JP7514092B2 - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

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

Olefin polymers are molded by various molding methods and are used in a wide range of applications. For example, extrusions of ethylene polymers are used for films or sheets used in packaging food, liquids, daily necessities, etc. The properties required of olefin polymers vary depending on the molding method or application, but for example, when performing T-die molding, they are required to have processing performance such as stable molding even at high speeds (high-speed film-forming processability) and small neck-in.

Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branching structure, which gives it high melt tension and good moldability, such as small neck-in, and it is used in a variety of applications. However, the mechanical strength of the molded product, such as tensile strength, tear strength, and impact strength, is low, and problems remain, such as poor high-speed film formation processability in T-die molding.

On the other hand, ethylene polymers produced using Ziegler or metallocene catalysts, in contrast to LDPE, have high tensile strength, tear strength, and impact strength due to their molecular structure, and are therefore used in applications where mechanical strength is required, but have problems such as low melt tension and poor moldability.

To solve these problems, methods have been proposed for producing ethylene polymers having long chain branches in the presence of a solid catalyst component consisting of two types of transition metal compounds and a solid support (Patent Documents 1 and 2, etc.).

Recently, a technique has been reported for producing an ethylene-based polymer with many long-chain branches with high catalytic activity using only one type of bridged (2-indenyl)(1-indenyl) transition metal compound (Patent Documents 3, 4, 5, etc.). Specifically, for example, Patent Document 4 describes that ethylene and 1-hexene were copolymerized in the presence of dimethylsilylene(2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indenyl)zirconium dichloride, and an ethylene-based polymer with many long-chain branches was produced with high catalytic activity.

JP 2006-233208 A JP 2009-144148 A JP 2019-59933 A JP 2019-59723 A JP 2019-59724 A

When olefin-based polymers, such as ethylene-based polymers, are used in applications requiring high strength, such as pipes, it is desirable for the olefin-based polymers to have a high molecular weight. However, the techniques reported in Patent Documents 3 to 5 and the like leave room for further improvement in terms of increasing the molecular weight of the olefin-based polymers produced.

The present invention aims to provide a transition metal compound, an olefin polymerization catalyst, and a method for producing an olefin polymer, which can produce an olefin polymer, such as an ethylene polymer, having a large amount of long chain branching and a high molecular weight.

The inventors conducted extensive research to solve the above problems, and discovered that the above problems can be solved by introducing a substituent into a specific position of the 2-indenyl ring of a bridged (2-indenyl)(1-indenyl) transition metal compound, thus completing the present invention.

The gist of the present invention is as follows.
[1]
A transition metal compound [A] represented by the following general formula [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 ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R 14 , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent 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 ^;
R3 and ^R4 each independently represent 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;
Adjacent substituents among R ¹ to R ⁶ may be bonded to each other to form a ring which may have a substituent;
Adjacent substituents among ^R to ^R may be bonded to each other to form a ring which may have a substituent,
Adjacent substituents among R ¹² to R ¹⁶ may be bonded to each other to form a ring which may have a substituent;
R ⁹ and R ¹² or R ¹⁶ may be bonded to each other to form a ring which may have a substituent.
R ¹⁷ and R ¹⁸ 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 ⁵ , R ⁶ and R ⁸ to R ¹⁸ 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;
^R3 and ^R4 each independently represent 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, and may be bonded to each other to form a ring which may have a substituent;
The transition metal compound [A] according to the above [1], wherein R ⁷ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an optionally substituted aromatic five-membered heterocyclic group containing at least one atom selected from nitrogen, oxygen and sulfur in the heterocycle.

[3]
In the general formula [1],
Q is a silicon atom;
R ¹ , R ² , R ⁵ , R ⁶ and R ⁸ to R ¹⁸ each independently represent 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 the above [2], wherein R ³ and R ⁴ each independently represent 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 may be bonded to each other to form a ring which may have a substituent.

[4]
The transition metal compound [A] according to the above [3], wherein in the above general formula [1], R ¹ and R ⁶ are hydrogen atoms.

[5]
The transition metal compound [A] according to the above [4], wherein in the above general formula [1], R ² and R ⁵ are hydrogen atoms.

[6]
The transition metal compound [A] according to the above [5], wherein in the above general formula [1], R ⁷ and R ⁸ are hydrogen atoms.

[7]
The transition metal compound [A] according to the above [6], wherein in the above general formula [1], R ⁹ and R ¹⁰ are hydrogen atoms.

[8]
The transition metal compound [A] according to the above [7], wherein, in the above general formula [1], R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms and may be bonded to each other to form a ring which may have a substituent.

[9]
An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of [1] to [8] above.
[10]
Furthermore, [B] [B-1] an organometallic compound,
[B-2] an organoaluminum oxy compound; and [B-3] at least one compound selected from the group consisting of a compound that reacts with the transition metal compound [A] to form an ion pair.

[11]
A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to [9] or [10] above.

[12]
The method for producing an olefin polymer according to [11] above, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having from 3 to 20 carbon atoms.

The transition metal compound, olefin polymerization catalyst, and olefin polymer production method according to the present invention make it possible to produce olefin polymers, such as ethylene polymers, which have many long chain branches and high molecular weights.

The transition metal compound and the like according to the present invention will be described in further detail below.
[Transition metal compound [A]]
The transition metal compound [A] according to the present invention (hereinafter, may be referred to as “component (A)”) is represented by the following general formula [1].

《M, n, X》
In the general formula [1], M is a transition metal atom of Group 4 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, preferably 1 or 2, 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, 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, or an oxygen-containing group.

When n is 2 or more, the multiple Xs may be the same or different and may be bonded to each other to form a ring. When multiple rings are present, the rings may be the same or different.

The halogen atom includes fluorine, chlorine, bromine, iodine, etc., and is preferably chlorine or bromine.
Examples of the hydrocarbon group include:
linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl;
Linear or branched alkenyl groups or unsaturated double bond-containing groups such as vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-dien-1-yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group), buta-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3-methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, and prenyl group (3-methylbut-2-en-1-yl group);
linear or branched alkynyl groups or unsaturated triple bond-containing groups such as an ethynyl group, a prop-2-yn-1-yl group, or a propargyl group (a prop-1-yn-1-yl group);
Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups, such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group);
cyclic saturated hydrocarbon groups 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, and a 2-adamantyl group;
Examples of aromatic substituents include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a duryl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the above hydrocarbon groups, methyl, iso-butyl, neopentyl, cyamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.

Among the above halogen-containing groups, a pentafluorophenyl group is preferred.
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, and a trimethylsilylmethyl group.

Among the above silicon-containing groups, a trimethylsilylmethyl group is preferred.
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 isopropoxy group, and a tert-butoxy group are preferred.
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 above sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) is preferred.
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 preferred.
The phosphorus-containing group may, for example, be a hexafluorophosphate anion.

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by _BR4 (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

The aluminum-containing group may, for example, be

(M represents M in the general formula (1) above.)
Examples of the groups include groups represented by AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like) which can form the following formula:

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

Examples of neutral ligands that can be coordinated with lone pairs include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

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, more preferably a silicon atom.

<<R ¹ to R ¹⁸ >>
In the general formula [1],
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R 14 , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent 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 ³ and R ⁴ are each independently 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.

