group, tert - pentyl group, pentan - 3 - yl group, iso - hexyl group, 1,1 - dimethylbutyl group, 3,3 - dimethylbutyl group, texyl group, 3 - methylpentan - 3 - yl group, heptan - 4 - yl group, 2,4 - dimethylpentan - 2 - yl group, 3 - ethylpentan - 3 - yl group, 4,4 - dimethylpentyl group, 4 - methylheptan - 4 - yl group, 4 - propylheptan - 4 - yl group, 2,4,4 - trimethylpentan - 2 - yl group are preferable, and methyl group, ethyl group, 1 - propyl group, 1 - butyl group, 1 - pentyl group, 1 - hexyl group, iso - propyl group, tert - butyl group, neopentyl group, 2,4 - dimethylpentan - 2 - yl group, 2,4,4 - trimethylpentan - 2 - yl group are more preferable.

[0044] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group, a methallyl group, a pent-4-en-1-yl group, a prenyl group, a penta-1,4-dien-3-yl group, a hex-5-en-1-yl group, a 2-methylpent-4-en-2-yl group, a 2-(cyclopentadienyl)propan-2-yl group, and a 2-(cyclopentadienyl)ethyl group are preferable, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, and a hex-5-en-1-yl group are more preferable.

[0045] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, an ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a pent-3-yn-1-yl group, a pent-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a hex-4-yn-1-yl group, and a hex-5-yn-1-yl group are preferable, and a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, and a but-3-yn-1-yl group are more preferable.

[0046] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group are preferred, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group are more preferred.

[0047] Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group are preferred, and cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-adamantyl group are more preferred.

[0048] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group are preferred, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group are more preferred.

[0049] Examples of the halogen-containing group include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, and trifluoromethylthio group.

[0050] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, a trifluoromethylthio group are preferable, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group are more preferable.

[0051] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenylmethylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group.

[0052] Among the silicon-containing groups, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a cyclopentadienyldimethylsilyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, an indenyl diphenylsilyl group, a fluorenyldimethylsilyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-triphenylsilylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group are preferable, and a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group are more preferable.

[0053] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyl-oxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a tolyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group.

[0054] Among these oxygen-containing groups, an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 10 carbon atoms is more preferable. Specifically, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyl-oxy group, benzyloxy group, phenoxy group, naphthoxy group, toluoyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, dibenzofuryl group are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group are more preferable.

[0055] Examples of the nitrogen-containing group include an amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, isoquinolyl group, tetrahydro-isoquinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group.

[0056] Among the nitrogen-containing groups, an amino group having 1 to 20 carbon atoms is preferable, and an amino group having 1 to 10 carbon atoms is more preferable. Specifically, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group are more preferable.

[0057] Examples of the sulfur-containing group include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, thiazolidinyl group.

[0058] Among the sulfur-containing groups, thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, thiazolyl group, benzothiazolyl group are preferred.

[0059] R 2 ~R 5 Among the adjacent substituents of 2 R 3 and R 3 R 4 and R 4 R 5may combine with each other to form a ring which may have a substituent. As the ring formed in this case, a 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may have a substituent and is fused to the indenyl ring portion is preferable. When there are a plurality of rings, these may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure combining the ring and the indenyl ring portion of the parent nucleus include a substituted benzindenyl ring, an unsubstituted tetrahydroindacene ring, a substituted tetrahydroindacene ring, and a substituted cyclopentatetrahydronaphthalene, and a substituted benzindenyl ring, an unsubstituted tetrahydroindacene ring, and a substituted tetrahydroindacene ring are preferable.

[0060] R 7 and R 8 may combine with each other to form a ring containing Q. As the ring formed in this case, a 3- to 8-membered ring which may have a substituent and is saturated or unsaturated is preferable. Although not particularly limited as long as the effects of the present invention are achieved, the ring is preferably a 4- to 6-membered ring. In this case, as the structure combining R 7 and R 8 and Q, examples include a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletane) ring, a substituted silacyclopentane (silolane) ring, a substituted silacyclohexane (silinane) ring, and a substituted silafluorene ring, and a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferable.

[0061] R 1 and R 6is, independently of each other, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, still more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

[0062] R 7 and R 8 are, independently of each other, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, still more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, and particularly preferably a methyl group.

[0063] R 2 ~R 5 are, independently of each other, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, still more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 、R 3 、R 4 、R 5At least one of them is a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. R 2 ~R 5 Among them, when adjacent substituents (e.g., R 2 and R 3 , R 3 and R 4 , R 4 and R 5 ) are not bonded to each other, they are preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, still more preferably a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and particularly preferably a methyl group or a phenyl group.

[0064] 《Preferred embodiments of transition metal compound [A]》 Preferred embodiments of the transition metal compound [A] include In the general formula [1], M is a zirconium atom or a hafnium atom, X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, Q is a carbon atom or a silicon atom, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, R 2 , R 3 , R 4 , R 5At least one of them is a transition metal compound [A-1] which is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms. In a more preferred embodiment, In the general formula [1], Q is a silicon atom, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, R 2 、R 3 、R 4 、R 5 At least one of them is a transition metal compound [A-2] which is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. In a more preferred embodiment of the transition metal compound [A-2], in the general formula [1], R 1 and R 6 are hydrogen atoms, R 2 ~R 5 At least one of them is a transition metal compound [A-3] which is a hydrocarbon group having 1 to 20 carbon atoms and the rest are hydrogen atoms. In a more preferred embodiment of the transition metal compound [A-3], in the general formula [1], R 2 、R 3 、R 4 、R 5 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. A transition metal compound [A-4] is mentioned. In a more preferred embodiment of the transition metal compound [A-4], in the general formula [1], R 3 and R 4Examples of the transition metal compound [A-5] include those that combine with each other to form a ring which may have a substituent.

[0065] 《Examples of transition metal compound [A]》 Specific examples of the transition metal compound [A] are shown below, but the scope of the present invention is not particularly limited thereby. However, R in [Table 3] 2 and R 5 where both substituents are hydrogen, and the combination where both R 3 and R 4 substituents in [Table 4] are hydrogen is not included.

[0066] For convenience, the ligand structure excluding the part represented by MXn (metal part) of the transition metal compound [A] is divided into five parts: the 2-indenyl ring part, the 2-indenyl ring part R 1 and R 6 substituents, the 2-indenyl ring part R 2 and R 5 substituents, the 2-indenyl ring part R 3 and R 4 substituents, and the structure of the bridging part. The abbreviation of the 2-indenyl ring part is α, the abbreviation of the 2-indenyl ring part R 1 and R 6 substituents is β, the abbreviation of the 2-indenyl ring part R 2 and R 5 substituents is γ, the abbreviation of the 2-indenyl ring part R 3 and R 4 substituents is δ, and the abbreviation of the structure of the bridging part is ε. The abbreviations of each substituent are shown in [Table 1] to [Table 5].

[0067] [Table 1] Note that the wavy line in the above [Table 1] indicates the bonding site with the bridging part.

[0068] [Table 2] R in the above [Table 2] 1 and R 6The substituents may be the same as or different from each other in their combination.

