JP2021155345A - Transition metal compound, olefin polymerization catalyst, and method for producing olefin polymer - Google Patents

Abstract

To provide a transition metal compound that can produce olefin-based polymer typified by ethylene-based polymer having many long-chain branches introduced, high molecular weight, and narrow molecular weight distribution, and to provide an olefin polymerization catalyst and a method for producing olefin polymer.SOLUTION: Provided is, as an example, a transition metal compound represented by the formula (A-1).SELECTED DRAWING: None

Description

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

Olefin polymers are molded by various molding methods and are used in various applications. For example, an extrusion-molded ethylene-based polymer is used for a film or sheet used for packaging foods, liquids, daily necessities, and the like. The properties required for the olefin polymer differ depending on the molding method or application, but for example, when performing T-die molding, stable molding is possible even at high speed (high-speed film formation processability), and neck-in. Is required to have processing performance such as small size.

Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complicated long-chain branched structure, so that it has a large melt tension, and as a result, it has good molding processability such as a small neck-in, so it can be used for various purposes. It is offered to. However, there are still problems that the mechanical strength such as tensile strength, tear strength or impact resistance of the molded product is low, and the high-speed film formation processability in T-die molding is inferior.

On the other hand, ethylene-based polymers produced using Ziegler-Natrix or metallocene-catalyzed materials, in contrast to LDPE, have high tensile strength, tear strength or impact resistance due to their molecular structure and are therefore mechanical. Although it is used for applications that require strength, it has a problem that the melt tension is small and the molding processability is inferior.

In order to solve these problems, a method for producing an ethylene polymer having a long chain branch in the presence of a solid catalyst component composed of two kinds of transition metal compounds and a solid carrier (Patent Documents 1, 2 and the like). Has been proposed.

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

Japanese Unexamined Patent Publication No. 2006-233208 JP-A-2009-144148 JP-A-2019-59933 Japanese Unexamined Patent Publication No. 2019-59723 Japanese Unexamined Patent Publication No. 2019-59724

By the way, when an olefin polymer represented by an ethylene polymer is used in an application such as a pipe where high strength is required, it is desirable that the olefin polymer has characteristics such as high molecular weight and narrow molecular weight distribution. Is done. However, the techniques reported in Patent Documents 3 to 5 and the like have room for further improvement from the viewpoint of increasing the molecular weight of the produced olefin polymer and narrowing the molecular weight distribution.

Therefore, the present invention presents a transition metal compound capable of producing an olefin polymer typified by an ethylene polymer, which has a large number of long-chain branches, a high molecular weight, and a narrow molecular weight distribution, a catalyst for olefin polymerization, and a catalyst for olefin polymerization. An object of the present invention is to provide a method for producing an olefin polymer.

As a result of diligent research to solve the above problems, the present inventors have conducted the above by introducing a substituent at a specific position on the 2-indenyl ring of the crosslinked (2-indenyl) (1-indenyl) type transition metal compound. We have found that the problem can be solved and completed the present invention.

The gist of the present invention is as follows.
[1]
The transition metal compound [A] represented by the following general formula [1].

(In the general formula [1], M is a Group 4 transition metal atom in 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 neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a 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-based derivative group. But they may be different, they may combine with each other to form a ring,
Q is a Group 14 atom of the periodic table,
R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen atoms and 1 to 40 carbon atoms. A hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.
R ² and R ⁵ are independently hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, respectively.
Adjacent substituents of R ^{1 to} R ⁶ may be bonded to each other to form a ring which may have a substituent.
Adjacent substituents of R ^{7 to} R ¹² may be bonded to each other to form a ring which may have a substituent.
R ¹³ and R ¹⁴ 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 is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group.
Q is a carbon atom or a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ independently have 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, and a nitrogen-containing group having 1 to 20 carbon atoms. Alternatively, it is a sulfur-containing group having 1 to 20 carbon atoms.
R ⁷ may have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a substituent containing at least one atom selected from nitrogen, oxygen, and sulfur in the heterocycle. The transition metal compound [A] of the above [1], which is an aromatic complex five-membered ring substituent.

[3]
In the general formula [1],
Q is a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20 or a nitrogen-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ are independently each of 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] of the above [2].

[4]
In the general formula [1], the transition metal compound [A] of the above [3] in which ^{R 1} and R ^{6 are hydrogen atoms.}
[5]
In the general formula [1], the transition metal compound [A] of the above [4] in which ^{R 3} and R ^{4 are hydrogen atoms.}

[6]
In the general formula [1], the transition metal compound [A] of the above [5] in which ^{R 7} and R ^{8 are hydrogen atoms.}
[7]
In the general formula [1], the transition metal compound [A] of the above [6] in which ^{R 10} and R ^{11 are hydrogen atoms.}

[8]
In the general formula [1], the transition metal compound [A] of the above [7], wherein at least one of ^{R 2} and R ^{5 is a hydrocarbon group having 1 to 20 carbon atoms.}
[9]
A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of [1] to [8].