The hydrocarbon groups having 1 to 40 carbon atoms represented by R ¹ to R ¹⁸ include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples thereof include the specific examples of hydrocarbon groups given above as examples of X.

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. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include:
Methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decanyl, 1-undecanyl, 1-dodecanyl, 1-eicosanyl, isopropyl, sec-butyl, tert-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl (1,1-dimethylpropyl), cyamyl, pentan-3-yl, 2-methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl (2-methylpentan-2-yl), 3-methylpentane linear or branched alkyl groups having 1 to 40 carbon atoms, such as 2-methylpentan-2-yl, 4-methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, 3,3-dimethylbut-2-yl, hexane-3-yl, 2-methylpentan-3-yl, heptan-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, and 2,4,4-trimethylpentan-2-yl;
Vinyl group, allyl group, propenyl group, isopropenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, isopentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, 2-methyl-but-3-en-2-yl group, pent-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en- 1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethyl-pent-1-en-3 linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, such as 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-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group;
Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, such as but-1-yn-yl group, pent-4-yn-2-yl group, hex-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, 2,2-dimethyl-but-3-yn-1-yl group, hex-4-yn-1-yl group, and hex-5-yn-1-yl group;
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-phenylphenyl phenylmethyl 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-i so-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)propane- aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as a 2-yl group, a (tetrahydro-1-indacenyl)diphenylmethyl group, a 2-(tetrahydro-1-indacenyl)ethyl group, a 2-(1-benzoindenyl)propan-2-yl group, a (1-benzoindenyl)diphenylmethyl group, a 2-(1-benzoindenyl)ethyl group, a 2-(9-fluorenyl)propan-2-yl group, a (9-fluorenyl)diphenylmethyl group, a 2-(9-fluorenyl)ethyl group, a 2-(1-azulenyl)propan-2-yl group, a (1-azulenyl)diphenylmethyl group, and a 2-(1-azulenyl)ethyl group;
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-methylcyclohex Sil 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, cyclooctatrienyl 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;
Examples of aromatic substituents having 6 to 40 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a 3,5-di-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, pentan-3-yl, isohexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, heptane-4-yl, Preferred are 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, and 2,4,4-trimethylpentan-2-yl group, and more preferred are 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, and 2,4,4-trimethylpentan-2-yl group.

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

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl groups, propargyl groups, but-2-yn-1-yl groups, but-3-yn-1-yl groups, pent-3-yn-1-yl groups, pent-4-yn-1-yl groups, 3-methyl-but-1-yn-1-yl groups, 3,3-dimethyl-but-1-yn-1-yl groups, hex-4-yn-1-yl groups, and hex-5-yn-1-yl groups are preferred, with prop-2-yn-1-yl groups, propargyl groups, but-2-yn-1-yl groups, and but-3-yn-1-yl groups being more preferred.

Among the aromatic 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, rt-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, etc. are preferred, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, and cinnamyl group are more preferred.

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-benzylcyclohexyl group, Preferred are cycloheptyl, cyclooctyl, cyclooctenyl, cyclooctadienyl, 4-cyclohexyl-tert-butyl, norbornyl, 2-methylbicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.2]octan-1-yl, 1-adamantyl, 2-adamantyl, pentalenyl, indenyl, and fluorenyl groups, and more preferred are cyclopentyl, cyclopentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, and 1-adamantyl groups.

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

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a di-tert-butyl-fluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a bistrifluoromethoxyphenyl group, a trifluoromethylthiophenyl group, a bistrifluoromethylthiophenyl group, a fluorobiphenyl group, a difluorobiphenyl group, a trifluoromethylthiophenyl group, a ... 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, trifluoromethylthio group, etc.

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

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 indenyldimethylsilyl group, and a di-n-butyl(indenyl) Examples of such groups include silyl groups, indenyldiphenylsilyl groups, fluorenyldimethylsilyl groups, di-n-butyl(fluorenyl)silyl groups, fluorenyldiphenylsilyl groups, 4-trimethylsilylphenyl groups, 4-triethylsilylphenyl groups, 4-tri-iso-propylsilylphenyl groups, 4-tert-butyldiphenylsilylphenyl groups, 4-triphenylsilylphenyl groups, 4-tris(trimethylsilyl)silylphenyl groups, and 3,5-bis(trimethylsilyl)phenyl groups.

Among the silicon-containing groups, preferred are trimethylsilyl, triethylsilyl, tri-isopropylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, 4-triphenylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups, and more preferred are trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups.

Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a methallyloxy group, a prenyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an isopropylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an isopropoxyphenoxy 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, an Examples of the alkyl group include pyryl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl 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, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, and dibenzofuryl group.

Among the oxygen-containing groups, alkoxy groups having 1 to 20 carbon atoms (preferably 1 to 10) are preferred, specifically methoxy groups, ethoxy groups, iso-propoxy groups, allyloxy groups, n-butoxy groups, tert-butoxy groups, prenyloxy groups, benzyloxy groups, phenoxy groups, naphthoxy groups, toluyloxy groups, iso-propylphenoxy groups, allylphenoxy groups, tert-butylphenoxy groups, methoxyphenoxy groups, biphenyloxy groups, binaphthyloxy groups, allyloxymethyl groups, benzyloxymethyl groups, phenoxymethyl groups, methoxyethyl groups, methoxyallyl groups, benzyloxyallyl groups, phenoxyallyl groups, dimethoxymethyl groups, dioxolanyl groups, tetramethyldioxolanyl groups, dioxanyl groups, dimethyldioxanyl groups, methoxyphenyl groups, is o-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, furyl group, benzofuryl group, dibenzofuryl group, etc. are preferred, 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 preferred.

Examples of the nitrogen-containing group include an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3 , 5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl 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, 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, etc.

Among the nitrogen-containing groups, amino groups having 1 to 20 carbon atoms (preferably 1 to 10) are preferred, 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, tetramethyljulolidinyl 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, etc. are preferred, 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, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group are more preferred.

Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenylthio Examples of such groups include allyl 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, and thiazolidinyl group.

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

Adjacent substituents among R ¹ to R ⁶ (e.g., R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ ) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring condensed with the indenyl ring portion and made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may have a substituent. When a plurality of rings are present, they may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring portion of the mother nucleus include a benzoindenyl ring, a tetrahydroindacenyl ring, and a tetrahydrobenzoindenyl ring (which may have a substituent), and a benzoindenyl ring and a tetrahydroindacenyl ring (which may have a substituent) are preferred.

Adjacent substituents among R ⁷ to R ¹¹ (e.g., R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ ) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring condensed with the indenyl ring portion and made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may have a substituent. When a plurality of rings are present, they may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring portion of the mother nucleus include a benzoindenyl ring, a tetrahydroindacenyl ring, a tetrahydrobenzoindenyl ring, a tetrahydrofluorenyl ring, and a fluorenyl ring (which may have a substituent), and a benzoindenyl ring and a tetrahydroindacenyl ring (which may have a substituent) are preferred.