[0069]

Table 3

[0070]

Table 4

[0071]

Table 5

[0072] Specific examples of the metal moiety MXn include TiF2, TiCl2, TiBr2, TiI2, Ti(Me)2, Ti(Bn)2, Ti(Allyl)2, Ti(CH2-tBu)2, Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), Ti(CH2-Si(Me)3)2, Ti(ОMe)2, Ti(ОiPr)2, Ti(NMe2)2, Ti(ОMs)2, Ti(ОTs)2, Ti(ОTf)2, ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(Allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(ОMe)2, Zr(ОiPr)2, Zr(NMe2)2, Zr(ОMs)2, Zr(ОTs)2, Zr(ОTf)2, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(CH2-tBu)2, Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(ОMe)2, Hf(ОiPr)2, Hf(NMe2)2, Hf(ОMs)2, Hf(ОTs)2, Hf(ОTf)2. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe2 is a dimethylamino group, ОMs is a methanesulfonate group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

[0073] According to the above notation, the 2-indenyl ring moiety is α-1 in [Table 1], the 2-indenyl ring moiety R 1 and R 6 substituents are β-1 in [Table 2], the 2-indenyl ring moiety R 2 and R 5 substituents are both γ-2 in [Table 3], the 2-indenyl ring moiety R 3and R 4 When all the substituents are the combination of δ-1 in [Table 4] and the crosslinked part is ε-34 in [Table 5], and MXn of the metal part is ZrCl2, the compound represented by the following formula [5] is exemplified.

[0074]

Chemical formula

[0075] Also, when the 2-indenyl ring part is α-3 in [Table 1], the 2-indenyl ring part R 1 and R 6 the substituents are β-2 in [Table 2], the 2-indenyl ring part R 2 and R 5 When all the substituents are the combination of γ-1 in [Table 3] and the crosslinked part is ε-31 in [Table 5], and MXn of the metal part is HfMe2, the compound represented by the following formula [6] is exemplified.

[0076]

Chemical formula

[0077] Also, when the 2-indenyl ring part is α-1 in [Table 1], the 2-indenyl ring part R 1 and R 6 the substituents are β-1 in [Table 2], the 2-indenyl ring part R 2 the substituents are γ-7 in [Table 3], the 2-indenyl ring part R 3 and R 4 When all the substituents are the combination of δ-1 in [Table 4], the 2-indenyl ring part R 5 the substituents are γ-2 in [Table 3], and the crosslinked part is the combination of ε-6 in [Table 5], and MXn of the metal part is Ti(1,3-pentadienyl), the compound represented by the following formula [7] is exemplified.

[0078]

Chemical formula

[0079] Further, the transition metal compound [A] has no plane of symmetry in the 2-indenyl ring moiety, and the substituents R of the bridging moiety 13 and R 14 If they are not the same, for example, there exist two types of structural isomers represented by the following general formula [8a] or [8b].

[0080]

Chemical formula

[0081] Purification, fractionation of these structural isomer mixtures, or selective production of structural isomers can be carried out by known methods, and the production method is not particularly limited. Known production methods include, in addition to those mentioned as the production method of the transition metal compound [A], the production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", JP-T-2011-502192, etc.

[0082] Within the range of the transition metal compound [A], the transition metal compound may be used alone, two or more thereof may be used in combination, a structural isomer mixture may be used, a structural isomer may be used alone, or two or more structural isomer mixtures may be used. As described above, according to the present invention, a high molecular weight olefin polymer can be produced with a narrow molecular weight distribution using only the transition metal compound [A] as the transition metal compound constituting the olefin polymerization catalyst. However, within a range where this effect is not impaired, one or more transition metal compounds different from the transition metal compound [A] may be used in combination as the transition metal compound. At this time, the transition metal compound [A] may be in any of the above-described modes.

[0083] 《Production Method of Transition Metal Compound [A]》 The transition metal compound [A] can be produced using a conventionally known method, and examples of typical synthetic routes are shown below, but the production method is not particularly limited. In the following [Formula 1] and [Formula 4], R1 ~R 8 , Q, M, X and n are as defined in the general formula [1] above.

[0084] The substituted indene compound as the starting material can be produced by known methods, and the production method is not particularly limited. Examples of known production methods include those disclosed in "Organometallics 1994, 13, 954.", "Organometallics 2006, 25, 1217.", JP-T-2006-509059, "Bioorg. Med. Chem. 2008, 16, 7399.", WO2009 / 080216, "Organometallics 2011, 30, 5744.", JP-T-2011-500800, "Organometallics 2012, 31, 4962.", "Chem. Eur. J. 2012, 18, 4174.", JP-A-2012-012307, JP-A-2012-121882, JP-A-2014-196319, JP-T-2014-513735, JP-A-2015-063495, JP-A-2016-501952, etc.

[0085] Among the substituted indene compounds, those unsubstituted at the 2-position can be brominated at the 2-position by the following known methods, and the production method is not particularly limited.

[0086] Among the substituted indene compounds, the 4-substituted indene compound can produce the corresponding coupling product by known methods such as the Suzuki-Miyaura coupling reaction using the following palladium catalyst, and the production method is not particularly limited.

[0087] [Chemical formula]

[0088] Similarly, there are indene compound 5-membered ring partial double bond position isomers, and a mixture of these isomers may also be used. In addition, various boronic acid esters, boroxines, and other boron compounds may be used instead of the boronic acid. The reaction mixture of the halogen compound, the metal reagent, and then the boron compound may be used without isolation and purification. A nickel catalyst or an iron catalyst may be used instead of the palladium catalyst. Examples of known production methods include, in addition to those described above, JP-A-2014-196274 and the like.

[0089] In the production of the coupling product, instead of the Suzuki-Miyaura coupling with a boron compound, a Negishi coupling with an organozinc reagent, a Mizoroki-Heck reaction with an alkene compound, a Hiyama coupling with an organosilicon compound, a Sonogashira-Hagiwara coupling with a terminal alkyne compound, a Migita-Kosugi-Stille coupling with an organotin compound, a Kumada-Tamao-Corriu coupling with an organomagnesium compound, a Buchwald-Hartwig coupling, a Goldberg amination reaction, or a Ullmann ether synthesis reaction may be used. Examples of known production methods include, in addition to those described above, JP-A-8-183814, JP-T-2005-529865, JP-T-2006-509046, and the like.

[0090] The transition metal compound [A] and the precursor compound (ligand) can be produced by a known method using various substituted indene compounds produced by the above methods and the like. When Q is a silicon atom, a germanium atom, or a tin atom, it can be produced by the following methods, and the production method is not particularly limited.

[0091]

Chemical formula

[0092] In the above [Formula 4], in the synthesis of the precursor compound (ligand), the organomagnesium reagent prepared from the 2-brominated substituted indene compound and the organolithium reagent prepared from 1,2,3,4-tetramethyl-1,3-cyclopentadiene preferably react with the chloride containing Q step by step, and the order may be either. After the reaction with the organometallic reagent in the first step, the by-produced inorganic compound may be removed under an inert atmosphere, or the reaction product may be isolated by operations such as distillation, crystallization or washing and then used. When reacting with the organometallic reagent in the second step, it is preferable to add 0.1 to 5.0 equivalents of DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropyleneurea) or HMPA (hexamethylphosphoric triamide) etc. to the organometallic reagent, more preferably DMI, and it is 1.0 to 2.0 equivalents. In addition, although there are indenyl compound 5-membered ring partial double bond position isomers in the substituted indene compound and the precursor compound (ligand), a mixture of these isomers may be used.

[0093] As known production methods of the transition metal compound [A] and the precursor compound (ligand), for example, in addition to those shown above, WO2018-185176 can be mentioned.

[0094] [Catalyst for olefin polymerization] The olefin polymerization catalyst of the present invention contains the transition metal compound [A] of the present invention. Typical examples of the olefin polymerization catalyst of the present invention include ethylene polymerization catalysts.

[0095] (Compound [B]) The olefin polymerization catalyst of the present invention is [B-1] an organometallic compound (hereinafter, also referred to as "component (B-1)"), [B-2] an organoaluminum oxy compound (hereinafter, also referred to as "component (B-2)"), and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair (hereinafter, also referred to as "component (B-3)") Preferably contains at least one compound [B] selected from the group consisting of (hereinafter also referred to as "component (B)").