[10]
Furthermore, [B] [B-1] organometallic compounds,
[9] The above-mentioned [9], which comprises at least one compound selected from the group consisting of [B-2] an organic aluminum oxy compound and a compound which reacts with [B-3] a transition metal compound [A] to form an ion pair. Catalyst for olefin polymerization.

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

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

According to the transition metal compound, the catalyst for olefin polymerization, and the method for producing an olefin polymer according to the present invention, an olefin-based polymer typified by an ethylene-based polymer in which many long-chain branches are introduced, the molecular weight is high, and the molecular weight distribution is narrow. A polymer can be produced.

Hereinafter, the transition metal compound and the like according to the present invention will be described in more detail.
[Transition metal compound [A]]
The transition metal compound [A] according to the present invention (hereinafter, 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, in which the transition metal compound [A] is selected to be electrically neutral.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a 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-based 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, a plurality of Xs may be the same or different from each other, or may be combined with each other to form a ring. When a plurality of the rings are present, the rings may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine or bromine.
Examples of the hydrocarbon group include
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2- Il group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3) -Methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamil group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 , 3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 4,4-dimethylpentyl group and other linear or branched alkyl groups;
Vinyl group, allyl group, propenyl group (propa-1-ene-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-diene-1) -Il group), porcine-3-ene-1-yl group, crotyl group (but-2-en-1-yl group), porcine-3-en-2-yl group, metalryl group (2-methylallyl group) , Buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbuta-3-ene-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) A linear or branched alkenyl group such as group) or an unsaturated double bond-containing group;
Linear or branched alkynyl groups such as ethynyl group, propa-2-in-1-yl group, propargyl group (propa-1-in-1-yl group) or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group (4-iso-propylbenzyl group), 2,4,6 Aromatic-containing linear chain such as -tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group) Or branched alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, trill group (methylphenyl group), xsilyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3) 5,6-Tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Examples thereof include aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group and ferrosenyl group.

Among the above hydrocarbon groups, a methyl group, an iso-butyl group, a neopentyl group, a siamil group, a benzyl group, a phenyl group, a tolyl group, a xsilyl group, a mesityl group and a cumenyl group are preferable.

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 and a trifluorophenyl group. , Tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion.

Among the halogen-containing groups, a pentafluorophenyl group is preferable.
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, and a tris (tris). Trimethylsilyl) silyl group, trimethylsilylmethyl group and the like can be mentioned.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
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 and a benzyloxy group. Group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group , 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, periodate anion.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.
Examples of the sulfur-containing group include a mesyl group (methanesulphonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), a nonafryl group (nonafluorobutanesulfonyl group), and the like. Examples thereof include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a trifurate group (trifluoromethanesulfonate group), and a nonafrate group (nonafluorobutanesulfonate group).

Among the sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) is preferable.
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 and a piperidinyl. Examples thereof include a group, a morpholic group, a pyrrolyl group, and a bistrifurylimide group.

Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.
Examples of the phosphorus-containing group include hexafluorophosphate anion.

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, and (benzyl) (tris (pentafluorophenyl)). ) Borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is an aryl group or halogen atom which may independently have a hydrogen, an alkyl group, a substituent, etc. The group represented by) is mentioned.

Examples of the aluminum-containing group include, for example.

(M represents M in the general formula (1))
_{Examples thereof include a group represented by AlR 4} (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.) capable of forming the above.

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), and a 2,4-hexadienyl group. , 1,4-Diphenyl-1,3-Pentadienyl group, cyclopentadienyl group and the like, metallocyclopentene groups can be mentioned.

Examples of the neutral ligand capable of coordinating with a lone electron pair include ethers such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, pyridine, picolin and lutidine. Examples thereof include heterocyclic compounds such as oxazoline, oxazole, thiazole, imidazole and thiophene, and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine.

<< Q >>
In the general formula [1], Q is a Group 14 atom of the periodic table, for example, a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom. Is.

《R ^{1 to} R ¹⁴ 》
In the general formula [1],
R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen atoms and 1 to 40 carbon atoms. A hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.
R ² and R ⁵ are independently hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups.

Examples of the hydrocarbon groups having 1 to 40 carbon atoms as R ^{1 to} R ¹⁴ include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples thereof include the above-mentioned example of X. Specific examples of hydrocarbon groups can be given.