Adjacent substituents among R ¹² to R ¹⁶ (e.g., R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁶ ) may be bonded to each other to form a ring that may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring made of a saturated hydrocarbon (excluding the hydrocarbon of the benzene ring portion) or an unsaturated hydrocarbon that may have a substituent and is condensed with the benzene ring portion. In addition, when there are multiple 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 exhibited, the ring is more preferably a 5- or 6-membered ring, and in this case, the structure formed by combining the ring and the benzene ring portion of the mother nucleus is preferably, for example, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetrahydronaphthalene ring, an octahydroanthracene ring, a dihydroindene ring, or a hexahydroindacene ring.

R ⁹ and R ¹² or R ¹⁶ (e.g., R ⁹ and R ¹² , and R ⁹ and R ¹⁶ ) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 6-membered ring which is condensed with the indenyl ring portion and the benzene ring portion and which may have a substituent and is made of a saturated hydrocarbon (excluding the hydrocarbons of the indenyl ring portion and the benzene ring portion) or an unsaturated hydrocarbon. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 6-membered ring. In this case, the structure formed by combining the ring with the indenyl ring portion and the benzene ring portion of the mother nucleus is, for example, a cyclopentaphenanthrene ring, a dihydrocyclopentaphenanthrene ring, or a cyclopentafluorene ring.

R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring containing Q. In this case, the ring formed is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. 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, and in this case, examples of the structure formed by combining R ¹⁷ and R ¹⁸ with Q include a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletan) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane), and a substituted silafluorene ring, and a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferred.

R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently 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, and more preferably a hydrogen atom.

^R3 and ^R4 are each independently preferably 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 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 even more preferably a hydrocarbon group having 1 to 20 carbon atoms.

R ¹¹ to R ¹⁸ are each independently 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, and 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.

In addition, in at least one of ^R7 and ^R11 , particularly in ^R7 , the oxygen-containing group, nitrogen-containing group or sulfur-containing group may be a heterocyclic aromatic group described later.

<<Preferred embodiment of transition metal compound [A]>>
A preferred embodiment of the transition metal compound [A] is
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 ⁵ , R ⁶ and R ⁸ to R ¹⁸ 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;
^R3 and ^R4 each independently represent 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, and may be bonded to each other to form a ring which may have a substituent;
Examples of the transition metal compound [A-1] include a compound in which R ⁷ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an optionally substituted aromatic five-membered heterocyclic substituent containing at least one atom selected from nitrogen, oxygen, and sulfur in the heterocycle.

More preferred embodiments of the transition metal compound [A-1] include the following:
In the general formula [1],
Q is a silicon atom;
R ¹ , R ² , R ⁵ , R ⁶ and R ⁸ to R ¹⁸ each independently represent 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;
Examples of the transition metal compound [A-2] include those in which R ³ and R ⁴ each independently represent 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 which may be bonded to each other to form a ring which may have a substituent.

A more preferred embodiment of the transition metal compound [A-2] is the transition metal compound [A-3] in which R ¹ and R ⁶ in the general formula [1] are hydrogen atoms.
A more preferred embodiment of the transition metal compound [A-3] is the transition metal compound [A-4] in which R ² and R ⁵ in the general formula [1] are hydrogen atoms.

A more preferred embodiment of the transition metal compound [A-4] is the transition metal compound [A-5] in which R ⁷ and R ⁸ in the general formula [1] are hydrogen atoms.
A more preferred embodiment of the transition metal compound [A-5] is the transition metal compound [A-6] in which R ⁹ and R ¹⁰ in the general formula [1] are hydrogen atoms.

A more preferred embodiment of the transition metal compound [A-6] is the transition metal compound [A-7], in which R ³ and R ⁴ in the general formula [1] each independently represent a hydrocarbon group having 1 to 20 carbon atoms and may be bonded to each other to form a ring which may have a substituent.

In the transition metal compound [A], examples of the heterocyclic aromatic group which is one of the options for ^R7 and ^R11 and has a five-membered skeleton containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur (hereinafter also referred to as a "hetero five-membered ring") and which may have a substituent include groups represented by the following general formulas [4a] to [4h].

In the general formulae [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R ^d is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different.

The wavy lines in the general formulae [4a] to [4h] indicate the bonding sites to the indenyl ring.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned R ¹ to R Among the examples of the hydrocarbon group having 1 to 40 carbon atoms given above as ¹⁴ , those having 1 to 20 carbon atoms are preferred, and preferably, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an allyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctenyl group, a norbornyl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylethyl group, a 4-phenylethyl group, a 5-phenylethyl group, a 6-phenylethyl group, a 7-phenylethyl group, a 8-phenylethyl group, a 9-phenylethyl group, a 10-phenylethyl group, a 11-phenylethyl group, a 12-phenylethyl group, a 13-phenylethyl group, a 14-phenylethyl group, a 15-phenylethyl group, a 16-phenylethyl group, a 17-phenylethyl group, a 18-phenylethyl group, a 19-phenylethyl group, a 20-phenylethyl group, a 21-phenylethyl group, a 22-phenylethyl group, a 23-phenylethyl group, a 24-phenylethyl group, a 25-phenylethyl group, a 26-phenylethyl group, a 27-phenylethyl group, a 28 Examples of the alkyl group include a propyl group, a cinnamyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, and a ferrocenyl group, and more preferably, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, an iso-propyl group, a sec-butyl group, a tert-butyl group, an iso-butyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a biphenyl group, and a terphenyl group.

^Rd may be independently bonded to adjacent ^Rds to form a saturated or unsaturated hydrocarbon group which may have a substituent and which is condensed to the 5-membered heterocyclic ring moiety and which constitutes a 5- to 8-membered ring together with the atoms of the 5-membered heterocyclic ring moiety. The 5- to 8-membered ring is not particularly limited as long as the effects of the present invention are exhibited, but is preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining this ring with the 5-membered heterocyclic ring moiety of the mother nucleus include a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

Among the heterocyclic aromatic groups represented by the general formulae [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred.
Among the heterocyclic aromatic groups represented by the general formula [4a], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, and a 5-methyl-2-thienyl group are preferred.

<<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 thereto.

For convenience, the ligand structure of the transition metal compound [A] excluding the portion represented by MXn (metal portion) is divided into eight structures: a 2-indenyl ring portion, a 1-indenyl ring portion, R ¹ , R ⁶ and R ⁸ substituents of the indenyl ring portion, R ² , R ⁵ and R ¹¹ substituents of the indenyl ring portion, R ³ , R ⁴ , R ⁹ and R ¹⁰ substituents of the indenyl ring portion, R ⁷ substituent of the 1-indenyl ring portion, Ar substituent at the 4-position of the 1-indenyl ring, and a bridging portion. The abbreviation for the 2-indenyl ring moiety is α, the abbreviation for the 1-indenyl ring moiety is β, the abbreviation for the R ¹ , R ⁶ and R ⁸ substituents on the indenyl ring moiety is γ, the abbreviation for the R ² , R ⁵ and R ¹¹ substituents on the indenyl ring moiety is δ, the abbreviation for the R ³ , R ⁴ , R ⁹ and R ¹⁰ substituents on the indenyl ring moiety is ε, the abbreviation for the R ⁷ substituent on the 1-indenyl ring moiety is ζ, the abbreviation for the Ar substituent at the 4-position of the 1-indenyl ring is η, and the abbreviation for the structure of the bridged moiety is θ, and the abbreviations for the substituents are shown in [Table 1] to [Table 8].