[0096] Examples of the organometallic compound [B-1] include organometallic compounds represented by the following general formulas (B-1a), (B-1b), or (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 represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 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 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 represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, M b is selected from Mg, Zn, and Cd, X represents a halogen atom, r is a number where 0 < r ≦ 2, s is a number where 0 ≦ s ≦ 1, t is a number where 0 ≦ t ≦ 1, and r + s + t = 2.〕

[0097] As the organometallic compound [B-1], the compounds disclosed in Japanese Patent Application Laid-Open No. 11-315109 by the present applicant and EP0874005A can be used without limitation.

[0098] As the organometallic compound [B-1], those represented by the general formula (B-1a) are preferable. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri(2-ethylhexyl)aluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, diisobutylaluminum ethoxide, etc. may be mentioned. These are used singly or in combination of two or more.

[0099] As the organoaluminum oxy compound [B-2], an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such an organoaluminum oxy compound is used singly or in combination of two or more.

[0100] As the compound [B-3] that reacts with the transition metal compound [A] to form an ion pair, Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Patent No. 5321106, etc., and furthermore, heteropoly compounds and isopoly compounds can be used without limitation.

[0101] In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound [B-2] such as methylaluminoxane is used in combination as a cocatalyst component, it not only exhibits very high catalytic activity with respect to olefins such as ethylene, but also reacts with active hydrogen in the solid carrier to easily prepare a solid carrier component containing the cocatalyst component. Therefore, it is preferable to use the organoaluminum oxy compound [B-2] as the component (B).

[0102] (Solid support [S]) The olefin polymerization catalyst of the present invention preferably contains a solid carrier [S] (hereinafter also referred to as "carrier [S]" or "component (S)"). The solid carrier [S] is an inorganic compound or an organic compound and is a granular or particulate solid. As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound is preferable.

[0103] Specific examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures containing these. Additionally, for example, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be used. Among these, those with SiO2 and / or Al2O3 as the main component are preferred as the porous oxide. The porous oxide may contain a small amount of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, etc.

[0104] Although the properties of the porous oxide vary depending on the type and manufacturing method, the porous oxide used in the present invention typically has a cumulative 50% particle size in the volume distribution measured by the laser light diffraction scattering method of 10 to 300 μm, preferably 20 to 200 μm, more preferably 40 to 150 μm, still more preferably 50 to 100 μm, and particularly preferably 60 to 80 μm. Its specific surface area is usually in the range of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, more preferably 200 to 600 m 2 / g, still more preferably 250 to 500 m 2 / g, and particularly preferably 300 to 400 m 2 / g. The pore volume is usually in the range of 0.3 to 3.0 cm 3 / g, preferably 0.5 to 2.5 cm 3 / g, more preferably 0.8 to 2.0 cm 3 / g, still more preferably 1.0 to 1.7 cm 3 / g, and particularly preferably 1.2 to 1.4 cm 3 / g. Such a porous oxide is calcined at 100 to 1000 °C, preferably 150 to 700 °C, more preferably 200 to 500 °C, and still more preferably 220 to 300 °C for use as needed.

[0105] Examples of the solid aluminoxane compound include at least one aluminoxane selected from aluminoxanes having a structure represented by the following general formula (S-a) or (S-b), and aluminoxanes having a structure composed of a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d).

[0106]

Chemical formula

[0107] In general formulas (S-a) to (S-d), R e is each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, ethylphenyl group, etc. Methyl group, ethyl group, and isobutyl group are preferred, and methyl group is particularly preferred. Also, a part of R e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R e . In (S-c) and (S-d), a straight line that is not connected to an atom on one side indicates a bond with another atom not shown in the figure.

[0108] In the general formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, particularly preferably 10 to 100. In the general formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s, and t are selected so that the aluminoxane can maintain a substantially solid state under the reaction environment in which it is used.

[0109] Unlike conventional carriers for olefin polymerization catalysts, the solid aluminoxane compound does not contain inorganic solid components such as silica and alumina, or organic polymer components such as polyethylene and polystyrene, but is solidified with an alkylaluminum compound as the main component. "Solid state" means that the aluminoxane component substantially maintains a solid state under the reaction environment in use. More specifically, as will be described later, when preparing an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) by contacting the transition metal compound [A] with the aluminoxane component, and when performing the polymerization (e.g., suspension polymerization) of an olefin (e.g., ethylene) using the prepared olefin polymerization catalyst, the aluminoxane component substantially maintains a solid state.

[0110] The simplest way to determine whether the aluminoxane component is in a solid state is by visual confirmation. However, for example, during polymerization, it is often difficult to confirm by visual inspection. In that case, it is possible to judge from, for example, the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the aluminoxane component elutes to some extent under the polymerization environment, it does not deviate from the gist of the present invention. Indicators for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of existence of amorphous polymers. From the viewpoint of quantitativeness, polymer bulk density is preferable. The bulk density is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0111] The dissolution ratio of the solid aluminoxane compound in n-hexane maintained at a temperature of 25 °C is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0112] The dissolution ratio is determined by adding 2 g of the solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution part using a G-4 glass filter, and measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of the aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

[0113] As the solid aluminoxane compound, known solid aluminoxanes can be used without limitation. For example, the solid polyaluminoxane composition described in International Publication No. 2014 / 123212 can also be used. Examples of known production methods include those described in Japanese Patent Publication No. 7-42301, Japanese Unexamined Patent Application Publication No. 6-220126, Japanese Unexamined Patent Application Publication No. 6-220128, Japanese Unexamined Patent Application Publication No. 11-140113, Japanese Unexamined Patent Application Publication No. 11-310607, Japanese Unexamined Patent Application Publication No. 2000-38410, Japanese Unexamined Patent Application Publication No. 2000-95810, International Publication No. 2010 / 55652, etc.

[0114] The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle sizes of 100 or more particles, and performing weight averaging. First, the particle size of each particle is obtained by sandwiching the particle image with two parallel lines in the horizontal and vertical directions respectively and measuring the length, and is calculated by the following formula. Particle size = ((horizontal length) 2 + (vertical length) 2 ) 0.5 Next, the weight average particle size of the solid aluminoxane compound is determined by the following formula using the particle size obtained above. Average particle size = Σnd 4 / Σnd 3 (n; number of particles, d; particle size)

[0115] The solid aluminoxane compound has a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 800 m 2 / g, and a pore volume of 0.1 to 2.5 cm 3 / g is desirable.

[0116] As the inorganic halide, MgCl2, MgBr2, MnCl2, MnBr2, etc. are used. The inorganic halide may be used as it is as obtained, or may be used after being pulverized by a ball mill or a vibration mill. Also, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate obtained by precipitating it into fine particles with a precipitating agent can also be used.

[0117] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked parallel to each other with a weak binding force, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Also, as these clays, clay minerals, and ion-exchangeable layered compounds, not limited to natural products, synthetic products can also be used.

[0118] Examples of the clay, clay mineral, or ion-exchangeable layered compound include ion-crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl2 type, CdI2 type, etc. Furthermore, examples of the clay and clay mineral include kaolin, bentonite, kibushi clay, gyrolite clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc.

[0119] Examples of the ion-exchangeable layered compound include crystalline acidic salts of polyvalent metals such as 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, and γ-Ti(NH4PO4)2·H2O.

[0120] Such clay, clay mineral, or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, for pores with a radius of 20 Å or more measured by the mercury intrusion method. Here, the pore volume is measured in the range of pore radii from 20 to 30000 Å by the mercury intrusion method using a mercury porosimeter. When a carrier having a pore volume of less than 0.1 cc / g for pores with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0121] It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any treatment such as surface treatment for removing impurities adhering to the surface and treatment affecting the crystal structure of the clay can be used. Specifically, examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. The alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and organic substance treatment, ion complexes, molecular complexes, organic derivatives, etc. can be formed to change the surface area and the interlayer distance.

[0122] The ion-exchangeable layered compound may be a layered compound in a state where the interlayer is expanded by utilizing ion-exchangeability and exchanging the exchangeable ions between the layers with another large and bulky ion. Such a bulky ion plays a role as a pillar supporting the layered structure and is usually called a pillar. Further, introducing another substance into the interlayer of the layered compound in this way is called intercalation. Examples of guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group or the like), 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ [Fe3O(OCOCH3)6] + and metal hydroxide ions such as these. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (where R represents a hydrocarbon group or the like), colloidal inorganic compounds such as SiO2, etc. can also coexist. Further, examples of the pillar also include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between the layers.

[0123] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as obtained, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Furthermore, it may be used alone or in combination of two or more. Among these, preferred ones are clay or clay minerals, and particularly preferred ones are montmorillonite, vermiculite, pecholite, teniolite, and synthetic mica.

[0124] ​​Examples of the organic compound that can be used as the carrier [S] include granular or particulate solids having a particle size in the range of 1 to 300 μm. Specifically, polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof can be exemplified.

[0125] <Usage and addition order of each component> The olefin polymerization catalyst according to the present invention can be prepared by mixing and contacting component (A), optionally component (S), and optionally component (B) in an inert hydrocarbon. As a method of contacting each component, paying attention to the order of contact, for example, (i) A method of contacting component (B) with component (A), (ii) A method of contacting component (S) with component (A), (iii) A method of contacting component (S) with component (B) and then contacting component (A), (iv) A method of contacting component (A) with component (B) and then contacting component (S), (v) A method of contacting component (S) with component (B) and then contacting a mixture of component (A) and component (B), (vi) A method of contacting component (S) with component (B), further contacting component (B), and then contacting a mixture of component (A) and component (B) and the like can be mentioned. When a plurality of types of component (B) are used, the component (B)s may be the same or different from each other. Among the above methods, (i), (ii), (iii), and (iv) are preferable.

[0126] In each of the methods showing the above contact order forms, in the step including the contact between component (S) and component (B) and the step including the contact between component (S) and component (A), by coexisting component (G), fouling during the polymerization reaction is suppressed or the particle properties of the produced polymer are improved. As component (G), a compound having a polar functional group can be used, and a nonionic surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, a polyalkylene oxide alkyl ether, an alkyldiethanolamine, a polyoxyalkylene alkylamine, a glycerin fatty acid ester, an N-acyl amino acid are more preferable. These may be used alone or in combination of two or more.

[0127] Examples of the solvent used for the preparation of the olefin polymerization catalyst according to the present invention include an inert hydrocarbon solvent. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof can be mentioned. Depending on the type of olefin to be polymerized, the olefin itself can also be used as a solvent.

[0128] In the contact of component (B) and component (S), they are chemically bonded by the reaction between the reaction sites in component (B) and the reaction sites in component (S), and a contact product of component (B) and component (S) is formed. The contact time between component (B) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200 °C, preferably -20 to 120 °C. If the initial contact between component (B) and component (S) is carried out abruptly, component (S) may disintegrate due to the exothermic reaction or reaction energy, deteriorating the morphology of the resulting solid catalyst component. When this is used in polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, at the initial stage of the contact between component (B) and component (S), for the purpose of suppressing the exothermic reaction, it is preferable to carry out the contact at a lower temperature, or to control the exothermic reaction and react at a rate that can maintain the initial contact temperature. The same applies when component (B) and component (S) are brought into contact and then component (B) is further brought into contact. The contact weight ratio of component (B) to component (S) (weight of component (B) / weight of component (S)) can be arbitrarily selected. However, the higher the contact weight ratio, the more component (A) can be brought into contact, and the catalytic activity per unit weight of the solid catalyst component can be improved.

[0129] The contact weight ratio of component (B) to component (S) [= weight of component (B) / weight of component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2.0. When the contact product of component (B) and component (S) is brought into contact with component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually within the range of -50 to 200 °C, preferably -50 to 100 °C.

[0130] Component (B-1) is used in an amount such that the molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) is usually 0.01 to 100,000, preferably 0.05 to 50,000. Component (B-2) is used in an amount such that the molar ratio [(B-2) / M] of component (B-2) (in terms of aluminum atoms) to all transition metal atoms (M) in component (A) is usually 10 to 500,000, preferably 20 to 100,000. Component (B-3) is used in an amount such that the molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) is usually 1 to 10, preferably 1 to 5. The ratio of component (B) to all transition metal atoms (M) in component (A) can be determined by inductively coupled plasma optical emission spectrometry (ICP spectrometry).

[0131] For olefin polymerization, the olefin polymerization catalyst according to the present invention can be used as it is, or it can also be used after prepolymerizing an olefin with this olefin polymerization catalyst to form a prepolymerized solid catalyst component. The prepolymerized solid catalyst component can usually be prepared by prepolymerizing an olefin (e.g., ethylene) in an inert hydrocarbon solvent in the presence of the olefin polymerization catalyst according to the present invention, and it can be carried out by any of batch, semi-continuous, and continuous methods, and can also be carried out under reduced pressure, normal pressure, or increased pressure. Furthermore, it is desirable that the prepolymerized solid catalyst component is produced in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid catalyst component by prepolymerization.

[0132] After separating the prepolymerized solid catalyst component formed in an inert hydrocarbon solvent from the suspension, it may be suspended again in an inert hydrocarbon, and an olefin (e.g., ethylene) may be introduced into the resulting suspension, or an olefin (e.g., ethylene) may be introduced after drying. The prepolymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the prepolymerization time is about 0.5 to 100 hours, preferably 1 to 50 hours. For prepolymerization, an olefin mainly composed of ethylene is preferably used.

[0133] As the form of the solid catalyst component used for prepolymerization, those already described can be used without limitation. Further, component (B) is used as necessary, and in particular, the organoaluminum compound [B-1a] represented by the general formula (B-1a) is preferably used. When component (B) is used, component (B) is used in an amount such that the molar ratio (Al / M) of the aluminum atom (Al) in component (B) to the transition metal atom (M) in the transition metal compound [A] is 0.1 to 10,000, preferably 0.5 to 5,000.

[0134] The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is usually 1 to 1,000 g / L, more preferably 10 to 500 g / L, in terms of the olefin polymerization catalyst / polymerization volume ratio. At the time of prepolymerization, the above-mentioned component (G) may coexist for the purpose of suppressing fouling or improving the particle properties. Further, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, suppressing the generation of heat spots and seating during polymerization, and suppressing the generation of polymer lumps, component (G) may be brought into contact with the prepolymerized solid catalyst component once generated by prepolymerization.

[0135] The temperature at the time of bringing the above-mentioned component (G) into contact is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. When bringing the olefin polymerization catalyst according to the present invention into contact with component (G), component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst according to the present invention.

[0136] The mixing contact between the olefin polymerization catalyst according to the present invention and component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same ones as described above. In the method for producing an olefin polymer according to the present invention, as the olefin polymerization catalyst, a preliminarily polymerized solid catalyst component that has been dried (hereinafter also referred to as "dried preliminarily polymerized catalyst") can be used. The drying of the preliminarily polymerized solid catalyst component is usually carried out after removing the hydrocarbon as the dispersion medium by filtration or the like from the suspension of the obtained preliminarily polymerized catalyst.