The wavy lines in Tables 1 and 2 indicate the bond sites with the crosslinked moieties.

The R ¹ , R ⁶ and R ⁸ substituents in Table 3 may be the same or different from each other in their combination.

The R ² , R ⁵ and R ¹¹ substituents in Table 4 may be the same or different from each other in their combination.

The R ³ , R ⁴ , R ⁹ and R ¹⁰ substituents in Table 5 may be the same or different from each other in combination, provided that the R ³ and R ⁴ substituents are not ε-1.

Specific examples of the metal portion 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(OMe) ₂ , Ti(OiPr) ₂ , Ti(NMe2) ₂ , Ti ₍ OMs) ₂ , Ti(OTs) ₂ , Ti(OTf) ₂ , ZrF ₂ , _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(OMe) ₂ , Zr(OiPr) ₂ , Zr( _{NMe2 ) 2} , Zr(OMs) ₂ , Zr(OTs) ₂ , Zr(OTf) 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(OMe) ₂ , Hf(OiPr) ₂ , Hf( _NMe2 ) ₂ , Hf(OMs) ₂ , Hf(OTs) ₂ , Hf(OTf) ₂ , and the like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an isopropoxy group, _NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

According to the above notation, when the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], the indenyl ring moiety R ¹ , R ⁶ and R ⁸ substituents are all γ-1 in [Table 3], the 2-indenyl ring moiety R ² and R ⁵ substituents are all δ-1 in [Table 4], the 1-indenyl ring 4-position Ar substituent is η-28 in [Table 7], the 1-indenyl ring moiety R ⁹ and R ¹⁰ substituents are ε-1 in [Table 5], the 1-indenyl ring moiety R ¹¹ substituent is δ-3 in [Table 4], and the bridging moiety is θ-20 in [Table 7], and the metal moiety MXn is ZrCl ₂ , the compound represented by the following formula [5] is exemplified.

The 2-indenyl ring moiety is α-1 in Table 1; the 1-indenyl ring moiety is β-1 in Table 2; the indenyl ring moieties R ¹ , R ⁶ and R ⁸ substituents are all γ-1 in Table 3; the 2-indenyl ring moiety R ² and R ⁵ substituents are all δ-2 in Table 4; the 2-indenyl ring moiety R ³ and R ⁴ substituents are ε-2 in Table 5; the 1-indenyl ring moiety R ⁷ substituent is ζ-30 in Table 6; the 1-indenyl ring moiety R ⁹ and R ¹⁰ substituents are ε-1 in Table 5; the 1-indenyl ring 4-position moiety Ar substituent is η-39 in Table 7; the 1-indenyl ring moiety R ¹¹ substituent is δ-1 in Table 4; and the bridging moiety is θ-4 in Table 8; and the metal moiety MXn is Zr(NMe ₂ ) In the case of ₂ , a compound represented by the following formula [6] is exemplified.

In addition, the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], the indenyl ring moiety R ¹ and R ⁶ substituents are all γ-2 in [Table 3], the indenyl ring moiety R ² , R ⁵ and R ¹¹ substituents are all δ-1 in [Table 4], the 1-indenyl ring moiety R ⁷ substituent is ζ-12 in [Table 6], the 1-indenyl ring moiety R ⁸ substituent is γ-1 in [Table 3], the 1-indenyl ring 4-position moiety Ar substituent is η-50 in [Table 7], the 1-indenyl ring moiety R ⁹ substituent is ε-3 in [Table 5], the 1-indenyl ring moiety R ¹⁰ substituent is ε-12 in [Table 5], the 1-indenyl ring moiety R ¹¹ substituent is δ-1 in [Table 4], and the bridging moiety is θ-31 in [Table 8]; and MXn of the metal moiety is HfMe. In the case of ₂ , a compound represented by the following formula [7] is exemplified.

In addition, the 2-indenyl ring moiety is an α-1,1-indenyl ring moiety in [Table 1], the β-1,2-indenyl ring moiety R ¹ and R ⁶ substituents in [Table 2] are all the γ-1,2-indenyl ring moiety R ² substituents in [Table 3], the δ-7,2-indenyl ring moiety R ³ and R ⁴ substituents in [Table 5], the ε-2,2-indenyl ring moiety R ⁵ substituent in [Table 4], the δ-2,1-indenyl ring moiety R ⁷ substituent in [Table 5], the ζ-1,1-indenyl ring moiety R ⁸ substituent in [Table 6], the γ-9,1-indenyl ring moiety R ⁹ and R ¹⁰ substituents in [Table 3], the ε-1,1-indenyl ring 4-position Ar substituent in [Table 5], the η-43,1-indenyl ring moiety R In the case where the ¹¹ substituents are composed of a combination of δ-1 in [Table 4] and the bridging portion is composed of a combination of θ-29 in [Table 8], and the metal portion MXn is Ti(1,3-pentadienyl), the compound represented by the following formula [8] is exemplified.

In addition, the transition metal compound [A] has two faces of the indenyl ring portion that are bonded to the central metal across the bridge portion (front and back). Therefore, when the 2-indenyl ring portion does not have a symmetrical plane, there are two structural isomers, as shown in the following general formula [9a] or [9b].

Similarly, when the substituents R ¹⁷ and R ¹⁸ in the bridging portion are not the same, there exist two structural isomers represented by the following general formulas [10a] and [10b], for example.

In addition, Ar in [9a], [9b], [10a] and [10b] represents an aromatic substituent. Purification and separation of these structural isomer mixtures, or selective production of structural isomers, can be performed by known methods, and the production method is not particularly limited. In addition to the known production methods listed as the production method of the transition metal compound [A], production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", JP-T-2011-502192, etc. can be mentioned.

In addition, within the scope of the transition metal compound [A], one type of transition metal compound may be used alone, two or more types may be used in combination, a mixture of structural isomers may be used, or one type of structural isomer may be used alone, or a mixture of two or more types of structural isomers may be used. In addition, one or more types of transition metal compounds other than the transition metal compound [A] may be used in combination within a range that does not impair the effects of the present invention. In this case, the transition metal compound [A] may be in any of the above-mentioned forms.

<<Method for producing transition metal compound [A]>>
The transition metal compound [A] can be produced by utilizing a conventionally known method, for example, the method described in [0101] to [0120] of JP2019-59723A, in which ^R1 to ^R18 , Q, M, X and n are read as defined in the above general formula [1].

[Olefin polymerization catalyst]
The olefin polymerization catalyst of the present invention contains the transition metal compound [A] of the present invention.
A representative example of the olefin polymerization catalyst of the present invention is an ethylene polymerization catalyst.

(Compound [B])
The olefin polymerization catalyst of the present invention preferably further comprises an organometallic compound [B-1], preferably an organometallic compound represented by the following general formula (B-1a), (B-1b) or (B-1c) (hereinafter also referred to as "component (B-1)");
R ^a _m Al (OR ^b ) _n H _p X _q ... (B-1a)
[In general formula (B-1a), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other, X represents a halogen atom, m represents a number satisfying 0<m≦3, n represents a number satisfying 0≦n<3, p represents a number satisfying 0≦p<3, q represents a number satisfying 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 general formula (B-1c), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different, M ^b is selected from Mg, Zn and Cd, X represents a halogen atom, r represents 0<r≦2, s represents 0≦s≦1, t represents 0≦t≦1, and r+s+t=2.]
[B-2] At least one compound [B] (hereinafter sometimes referred to as "component (B)") selected from the group consisting of an organoaluminum oxy compound (hereinafter sometimes referred to as "component (B-2)"), and [B-3] a compound that reacts with a transition metal compound (A) to form an ion pair (hereinafter sometimes referred to as "component (B-3)").