[0137] The drying of the preliminarily polymerized solid catalyst component is carried out by maintaining the preliminarily polymerized solid catalyst component at a temperature in the range of 70°C or lower, preferably 20 to 50°C, under the flow of an inert gas. The amount of volatile components of the obtained dried preliminarily polymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components of the dried preliminarily polymerized catalyst is preferably as small as possible. Although there is no particular lower limit, it is practically 0.001% by weight. The drying time is usually 1 to 48 hours, although it depends on the drying temperature.

[0138] Since the dried preliminarily polymerized catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dried preliminarily polymerized catalyst is used, it is not necessary to carry the solvent used in suspension in the gas-phase polymerization system, so that polymerization can be carried out stably.

[0139] [Method for producing olefin polymer] The method for producing an olefin polymer of the present invention is characterized by including a step of polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention. The step of polymerizing the olefin is preferably a step of homopolymerizing ethylene or a step of copolymerizing ethylene and an olefin having 3 to 20 carbon atoms.

[0140] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene polymer, the ethylene content in the ethylene polymer is preferably 70 mol% or more (assuming the total of monomer units is 100 mol%).

[0141] Examples of the polymerization method include liquid-phase polymerization methods such as solution polymerization and suspension polymerization, and gas-phase polymerization methods, and suspension polymerization method and gas-phase polymerization method are preferred. Specific 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; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; or mixtures thereof.

[0142] When polymerizing an olefin (e.g., ethylene) using the olefin polymerization catalyst according to the present invention, component (A) is usually used in an amount of 1×10 -12 ~1×10 -1 mol, preferably 1×10 -8 ~1×10 -2 mol per liter of the reaction volume. Further, component (B) is used, preferably a compound represented by the general formula (B-1a), or component (B-2) is used.

[0143] When polymerizing an olefin (e.g., ethylene), the lower limit of the polymerization temperature is usually 0°C, preferably 40°C, more preferably 60°C. A higher temperature is advantageous in terms of heat removal and the like in industrial-scale production. The upper limit is usually 200°C, preferably 170°C, and the polymerization pressure is usually atmospheric pressure to 100 kgf / cm 2 , preferably atmospheric pressure to 50 kgf / cm 2 . The polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Further, the polymerization can also be carried out in two or more stages with different reaction conditions.

[0144] The molecular weight of the olefin polymer obtained by the method for producing an olefin polymer according to the present invention can be adjusted by introducing hydrogen into the polymerization system or changing the polymerization temperature. During polymerization, the above-mentioned component (G) can be coexisted for the purpose of suppressing fouling or improving the particle properties.

[0145] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene polymer, the monomer supplied to the polymerization reaction is preferably ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of the olefin having 3 to 20 carbon atoms include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0146] Furthermore, a small amount of styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc. may be supplied as long as the effects of the present invention are not impaired.

[0147] Also, according to the method for producing an olefin polymer according to the present invention, an olefin polymer having a high molecular weight can be produced with a narrow molecular weight distribution. Due to the steric hindrance of the substituents R 2 ~R 5 on the 2-indenyl ring in the transition metal compound [A], the chain transfer reaction of the growing polymer chain is suppressed, so it is considered that the polymer has a higher molecular weight. In addition, the transition metal compound [A] has a symmetric structure of tetramethylcyclopentadiene and has fewer isomers than a silyl-bridged (2-indenyl)(1-indenyl) type compound. That is, since there are fewer active species of the catalyst, it is considered that the molecular weight distribution of the obtained polymer becomes narrower.

[0148] [Olefin polymer] The olefin polymer (e.g., ethylene polymer) produced by the method for producing an olefin polymer according to the present invention preferably satisfies the following requirements (1) to (7). (1) The melt flow rate (MFR) at 2.16 kg load at 190 °C is usually 0.01 g / 10 min or more and 30 g / 10 min or less, preferably 0.01 g / 10 min or more and 10 g / 10 min or less, more preferably 0.01 g / 10 min or more and 5 g / 10 min or less, still more preferably 0.01 g / 10 min or more and 1 g / 10 min or less, and particularly preferably 0.02 g / 10 min or more and 0.5 g / 10 min or less. (2) The density is usually 875 kg / m 3 or more and 965 kg / m 3 or less, preferably 885 kg / m 3 or more and 945 kg / m 3 or less, more preferably 900 kg / m 3 or more and 945 kg / m 3 or less, still more preferably 915 kg / m 3 or more and 945 kg / m 3 or less, and particularly preferably 930 kg / m 3 or more and 940 kg / m 3 or less. (3) Mn is usually 10,000 or more and 40,000 or less, preferably 12,000 or more and 36,000 or less, more preferably 14,000 or more and 33,000 or less, still more preferably 16,000 or more and 32,000 or less, and particularly preferably 18,000 or more and 30,000 or less. (4) Mw is usually 50,000 to 150,000, preferably 60,000 to 140,000, more preferably 70,000 to 135,000, still more preferably 75,000 to 130,000, and particularly preferably 80,000 to 125,000. (5) Mz is usually 200,000 to 400,000, preferably 210,000 to 390,000, more preferably 220,000 to 380,000, still more preferably 225,000 to 375,000, and particularly 230,000 to 370,000. (6) Mw / Mn is usually 5.0 or less, preferably 4.8 or less, more preferably 4.7 or less, still more preferably 4.6 or less, and particularly preferably 4.5 or less. (7) Mz / Mw is usually 4.0 or less, preferably 3.8 or less, more preferably 3.6 or less, and still more preferably 3.4 or less.

[0149] The value of the melt flow rate (MFR) strongly depends on the molecular weight. The smaller the MFR, the larger the molecular weight, and the larger the MFR, the smaller the molecular weight. Also, for example, it is known that the molecular weight of an ethylene-based polymer is determined by the composition ratio of hydrogen to ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga et al., "Catalytic Olefin Polymerization", Kodansha Scientific, 1990, p. 376). Therefore, it is possible to increase or decrease the MFR of the ethylene-based polymer by increasing or decreasing the hydrogen / ethylene ratio.

[0150] The value of the density depends on the α-olefin content of the ethylene-based polymer. The lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Also, for example, it is known that the α-olefin content in an ethylene-based polymer is determined by the composition ratio of α-olefin to ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p. 606 (1992)). Therefore, it is possible to produce an ethylene-based polymer having a density within the above range by increasing or decreasing the α-olefin / ethylene ratio.

[0151] Mn represents the number average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO), Mw represents the weight average molecular weight measured by GPC-VISCO, and Mz represents the Z average molecular weight measured by GPC-VISCO.

[0152] The olefin-based polymer (e.g., ethylene-based polymer) produced by the present invention may be pelletized.

[0153] The olefin-based polymer (e.g., ethylene-based polymer) produced according to the present invention may be blended with additives such as a weathering stabilizer, a heat stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an anti-fogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant, as long as the object of the present invention is not impaired.

[0154] The olefin-based polymer (e.g., ethylene-based polymer) produced according to the present invention can be processed by general film forming, blow molding, injection molding, and extrusion molding. Examples of the molded article obtained by processing the olefin-based polymer (e.g., ethylene-based polymer) produced according to the present invention include films, blow infusion bags, blow bottles, gasoline tanks, tubes by extrusion molding, pipes, tear-off caps, injection molded articles such as daily sundries, fibers, and large molded articles by rotational molding.