As the organometallic compound [B-1], the compounds disclosed in JP-A-11-315109 or EP0874005A can be used without any restrictions.
The organometallic compound [B-1] is preferably one represented by the general formula (B-1a), and specific examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; methylaluminum dichloride, ethylaluminum dichloride, and the like; aluminum hydride, isopropylaluminum dichloride, ethylaluminum dibromide and other alkylaluminum dihalides; 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 and other alkylaluminum hydrides; and dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, diisobutylaluminum ethoxide and other dialkylaluminum alkoxides.

These may be used alone or in combination of two or more.
The organoaluminum oxy compound [B-2] is preferably an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum, and more preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds may be used alone or in combination of two or more.

As the compound [B-3] that reacts with the transition metal compound (A) to form an ion pair, Lewis acids, ionic compounds, borane compounds, carborane compounds, heteropoly compounds, and isopoly compounds described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106, can be used without limitation.

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, not only does it exhibit extremely high catalytic activity for olefins such as ethylene, but it also reacts with active hydrogen in the solid support to easily prepare a solid support component containing the cocatalyst component, so it is preferable to use the organoaluminum oxy compound [B-2] as the component (B).

(Solid Carrier [S])
The olefin polymerization catalyst of the present invention preferably contains a solid support [S] (hereinafter sometimes referred to as "support [S]" or "component (S)").

The solid carrier [S] is an inorganic compound or an organic compound, and is a granular or fine particle solid.
The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound.

Specifically, the porous oxide may be SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a composite or mixture containing these, and may further be, for example, natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Among these, the porous oxide is preferably one containing SiO ₂ and/or Al ₂ O ₃ as the main component.

The porous oxide may contain small amounts of _{carbonates, sulfates, nitrates, and oxides such as Na2CO3 , K2CO3 , CaCO3} , _MgCO3 , _Na2SO4 , _Al2 ( _SO4 ) ₃ , _{BaSO4 , KNO3} , Mg( _NO3 ) ₂ , Al( _NO3 ) ₃ , _Na2O , _K2O , and _Li2O .

Although the properties of the porous oxide vary depending on the type and production method, the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, a specific surface area of 50 to 1000 m ² /g, preferably 100 to 700 m ² /g, and a pore volume of 0.3 to 3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., as necessary, before use.

The solid aluminoxane compound may be selected from at least one of aluminoxanes having a structure represented by the following general formula (S-a) or (S-b), and aluminoxanes having a structure including a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d).

In the general formulae (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, and specifically includes hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, and ethylphenyl groups, of which methyl, ethyl, and isobutyl groups are preferred, and methyl is particularly preferred. In addition, R ^e may be partially substituted with halogen atoms such as chlorine and 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 not connected to an atom on one side indicates a bond with another atom not shown.

In the general formulae (S-a) and (S-b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the general formulae (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 be maintained in a substantially solid state in the reaction environment in which it is used.

The solid aluminoxane compound is different from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina or organic polymer components such as polyethylene or polystyrene, but is solidified with an alkylaluminum compound as the main component. "Solid" means that the aluminoxane component substantially maintains a solid state in the reaction environment in which it is used. More specifically, it means that the aluminoxane component substantially maintains a solid state when the transition metal compound [A] is contacted with the aluminoxane component to prepare an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) as described below, and when the prepared olefin polymerization catalyst is used to polymerize an olefin (e.g., ethylene) (e.g., suspension polymerization).

Whether the aluminoxane component is in a solid state is most easily confirmed by visual inspection, but visual inspection is often difficult, for example, during polymerization. In such cases, 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 adhesion to the reactor is small, the gist of the present invention will not be deviated from even if some of the aluminoxane component is eluted in the polymerization environment. Indicators for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitativeness. The bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

The solubility 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%.

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

As the solid aluminoxane compound, any known solid aluminoxane can be used without limitation, and for example, the solid polyaluminoxane composition described in WO 2014/123212 can be used. Known manufacturing methods include those described in JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000-38410, JP-A-2000-95810, WO 2010/55652, etc.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 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 averaging the sizes by weight. First, the particle size of each particle is determined by measuring the length of the particle image between two parallel lines in the horizontal and vertical directions, and then using the following formula:

Grain size = ((horizontal length) ² + (vertical length) ² ) ^0.5
Next, the weight average particle size of the solid aluminoxane compound is calculated from the particle size calculated above according to the following formula.

Weight average particle size=Σnd ⁴ /Σnd ³
(n: number of particles, d: particle size)
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.

As the inorganic halide, _MgCl2 , _MgBr2 , _MnCl2 , _MnBr2 , etc. can be used. The inorganic halide may be used as it is after it is obtained, or may be used after it is pulverized by a ball mill or a vibration mill. In addition, the inorganic halide may be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds with a crystal structure in which the planes formed by ionic bonds are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificially synthesized products can also be used.

Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type.

Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc.
Examples of the ion-exchangeable layered compound include _crystalline acid 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 .

Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc/g or more with a radius of 20 Å or more, as measured by mercury intrusion porosimetry, and more preferably 0.3 to 5 cc/g. Here, the pore volume is measured for a pore radius range of 20 to 30,000 Å by mercury intrusion porosimetry using a mercury porosimeter.

When a carrier having a pore volume of less than 0.1 cc/g and a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.
It is also preferable to subject the clay and clay minerals to chemical treatment. As the chemical treatment, any of surface treatments that remove impurities adhering to the surface and treatments that affect the crystalline structure of the clay can be used. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. In addition to removing impurities from the surface, acid treatment increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. In alkali treatment, the crystalline structure of the clay is destroyed, resulting in a change in the structure of the clay. In addition, salt treatment and organic treatment form ion complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

The ion-exchangeable layered compound may be a layered compound in which the space between layers is expanded by exchanging the exchangeable ions between layers with other large bulky ions by utilizing the ion exchangeability. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of another substance between layers of the layered compound is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ (R is a hydrocarbon group, etc.), and metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ and [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) ₄ , and colloidal inorganic compounds such as SiO ₂ can be coexisted. Examples of pillars include oxides generated by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as obtained, or may be used after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.

Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred.
Examples of organic compounds that can be used as the carrier [S] include granular or fine particle solids having a particle size in the range of 1 to 300 μm. Specific examples include 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 and styrene, and modified products thereof.

<How to use each ingredient and the order of addition>
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.

Regarding the method of contacting each component, when paying attention to the order of contact, for example,
(i) a method of contacting component (A) with component (B); (ii) a method of contacting component (S) with component (A); (iii) a method of contacting component (S) with component (B) and then with component (A); (iv) a method of contacting component (A) with component (B) and then with component (S); (v) a method of contacting component (S) with component (B) and then with a mixture of components (A) and (B),
(vi) A method of contacting component (S) with component (B), then with component (B), and then with a mixture of component (A) and component (B). When multiple types of component (B) are used, the components (B) may be the same or different. Of the above methods, (i), (ii), (iii) and (iv) are preferred.