[0155] The film obtained by processing the olefin-based polymer (e.g., ethylene-based polymer) produced according to the present invention is suitable for various packaging films such as water product packaging bags, liquid soup packaging bags, liquid paper containers, laminate base materials, special-shaped liquid packaging bags (such as standing pouches), standard bags, heavy bags, wrap films, sugar bags, oil product packaging bags, and food packaging, protective films, infusion bags, and agricultural materials. It can also be laminated with a base material such as nylon or polyester and used as a multilayer film.

Examples

[0156] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0157] [Measurement of various physical properties] The method for measuring the physical properties of the olefin-based polymer is shown below. <Melt Flow Rate (MFR)> The melt flow rate was measured under the conditions of 190°C and a load of 2.16 kg.

[0158] <Density (D)> The strand obtained during the MFR measurement was heat-treated at 100 °C for 30 minutes, and after leaving it to stand at room temperature for 1 hour, it was measured by the density gradient tube method.

[0159] <Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)> Using an Agilent GPC-viscosity detector (GPC-VISCO) PL-GPC220, the measurement was carried out as follows. Two Agilent PLgel Olexis were used as analytical columns, a differential refractometer and a 3-capillary viscometer were used as detectors, the column temperature was 145 °C, o-dichlorobenzene was used as the mobile phase, the flow rate was 1.0 ml / min, and the sample concentration was 0.1 wt%. Standard polystyrene manufactured by Tosoh Corporation was used. For molecular weight calculation, the measured viscosity was calculated from the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz / Mw) were determined from the measured universal calibration.

[0160] <Synthesis of transition metal compound [A]> [Synthesis Example 1-1] Into a 200 mL reactor that had been sufficiently dried and purged with argon, 15.2 g (78.8 mmol) of 7-phenyl 1-H indene obtained by the method described in "Special Table 2019-515997", 130 mL of dimethyl sulfoxide, and 3.13 g of water were added, cooled to 0 °C, N-bromosuccinimide was gradually added, and the mixture was stirred at room temperature for 1 hour. Then, it was cooled to 0 °C, water was added, and the soluble component was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled off, and the resulting residue was purified by silica gel column chromatography to obtain 9.12 g (yield 43%) of the target product represented by the following formula (A-1a) (hereinafter referred to as "compound (A-1a)"). 11H NMR (270 MHz, CDCl3) δ 7.49 - 7.19 (8H, m, Ar-H), 7.10 - 6.98 (1H, d, C=CH-C), 3.68 (2H, s, C-CH2-C) ppm

[0161]

Chem.

[0162] 〔Synthesis Example 1 - 2〕 0.76 g (31.1 mmol) of magnesium pieces were charged into a thoroughly dried and argon-substituted 200 mL reactor, and it was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A 20 mL diluted solution of the compound (A-1a) (4.21 g, 15.5 mmol) obtained in Synthesis Example 1-1 in tetrahydrofuran was added dropwise (after adding 1.0 mL, heated to reflux until the color of iodine disappeared with a dryer, and the remaining solution was added dropwise after the reaction started), and after completion of the dropwise addition, it was heated to reflux at 80 °C for 1 hour. This reaction solution was slowly added to a 15 mL diluted solution of 9.32 mL (77.6 mmol) of dimethylsilyl dichloride in n-hexane while cooling to -78 °C, and stirring was continued for 18 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 15 mL of tetrahydrofuran and 2.01 mL (18.6 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain Solution 1a. 2.33 g (19.1 mmol) of 1,2,3,4-tetramethyl-1,3-cyclopentadiene and 15 mL of tetrahydrofuran were charged into a thoroughly dried and argon-substituted 100 mL reactor, 12.8 mL of n-butyllithium solution (hexane solution, 1.56 M, 20.0 mmol) was added, and it was stirred at room temperature for 2 hours to obtain Solution 1b. This solution 1b was added dropwise to the solution 1a cooled to -78 °C, and stirring was continued for 15 hours while slowly returning to room temperature. An aqueous saturated ammonium chloride solution was added, the soluble components were extracted with ethyl acetate, the resulting fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was evaporated to dryness, and the residue obtained was purified by reverse-phase silica gel column chromatography to obtain 1.35 g (yield 23%) of the target product (hereinafter referred to as "compound (A-1L)") as a mixture of isomers represented by the following formula (A-1L). 1 H NMR (270 MHz, CDCl3) δ 7.56 - 7.11 (9H, m, Ar-H), 3.53 - 3.45 (2H, m, C-CH2-C), 3.01 (1H, s, Si-CH), 1.85 (6H, s, C-CH3), 1.78 (6H, s, C-CH3), 0.15 - 0.14 (6H, d, Si-CH3) ppm

[0163] [Chemical formula]

[0164] [Example 1A] 1.38 g (3.7 mmol) of the compound (A-1L) obtained in Synthesis Example 1-2, 37 mL of toluene, and 0.60 mL of tetrahydrofuran were charged into a thoroughly dried and argon-purged 100 mL reactor and stirred. To this solution, 4.67 mL (hexane solution, 1.59 M, 7.4 mmol) of an n-butyllithium solution was added at room temperature, and then stirring was continued in an oil bath at 40 °C for 3 hours. This solution was cooled to 0 °C, 0.87 g (3.7 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After evaporating the solvent of the reaction solution, dichloromethane was added to the resulting solid to prepare a suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the resulting solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and dried under reduced pressure to obtain 0.53 g (yield 27%) of a yellow powdery compound (hereinafter referred to as "compound (A-1)") represented by the following formula (A-1). 11H NMR (270 MHz, CDCl3) δ 7.73 - 7.71 (1H, m, Ar - H), 7.62 - 7.60 (2H, m, Ar - H), 7.46 - 7.26 (5H, m, Ar - H), 6.09 - 6.04 (2H, dd, Cp - H), 2.03 - 1.95 (12H, m, C - CH3), 0.91 (3H, s, Si - CH3), 0.90 (3H, s, Si - CH3) ppm FD - mass spectrometry (M + ): 530

[0165]

Chem.

[0166] 〔Synthesis Example 2 - 1〕 19.35 g (0.12 mol) of 3 - (2 - methylphenyl)propionic acid and 101.76 g (0.68 mol) of trifluoromethanesulfonic acid were charged into a 200 mL reactor that had been thoroughly dried and purged with argon, and the mixture was stirred at room temperature for 2.5 hours. The reaction solution was cooled to 0 °C, 100 mL of water was added, and the soluble components were extracted with methylene chloride. The obtained fraction was dried over sodium sulfate. After filtering off the sodium sulfate, the filtrate was evaporated to dryness, and the resulting residue was recrystallized from a system of methylene chloride and hexane. The precipitated crystals were collected by filtration. The filtrate was purified by silica gel column chromatography and combined with the crystal fraction to obtain 15.34 g (yield 88%) of the target product represented by the following formula (A - 2a) (hereinafter referred to as "Compound (A - 2a)"). 1 1H NMR (270 MHz, CDCl3) δ 7.62 - 7.30 (3H, m, Ar - H), 3.04 - 3.02 (2H, m, O = C - CH2 - C), 2.72 - 2.69 (2H, m, C - CH2 - C), 2.37 (3H, s, - CH3) ppm

[0167]

Chem.