In each of the methods showing the above contact order forms, in the process including contact of component (S) with component (B) and the process including contact of component (S) with component (A), fouling during the polymerization reaction is suppressed and the particle properties of the resulting polymer are improved by the coexistence of component (G). As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acyl amino acids being more preferred. These may be used alone or in combination of two or more.

Solvents used in the preparation of the olefin polymerization catalyst of the present invention include inert hydrocarbon solvents, 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; and mixtures thereof. Depending on the type of olefin to be polymerized, the olefin itself can also be used as the solvent.

In the contact between component (B) and component (S), the reactive sites in component (B) react with the reactive sites in component (S) to chemically bond them to form a contact product of component (B) and component (S). 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 made suddenly, component (S) will collapse due to the heat generated by the reaction or the reaction energy, and the morphology of the resulting solid catalyst component will deteriorate, and if this is used in polymerization, continuous operation will often be difficult due to poor polymer morphology. Therefore, in the initial contact between component (B) and component (S), it is preferable to contact them at a lower temperature in order to suppress the heat generated by the reaction, or to control the heat generated by the reaction and react at a rate that can maintain the initial contact temperature. The same applies when component (B) and component (S) are contacted and then component (B) is contacted. The contact weight ratio between component (B) and component (S) (weight of component (B)/weight of component (S)) can be selected arbitrarily, but a higher contact weight ratio allows more component (A) to be contacted, improving the catalytic activity per weight of the solid catalyst component.

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 contacted with component (A), the contact time is usually 1 minute to 20 hours, and preferably 1 minute to 10 hours, and the contact temperature is usually within the range of −50 to 200° C., and preferably −50 to 100° C.

Component (B-1) is used in an amount such that the molar ratio of component (B-1) to the total transition metal atoms (M) in component (A) [(B-1)/M] 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) (calculated as aluminum atoms) to the total 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 the total transition metal atoms (M) in component (A) is usually 1 to 10, and preferably 1 to 5. The ratio of component (B) to the total transition metal atoms (M) in component (A) can be determined by inductively coupled plasma atomic emission spectrometry (ICP analysis).

For olefin polymerization, the olefin polymerization catalyst according to the present invention can be used as is, but it can also be used after prepolymerizing an olefin with the olefin polymerization catalyst to form a prepolymerized solid catalyst component.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin (e.g., ethylene) or the like, usually in an inert hydrocarbon solvent, in the presence of the olefin polymerization catalyst according to the present invention, and can be carried out in any of batch, semi-continuous, and continuous modes, and can be carried out under reduced pressure, normal pressure, or increased pressure. Furthermore, it is desirable that the prepolymerization produces a prepolymerized solid catalyst component in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g, per gram of the solid catalyst component.

The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent may be separated from the suspension and then resuspended in the inert hydrocarbon, and an olefin (e.g., ethylene) may be introduced into the resulting suspension, or the 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 the prepolymerization, an olefin mainly composed of ethylene is preferably used.

The form of the solid catalyst component used in the preliminary polymerization can be any of those already mentioned, without any restrictions. Component (B) is used as necessary, and in particular, an organoaluminum compound [B-1a] represented by 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.

The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is usually 1 to 1000 g/L, preferably 10 to 500 g/L, in terms of the olefin polymerization catalyst/polymerization volume ratio. During the prepolymerization, the above-mentioned component (G) may be present to suppress fouling or improve particle properties.

In addition, in order to improve the fluidity of the prepolymerized solid catalyst component and to suppress the occurrence of heat spots, sheeting, and polymer lumps during polymerization, the prepolymerized solid catalyst component once produced by prepolymerization may be contacted with component (G).

The temperature when the component (G) is contacted is usually from -50 to 50°C, preferably from -20 to 50°C, and the contact time is usually from 1 minute to 20 hours, preferably from 5 minutes to 10 hours.
When the olefin polymerization catalyst according to the present invention is contacted 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, and 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.

The mixing and contacting of the olefin polymerization catalyst according to the present invention with the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include those similar to those mentioned above.
In the method for producing an olefin polymer according to the present invention, a prepolymerized solid catalyst component obtained by drying (hereinafter also referred to as a "dried prepolymerized catalyst") can be used as the olefin polymerization catalyst. Drying of the prepolymerized solid catalyst component is usually carried out after removing the hydrocarbon, which is the dispersion medium, from the obtained suspension of the prepolymerized catalyst by filtration or the like.

The prepolymerized solid catalyst component is dried by maintaining the prepolymerized solid catalyst component at a temperature of 70°C or less, preferably in the range of 20 to 50°C, under a flow of inert gas. The amount of volatile components in the obtained dried prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dried prepolymerized catalyst is preferably as small as possible, and there is no particular lower limit, but in practice it is 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

The dry prepolymerized catalyst has excellent fluidity and can be stably supplied to the polymerization reactor. In addition, the use of the dry prepolymerized catalyst makes it possible to carry out stable polymerization since it is not necessary to entrain the solvent used for suspension in the gas phase polymerization system.

[Production method of olefin polymer]
The process for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention.

A preferred embodiment of the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, in which ethylene is polymerized or ethylene is polymerized with an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention.

When the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, the ethylene content in the ethylene-based polymer is preferably 70 mol % or more (the total of the monomer units is taken as 100 mol %).

Examples of the polymerization method include liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods, with the suspension polymerization method and gas phase polymerization method being 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, and mixtures thereof.

When olefins (e.g., ethylene) are polymerized using the olefin polymerization catalyst according to the present invention, component (A) is used in an amount of usually 1×10 ^-12 to 1×10 ^-1 mol, preferably 1×10 ^-8 to 1×10 ^-2 mol, per liter of reaction volume. Also, component (B) is used, preferably a compound represented by formula (B-1a) or component (B-2).

When polymerizing an olefin (e.g., ethylene), the polymerization temperature has a lower limit of 0° C., preferably 40° C., and particularly preferably 60° C. Higher temperatures are 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 normal pressure to 100 kgf/cm ² , preferably normal pressure to 50 kgf/cm ² .

The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems, and can also be carried out in two or more stages with different reaction conditions.
The molecular weight of the olefin polymer obtained by the process for producing an olefin polymer according to the present invention can be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature. During the polymerization, the above-mentioned component (G) can be made to coexist for the purpose of suppressing fouling or improving particle properties.

When the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, the monomers supplied to the polymerization reaction are ethylene alone, or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of olefins 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, and 1-eicosene, and cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

In addition, small amounts of styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid may be supplied within a range that does not impair the effects of the present invention.

According to the method for producing an olefin polymer of the present invention, the transition metal compound [A] easily induces β-hydrogen elimination through β-agonistic interaction with the growing polymer chain, producing a macromer having a double bond at the end, and since a specific substituent is introduced into the metallocene transition metal compound [A], the transition metal compound [A] can efficiently incorporate the produced macromer, so that it is speculated that an olefin polymer (especially an ethylene-based polymer) having many long chain branches and a high molecular weight can be produced.

[Olefin polymer]
The olefin polymer (eg, ethylene-based polymer) produced according to the present invention may be pelletized.