[0168] 〔Synthesis Example 2 - 2〕 The target compound represented by the following formula (A-2b) (hereinafter referred to as "compound (A-2b)") was synthesized by the method described in Chem. Eur. J. 2017, 23, 13037-13041. 1 H NMR (270 MHz, CDCl3) δ 7.27 - 7.00 (3H, m, Ar-H), 6.90 - 6.88 (1H, m, C=CH-C), 6.58 - 6.55 (1H, m, C=CH-C), 3.30 - 3.29 (2H, m, C-CH2-C), 2.38 (3H, s, -CH3) ppm

[0169]

Chemical formula

[0170] 〔Synthesis Example 2-3〕 To a sufficiently dried and argon-substituted 500 mL reactor, 9.10 g (69.9 mmol) of the compound (A-2b) obtained in Synthesis Example 2-2, 115 mL of dimethyl sulfoxide, and 2.80 mL of distilled water were added. After cooling to 0 °C, 14.95 g (84.0 mmol) of N-bromosuccinimide was added little by little, and the temperature was raised to room temperature and then stirred for 2 hours. After cooling the reaction solution to 0 °C, distilled water was added, and the soluble components were extracted with ethyl acetate. The obtained fraction was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over sodium sulfate. After filtering off the sodium sulfate, the filtrate was evaporated to obtain a residue. To a sufficiently dried and argon-substituted 500 mL reactor, the obtained residue, 2.65 g (13.9 mmol) of p-toluenesulfonic acid monohydrate, and 165 mL of toluene were added, and the mixture was heated to reflux at 130 °C for 4 hours. Distilled water was added to the reaction solution, and the soluble components were extracted with ethyl acetate. The obtained fraction was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over sodium sulfate. After filtering off the sodium sulfate, the filtrate was evaporated, and the obtained residue was purified by silica gel column chromatography to obtain 9.7 g (yield 66%) of the target compound represented by the following formula (A-2c) (hereinafter referred to as "compound (A-2c)"). 11H NMR (270 MHz, CDCl3) δ 7.19 - 6.93 (4H, m, Ar-H), 3.50 (2H, s, C-CH2-C), 2.33 (3H, s, -CH3) ppm

[0171]

Chem.

[0172] [Synthesis Example 2-4] A 200 mL reactor that was thoroughly dried and purged with argon was charged with 0.74 g (30.3 mmol) of magnesium chips, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A 15 mL diluted solution of 3.13 g (15.0 mmol) of the compound (A-2c) obtained in Synthesis Example 2-3 in tetrahydrofuran was added dropwise (after adding 1.0 mL, heated to reflux with a dryer until the color of iodine disappeared, and the remaining solution was added dropwise after the reaction started), and after completion of the dropwise addition, heated to reflux at 80 °C for 1 hour. This reaction solution was slowly added to a 15 mL diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in n-hexane while cooling to -78 °C, and stirring was continued for 18 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 15 mL of tetrahydrofuran and 3.90 mL (36.2 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain Solution 2a. A 100 mL reactor that was thoroughly dried and purged with argon was charged with 2.22 g (18.2 mmol) of 1,2,3,4-tetramethyl-1,3-cyclopentadiene and 15 mL of tetrahydrofuran, 12.5 mL of an n-butyllithium solution (hexane solution, 1.56 M, 19.5 mmol) was added, and stirred at room temperature for 2 hours to obtain Solution 2b. This solution 2b was added dropwise to solution 2a cooled to -78 °C, and stirring was continued for 15 hours while slowly returning to room temperature. An aqueous saturated ammonium chloride solution was added, the soluble components were extracted with ethyl acetate, the resulting fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was evaporated to give a residue which was purified by reverse-phase silica gel column chromatography to give 1.89 g (41% yield) of the target product (hereinafter referred to as "Compound (A-2L)") as a mixture of isomers represented by the following formula (A-2L). 1 H NMR (270 MHz, CDCl3) δ 7.41 - 6.99 (4H, m, Ar-H), 3.48 - 3.29 (2H, m, C-CH2-C), 3.04 (1H, s, Si-CH), 2.47 - 2.36 (3H, m, Ind-CH3), 1.85 - 1.79 (12H, d, -CH3), 0.47 - 0.45 (6H, m, Si-CH3) ppm

[0173] [Chemical formula]

[0174] [Example 2A] 1.02 g (3.3 mmol) of the compound (A-2L) obtained in Synthesis Example 2-4, 33 mL of toluene, and 0.53 mL of tetrahydrofuran were charged into a thoroughly dried and argon-purged 100 mL reactor and stirred. To this solution, 4.20 mL (hexane solution, 1.59 M, 6.7 mmol) of n-butyllithium solution was added at room temperature, and stirring was continued in an oil bath at 40 °C for 3 hours. This solution was cooled to 0 °C, 0.79 g (3.4 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After evaporating the solvent of the reaction solution, dichloromethane was added to the resulting solid to prepare a suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the resulting solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.42 g (27% yield) of a yellow powdery compound (hereinafter referred to as "Compound (A-2)") represented by the following formula (A-2). 1 1H NMR (270 MHz, CDCl3) δ 7.53 - 7.51 (1H, d, Ar - H), 7.23 - 7.19 (1H, m, Ar - H), 7.07 - 7.05 (1H, d, Ar - H), 5.94 - 5.89 (2H, m, Ind - H), 2.47 (3H, s, Ar - CH3), 2.06 - 2.00 (12H, m, Cp - CH3), 0.94 (3H, s, Si - CH3), 0.91 (3H, s, Si - CH3) ppm FD - mass spectrometry (M + ): 468

[0175]

Chem.

[0176] [Comparative Example 1A] A yellow powdery compound represented by the following formula (A'-1) (hereinafter referred to as "compound (A'-1)") was synthesized by the method described in WO2018 - 185176.

[0177]

Chem.

[0178] [Comparative Example 2A] A yellow powdery compound represented by the following formula (A'-2) (hereinafter referred to as "compound (A'-2)") was synthesized by the method described in JP - A 2020 - 050614.

[0179]

Chem.

[0180] [Synthesis Example 3 - 1] In a 200 mL reactor that had been thoroughly dried and purged with argon, 0.74 g (30.3 mmol) of magnesium chips were charged, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A 20 mL diluted solution of 3.53 g (15.0 mmol) of 6-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method of Example 5 of JP-A-2001-253895 in tetrahydrofuran was added dropwise (after adding 1.0 mL, heated to reflux with a dryer until the color of iodine disappeared, and the remaining solution was added dropwise after the reaction started). After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a 15 mL diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in n-hexane while cooling at -78°C, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.62 mL (15.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain Solution 3a. In a 100 mL reactor that had been thoroughly dried and purged with argon, 2.22 g (18.2 mmol) of 1,2,3,4-tetramethyl-1,3-cyclopentadiene and 15 mL of tetrahydrofuran were charged, 12.5 mL of an n-butyllithium solution (hexane solution, 1.56 M, 19.5 mmol) was added, and the mixture was stirred at room temperature for 2 hours to obtain Solution 3b. This Solution 3b was added dropwise to Solution 3a cooled to -78°C, and stirring was continued for 15 hours while slowly returning to room temperature. An aqueous saturated ammonium chloride solution was added, the soluble components were extracted with ethyl acetate, the obtained fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled off and the resulting residue was purified by alumina column chromatography and further purified by distillation to remove impurities, whereby 1.34 g (yield 27%) of the target product represented by the following formula (A-3L) (hereinafter referred to as "Compound (A-3L)") was obtained as a mixture of isomers. 11H NMR (270 MHz, CDCl3) δ 7.33 - 7.00 (3H, m, Ar-H), 3.35 - 3.34 (2H, m, C-CH2-C), 3.01 (1H, s, Si-CH), 2.94 - 2.90 (4H, t, Ar-CH2-CH2), 2.14 - 2.07 (2H, m, CH2-CH2-CH2), 1.92 - 1.78 (12H, d, -CH3), 0.13 - 0.12 (6H, s, Si-CH3) ppm

[0181]

Chem.

[0182] [Example 3A] 1.34 g (3.3 mmol) of the compound (A-3L) obtained in Synthesis Example 3-1, 33 mL of toluene, and 0.53 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and purged with argon, and the mixture was stirred. To this solution, 4.20 mL (hexane solution, 1.59 M, 6.7 mmol) of an n-butyllithium solution was added at room temperature, and then stirring was continued in an oil bath at 40 °C for 3 hours. The solution was cooled to 0 °C, 0.79 g (3.4 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.70 g (yield 70%) of a yellow powdery compound represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)"). 1 1H NMR (270 MHz, CDCl3) δ 7.42 (2H, s, Ar-H), 5.82 (2H, s, Ind-H), 3.07 - 2.88 (4H, m, Ar-CH2-CH2), 2.13 - 2.01 (2H, m, CH2-CH2-CH2), 2.04 (6H, s, Cp-CH3), 1.98 (6H, s, Cp-CH3), 0.87 (6H, s, Si-CH3) ppm FD-mass spectrometry (M + ): 494

[0183]

Chem.

[0184] [Example 1] <Preparation of Solid Catalyst Component (X-1)> Using a reactor with a stirrer and an internal volume of 270 L, under a nitrogen atmosphere, as the solid support [S], silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative volume distribution of particle size by laser light diffraction scattering method: 50% particle size: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3 cm 3 / g, dried at 250 °C for 10 hours, hereinafter referred to as solid support [S-1].) 10 kg was suspended in 77 L of toluene and then cooled to 0 - 5 °C. To this suspension, 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) as component (B) was added dropwise over 30 minutes. At this time, the temperature inside the system was maintained at 0 - 5 °C. Next, after contacting these at 0 - 5 °C for 30 minutes, the temperature inside the system was raised to 95 °C over 1.5 hours and then continuously contacted at 95 °C for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant was removed by decantation, and further washed twice with toluene to prepare a toluene slurry with a total volume of 115 L. When a part of the obtained slurry was sampled and analyzed, the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L. Next, 30 mL of toluene and 1.63 mL (solid content weight: 0.2 g) of the slurry obtained above were charged into a reactor with a stirrer and an internal volume of 200 mL that had been sufficiently purged with nitrogen, under a nitrogen atmosphere. Next, 5.0 μmol of the toluene solution of compound (A-1) obtained in Example 1A was added as Zr, and these were contacted at a temperature of 20 - 25 °C for 1 hour. Then, the supernatant was removed by decantation, and further washed twice with hexane. Thereby, a slurry of solid catalyst component (X-1) with a total volume of 40 mL was prepared.

[0185] <Production of Olefin Polymer> Into a 1 L SUS autoclave with a sufficient nitrogen substitution, 500 mL of heptane was added under a nitrogen atmosphere. After that, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-1) in a slurry state were charged as the solid content. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 147.6 g of an ethylene-based polymer. The catalyst activity was 4,920 g-PE / g-solid catalyst component. The physical properties of the obtained ethylene-based polymer are shown in Table 6.

[0186] [Example 2] <Preparation of Solid Catalyst Component (X-2)> In Example 1, a slurry of the solid catalyst component (X-2) was prepared in the same manner as in Example 1, except that the compound (A-2) obtained in Example 2A was used instead of the compound (A-1).

[0187] <Production of Olefin-Based Polymer> Into a 1 L SUS autoclave with a sufficient nitrogen substitution, 500 mL of heptane was added under a nitrogen atmosphere. After that, ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-2) in a slurry state were charged as the solid content. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 199.4 g of an ethylene-based polymer. The catalyst activity was 6,650 g-PE / g-solid catalyst component. The physical properties of the obtained ethylene-based polymer are shown in Table 6.

[0188] [Comparative Example 1] <Preparation of Solid Catalyst Component (X-3)> In Example 1, a slurry of the solid catalyst component (X-3) was prepared in the same manner as in Example 1, except that the compound (A'-1) obtained in Comparative Example 1A was used instead of the compound (A-1).

[0189] <Production of Olefin Polymer> After adding 500 mL of heptane to a 1 L SUS autoclave with a sufficiently nitrogen-substituted internal volume under a nitrogen atmosphere, ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-3) in a slurry state were charged as the solid content. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 208.4 g of an ethylene-based polymer. The catalyst activity was 6,950 g-PE / g-solid catalyst component. The physical properties of the obtained ethylene-based polymer are shown in Table 6.

[0190] [Comparative Example 2] <Preparation of Solid Catalyst Component (X-4)> In Example 1, a slurry of the solid catalyst component (X-4) was prepared in the same manner as in Example 1, except that the compound (A'-2) obtained in Comparative Example 1A was used instead of the compound (A-1).

[0191] <Production of Olefin Polymer> After adding 500 mL of heptane to a 1 L SUS autoclave with a sufficiently nitrogen-substituted internal volume under a nitrogen atmosphere, ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-4) in a slurry state were charged as the solid content. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 80.0 g of an ethylene-based polymer. The catalyst activity was 2,670 g-PE / g-solid catalyst component. The physical properties of the obtained ethylene-based polymer are shown in Table 6.

[0192] [Example 3] <Preparation of Solid Catalyst Component (X-5)> In Example 1, a slurry of the solid catalyst component (X-5) was prepared in the same manner as in Example 1, except that the compound (A-3) obtained in Example 3A was used instead of the compound (A-1).

[0193] <Production of Olefin Polymer> 500 mL of heptane was added to a 1 L SUS autoclave with sufficient nitrogen substitution under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-5) in slurry form as a solid content were charged. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 76.5 g of an ethylene-based polymer. The catalyst activity was 7,650 g-PE / g-solid catalyst component. The physical properties of the obtained ethylene-based polymer are shown in Table 6.

[0194]

Table 6

[0195] In Examples 1 and 2 using the transition metal compound [A] of the present invention (a silyl-bridged (2-indenyl)(2,3,4,5-tetramethylcyclopentadienyl) type compound having a specific substituent on the 2-indenyl ring), compared with Comparative Example 1 using a silyl-bridged (2-indenyl)(2,3,4,5-tetramethylcyclopentadienyl) type compound having no such substituent and Comparative Example 2 using a silyl-bridged (2-indenyl)(1-indenyl) type compound, the number average molecular weight Mn of the obtained polymer increased and the molecular weight distribution became narrower.

Claims

1. A transition metal compound [A] represented by the following general formula [1]: 【Chemistry 1】 (In the general formula [1], M is a transition metal atom of Group 4 of the periodic table, n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, the anionic ligand being a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and when n is 2 or more, a plurality of groups represented by X may be the same or different and may be bonded to each other to form a ring; Q is an atom of Group 14 of the periodic table; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, R 2 , R 3 , R 4 , R 5 at least one of the groups is a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group; R 2 ~R 5 Adjacent substituents among these may be bonded to each other to form a ring which may have a substituent, R 7 and R 8 may be bonded to each other to form a ring containing Q, and this ring may have a substituent.

2. In the general formula [1], M is a zirconium atom or a hafnium atom; X's each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group; Q is a carbon atom or a silicon atom; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms.

3. In the general formula [1], Q is a silicon atom; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.

4. In the general formula [1], R 1 and R 6 The transition metal compound [A] according to claim 3, wherein is a hydrogen atom.

5. In the general formula [1], R 2 , R 3 , R 4 , R 5 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

6. In the general formula [1], R 3 and R 4 The transition metal compound [A] according to claim 5 , wherein:

7. An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 6.

8. [B-1] Organometallic compound, [B-2] an organoaluminum oxy compound, and [B-3] A compound that reacts with the transition metal compound [A] to form an ion pair The olefin polymerization catalyst according to claim 7, further comprising at least one compound [B] selected from the group consisting of:

9. A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7.

10. The method for producing an olefin polymer according to claim 9, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.

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