Olefin polymers (e.g., ethylene polymers) produced by the present invention may contain additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as necessary, within the scope of the present invention.

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

The films obtained by processing the olefin polymer (e.g., ethylene-based polymer) produced by the present invention are suitable for use in packaging bags for liquids, liquid soup bags, liquid paper containers, laminated rolls, specially shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy-duty bags, cling films, sugar bags, oil packaging bags, various packaging films for food packaging, protective films, infusion bags, agricultural materials, etc., and can also be used as multilayer films by bonding with substrates such as nylon and polyester.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[Measurement of various physical properties]
The methods for measuring the physical properties of the ethylene polymer are shown below.

<Melt flow rate (MFR)>
The measurement was carried out under conditions of 190° C. and a load of 2.16 kg (kgf).
<Density (D)>
The strand obtained when measuring MFR was heat treated at 100° C. for 30 minutes and then allowed to stand at room temperature for 1 hour, after which the MFR was measured by the density gradient tube method.

<Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw/Mn, Mz/Mw)>
The measurement was carried out using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent Corporation as follows.

Two Agilent PLgel Olexis analytical columns were used, a differential refractometer and a three-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 calculations, the actual viscosity was calculated using 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 obtained using actual universal calibration.

<Synthesis of Transition Metal Compound (A)>
[Synthesis Example 1-1]
In a 200 mL reactor that had been thoroughly dried and argon-substituted, 1.45 g (59.8 mmol) of magnesium pieces were charged and 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 20 mL of tetrahydrofuran were charged and stirred. Furthermore, 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 was dropped into the solution (after adding 1.0 mL, the solution was heated and refluxed with a dryer until the color of iodine disappeared, and the remaining liquid was dropped after the start of the reaction), and the solution 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 under cooling at -78°C, and the solution was stirred for 19 hours while returning to room temperature. The solvent and unreacted dimethylsilyl dichloride were distilled off from the reaction solution, and then 10 mL of tetrahydrofuran and 1.62 mL (15.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain a solution 1a.

5.02 g (15.0 mmol) of 7-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indene synthesized by the method of Example 2-2 of JP2017-145240A and 15 mL of tetrahydrofuran were charged into a thoroughly dried and argon-purged 100 mL reactor, and 10.2 mL of n-butyllithium solution (hexane solution, 1.55 M, 15.8 mmol) was added. The mixture was stirred at room temperature for 2 hours to obtain solution 1b.

This solution 1b was added dropwise to solution 1a cooled to -78°C, and stirring was continued for 15 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, and the soluble matter was extracted with hexane. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled off to obtain a residue, which was purified by silica gel column chromatography to obtain 2.76 g (yield 34%) of the target product represented by the following formula (A-1L) (hereinafter referred to as "compound (A-1L)") as an isomer mixture.
^1H NMR (270MHz, _CDCl3 ) δ 7.46-7.19 (7H,m,Ar-H&C=CH-C), 7.06 (1H,dd,J=5.4and1.9Hz,C=CH-C), 6.99 (1H,s,C=CH-C), 6.67 (1H,dd,J=5.4and1.9Hz,C=CH-C), 3.74 (3H,s, _-OCH3 ), 3.72 (1H,s,Si-CH), 3.32-3.07 (2H,m,Ar- _CH2 -C), 2.92-2.87 (4H,m,Ar-CH2 _{- CH2} ), 2.11-2.06 (2H,q,J=7.3Hz, _CH2 - _{CH2 --CH2} ), 1.44 (18H, s, --C( _CH3 ) ₃ ), 0.22 (3H, s, Si-- _CH3 ), 0.20 (3H, s, Si-- _CH3 ) ppm

Example 1A
In a 100 mL reactor that had been thoroughly dried and purged with argon, 1.10 g (2.01 mmol) of the compound (A-1L) obtained in Synthesis Example 1-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged and stirred. To the solution thus obtained, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and then stirring was continued for 3 hours in a 40 ° C. oil bath. This solution was cooled to 0 ° C., 0.47 g (2.01 mmol) of zirconium tetrachloride was added, and stirring was continued for 19 hours at room temperature. After distilling off the solvent from the reaction solution, dichloromethane was added to the obtained solid to adjust the suspension, and insoluble matter was removed with Celite on a glass filter. The obtained solution was concentrated under reduced pressure, and n-hexane was added to prepare a suspension. Insoluble matter was filtered off using a glass filter, and the residue was dried under reduced pressure to obtain 0.51 g (yield 36%) of a yellow powdery compound represented by the following formula (A-1) (dimethylsilylene(1,5,6,7-tetrahydro-s-2-indacenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indenyl)zirconium dichloride, hereinafter referred to as "transition metal compound (A-1)").
^1H NMR (270MHz, _CDCl3 ) δ 7.66-7.57 (1H, m, Ar-H), 7.48-7.37 (1H, m, Ar-H), 7.37-7.28 (3H, m, Ar-H), 7.27-7.17 (2H, m, Ar-H), 6.86 (1H, d, J=3.3Hz, Ind-H), 6.12 (1H, dd, J=2.6 and 0.8Hz, Ind-H), 6.10-6.04 (2H, m, Ind-H), 3.70 (3H, s, _-OCH3 ), 3.05-2.90 (4H, m, Ar- _CH2 - _CH2 ), 2.03 (2H, q, J=7.0Hz, CH ₂ - _CH2 - _CH2 ), 1.39 (18H,s,-C( _CH3 ) ₃ ), 1.11 (3H,s,Si- _CH3 ), 0.87 (3H,s,Si- _CH3 ) ppm
FD-mass spectrometry (M ⁺ ): 706

[Synthesis Example 2-1]
In a 200 mL reactor that had been thoroughly dried and argon-substituted, 0.97 g (40.0 mmol) of magnesium pieces were charged and 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. Furthermore, a 20 mL diluted solution of 3.35 g (15.0 mmol) of 2-bromo-5,6-dimethyl-1H-indene synthesized by the method described on pages 9-10 of International Publication No. 2000/035975 was dropped (after adding 1.0 mL, heated to reflux with a dryer until the color of iodine disappeared, and the remaining liquid was dropped after the start of the reaction), and the mixture was stirred at room temperature for 2 hours after the end of the dropwise addition. This reaction solution was slowly added to a 10 mL diluted solution of 8.96 mL (75.0 mmol) of dimethylsilyl dichloride in n-hexane under cooling at -78°C, and stirring was continued for 19 hours while returning to room temperature. The solvent and unreacted dimethylsilyl dichloride were distilled off from the reaction solution, and then 15 mL of tetrahydrofuran and 0.94 mL (10.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain a solution 2a.

3.65 g (10.0 mmol) of 4-methoxy-7-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indene synthesized by the method of Synthesis Example 4-2 in the Examples of JP2019-59723A and 15 mL of tetrahydrofuran were charged into a thoroughly dried and argon-purged 100 mL reactor, and 6.8 mL of n-butyllithium solution (hexane solution, 1.55 M, 10.5 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. A saturated aqueous solution of ammonium chloride was added, and the soluble matter was extracted with hexane. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled off and the residue obtained was purified by silica gel column chromatography to obtain 4.64 g (yield 82%) of the target product represented by the following formula (A-2L) (hereinafter referred to as "compound (A-2L)") as an isomer mixture.
^1H NMR (270MHz, _CDCl3 ) δ 7.41-6.64 (9H, s, Ar-H, C=CH-C), 3.93-3.88 (1H, m, Si-CH), 3.75 (3H, s, _-OCH3 ), 3.73 (3H, s, _-OCH3 ), 3.28-3.01 (2H, m, Ar- _CH2 -C), 2.26 (6H, s, _-CH3 ), 1.49-1.43 (18H, s, -C( _CH3 ) ₃ ), 0.30 (3H, s, Si- _CH3 ), 0.15 (3H, s, Si- _CH3 ) ppm.

Example 2A
In a 100 mL reactor that had been thoroughly dried and purged with argon, 1.13 g (2.00 mmol) of the compound (A-2L) obtained in Synthesis Example 2-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged and stirred. To this solution, 2.58 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.00 mmol) was added at room temperature, and then stirring was continued for 3 hours in a 40°C oil bath. This solution was cooled to 0°C, and 0.47 g (2.00 mmol) of zirconium tetrachloride was added, followed by stirring at room temperature for 19 hours. After distilling off the solvent from the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and insoluble matter was removed with Celite on a glass filter. The obtained solution was concentrated under reduced pressure, and n-hexane was added to prepare a suspension. Insoluble matter was filtered off using a glass filter, and the residue was dried under reduced pressure to obtain 0.94 g (yield 65%) of a yellow powdery compound represented by the following formula (A-2) (dimethylsilylene(5,6-dimethyl-2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl)zirconium dichloride, hereinafter referred to as "transition metal compound (A-2)").
^1H NMR (270MHz, _CDCl3 ) δ 7.42 (1H,s,Ar-H), 7.38 (2H,s,Ar-H), 7.30-7.27 (1H,d,J=8.0Hz,Ar-H), 7.10 (1H,s,Ar-H), 6.96-6.95 (1H,d,J=3.1Hz,Ar-H), 6.14-6.12 (1H,d,J=3.4H,Ind-H), 6.01-6.00 (1H,m,Ind-H), 5.83-5.82 (1H,m,Ind-H), 4.08 (3H,s, _-OCH3 ), -3.70 (3H,s, _-OCH3 ), 2.30 (3H,s,-CH ₃ ), 2.27 (3H, s, -CH ₃ ), 1.42 (18H, s, -C(CH ₃ ) ₃ ), 1.04 (3H, s, Si-CH ₃ ), 0.80 (3H, s, Si-CH ₃ ) ppm
FD-mass spectrometry (M ⁺ ): 722

[Comparative Example 1A]
A yellow powdery compound represented by the following formula (A-3) (dimethylsilylene(2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indenyl)zirconium dichloride, hereinafter referred to as “transition metal compound (A-3)”) was synthesized by the method of Example 2A of JP2019-059723A.

[Example 1]
<Preparation of solid catalyst component (X-1)>
Using a reactor equipped with a stirrer having an internal volume of 270 L, 10 kg of silica gel (manufactured by Fuji Silysia Chemical Co., Ltd., cumulative 50% particle size in volume distribution by laser light diffraction scattering method: 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 carrier [S-1]") as the solid carrier [S] was suspended in 77 L of toluene under a nitrogen atmosphere, and then cooled to 0 to 5° C. To this suspension, 19.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) as the component (B) was dropped over 30 minutes. At this time, the temperature in the system was kept at 0 to 5° C. Next, these were contacted at 0 to 5° C. for 30 minutes, and then the temperature in the system was raised to 95° C. over 1.5 hours, and then contacted at 95° C. for 4 hours. The temperature was then lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry having a total volume of 115 L. A portion of the obtained slurry was sampled and analyzed to find that the solid concentration was 122.6 g/L and the Al concentration was 0.612 mol/L.

Next, 30 mL of toluene and 1.63 mL of the toluene slurry (0.2 g solids) were placed in a 200 mL reactor equipped with a stirrer that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Next, 5.0 μmol of Zr in terms of the toluene solution of the transition metal compound (A-1) obtained in Example 1A was added, and these were contacted for 1 hour at a system temperature of 20 to 25°C, after which the supernatant liquid was removed by decantation and the mixture was washed twice with hexane. This resulted in the preparation of a total of 40 mL of slurry of the solid catalyst component (X-1).

<Production of ethylene polymer>
In a SUS autoclave having an internal volume of 1 liter and fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere, and 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-1) in a slurry state were charged, and the temperature and pressure were raised to 80° C. and 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum-dried at 80° C. for 10 hours, to obtain 46.7 g of an ethylene-based polymer. The catalytic activity was 2,330 g-PE/g-solid catalyst component.

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

<Production of ethylene polymer>
The same operation as in <Production of ethylene-based polymer> of Example 1 was carried out, except that 20.0 mg of the solid content of the solid catalyst component (X-2) in a slurry state was charged instead of the solid catalyst component (X-1), to obtain 88.5 g of an ethylene-based polymer. The catalytic activity was 8,850 g-PE/g-solid catalyst component. The results are shown in Table 9.

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

<Production of ethylene polymer>
The same operation as in <Production of ethylene-based polymer> of Example 1 was carried out, except that 250 mg of the solid content of the solid catalyst component (X-3) in a slurry state was charged instead of the solid catalyst component (X-1), to obtain 45.2 g of an ethylene-based polymer. The catalytic activity was 2,830 g-PE/g-solid catalyst component. The results are shown in Table 9.

In Examples 1 and 2, which used the transition metal compound [A] of the present invention (a bridged (2-indenyl) (1-indenyl) type compound having a substituent at a specific position of the 2-indenyl ring), the MFR of the resulting ethylene polymer was reduced and the molecular weight was increased, compared to Comparative Example 1, which used a bridged (2-indenyl) (1-indenyl) type compound without the aforementioned substituent.

Claims (8)

A transition metal compound [A] represented by the following general formula [1]:
(In the general formula [1], M is a transition metal atom of Group 4 of the periodic table,
n is 2 ;
X's are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms , or nitrogen-containing groups , and may be the same or different from each other , and the nitrogen-containing group is a dimethylamino group or a diethylamino group;
Q is an atom of Group 14 of the periodic table;
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms;
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent 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 ;
^R3 and ^R4 each independently represent 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 ³ and R ⁴ may be bonded to each other to form a 5- to 8-membered ring condensed with the indenyl ring moiety and made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon which may have a substituent ;
R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring containing Q, which may have a substituent, is a 3- to 8-membered ring, and is a saturated ring . In the general formula [1],
M is a zirconium atom or a hafnium atom ;
The transition metal compound [A] according to claim 1, wherein Q is a carbon atom or a silicon atom. The transition metal compound [A] according to claim 2, wherein in the general formula [1], Q is a silicon atom. The transition metal compound [A] according to claim 3 , wherein in the general formula [1], R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms. An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 4 . Furthermore, [B] [B-1] an organometallic compound,
The olefin polymerization catalyst according to claim 5, comprising at least one compound selected from the group consisting of [B-2] an organoaluminum oxy compound, and [B-3] a compound that reacts with the transition metal compound [A ] to form an ion pair. 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 5 or 6 . 8. The method for producing an olefin polymer according to claim 7 , 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.