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 above-mentioned hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include, for example.
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group , 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group , Tert-Pentyl group (1,1-dimethylpropyl group), sheamil group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (1,1-dimethylbutyl group) 2-Methylpentane-2-yl group), 3-methylpentane-2-yl group, 4-methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 -Dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, heptan-4 -Il group, 2,4-dimethylpentane-2-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4 A linear or branched alkyl group having 1 to 40 carbon atoms, such as a −yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group. ;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, crotyl group, buta-3-en-2-yl group, metalryl group, pig-1,3 -Dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-ene- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1 , 4-diene-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5- En-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-ene- 1-yl group, 3-methyl-penta-4-ene-1-yl group, 2-methyl-penta-4-ene-1-yl group, hexa-5-en-2-yl group, 4-methyl- Penta-3-ene-1-yl group, 3-methyl-penta-3-ene-1-yl group, 2,3-dimethyl-but-2-ene-1-yl group, 2-methylpenta-4-ene -2-Il group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1 , 3-Diene-1-yl group, 2,3-dimethyl-buta-1,3-diene-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadi) A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as an enyl) propan-2-yl group and a 2- (cyclopentadienyl) ethyl group;
Ethynyl group, propa-2-in-1-yl group, propargyl group, porcine-1-in-1-yl group, porcine-2-in-1-yl group, porcine-3-in-1-yl group, Penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta- 1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4-in-2-yl group, hexa-1- In-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, 2,2-dimethyl-but-3-in A linear or branched alkynyl group or unsaturated triplet having 2 to 40 carbon atoms such as a -1-yl group, a hexa-4-in-1-yl group, and a hexa-5-in-1-yl group. Bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl 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-phenylpentane-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-2 -Il group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-3-ene-1-yl group, 1,1,2-triphenylethyl group, trityl group (Triphenylmethyl group), tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2- (2-methylphenyl) ethyl group, 2- (4-) Methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) Ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropi Lu group, cinnamyl group (3-phenylallyl group), neofil group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutane-2-yl group , Cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) ) Propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, (1- Benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azulenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- Aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms such as (1-azulenyl) ethyl groups and unsaturated double bond-containing groups;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl 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] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-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), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill group, xsilyl group, mesityl group, cumenyl group, juryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl Group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl group , Plenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group, etc. Examples thereof include aromatic substituents having 6 to 40 carbon atoms.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 1-heptyl group. Group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl Group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, heptane-4-yl group, 2,4-dimethylpentane-2-yl group, 3-Ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentane-2-yl Groups are preferred, such as 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-dimethylpentane. A -2-yl group and a 2,4,4-trimethylpentane-2-yl group are more preferable.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, buta-3-ene-1-yl group, crotyl group and metallicl Group, penta-4-en-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-ene-1-yl group, 2-methylpenta-4-en-2- Il group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group and the like are preferable, and vinyl group, allyl group, buta-3-ene-1-yl group and penta. A -4-en-1-yl group, a prenyl group, and a hexa-5-ene-1-yl group are more preferable.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, propa-2-in-1-yl group, propargyl group, buta-2-in -1-yl group, buta-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-but-1-in-1 -Il group, 3,3-dimethyl-buta-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group and the like are preferable, and propa-2- More preferred are an in-1-yl group, a propargyl group, a buta-2-in-1-yl group and a buta-3-in-1-yl group.

Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4 , 6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl Group, Benzyl group, Kumil group, 1,1-diphenylethyl group, Trityl group, 2-Phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group , 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3) , 5-Di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neofil 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- A fluorenyl) diphenylmethyl group, a 2- (9-fluorenyl) ethyl group and the like are preferable, and a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group and a 3-phenylpropyl group are preferable. , Synamyl groups 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 and 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-methylcyclo Heptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [2.2 .1] Heptane-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like are preferable, and cyclopentyl group, cyclopentyl group, etc. More preferably, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group.

Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xsilyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group , Binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl group and the like are preferable, and phenyl group, trill group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group preferable.

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, and a 3,3,3-tri. Fluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl Group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl Group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethyl Biphenyl 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, tri Fluoromethylthio groups, etc. may be mentioned.

Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-tri Fluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, Trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, trifluoromethylthio group are preferable, and trifluoromethyl group is preferable. More preferably, a methyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group.

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, and a tris (tris). Trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, di-n-butyl (indenyl) silyl Group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri- Examples thereof include an iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris (trimethylsilyl) silylphenyl group, and a 3,5-bis (trimethylsilyl) phenyl group.

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-Triphenylsilylphenyl group, 3,5-bis (trimethylsilyl) phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4 -Tri-iso-propylsilylphenyl group and 3,5-bis (trimethylsilyl) phenyl group are more preferable.

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, and a metallicyloxy group. , Plenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxy Phenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl Group, methoxypropyl group, allyloxypropyl 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, frill group, methyl frill group, tetrahydrofuryl group , Pyranyl group, tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like.

Among the oxygen-containing groups, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, and a tert. -Butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, Allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldi Oxanyl 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, frill group, methyl frill group, tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group and phenoxy are preferable. 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, frill group, methyl frill group, benzofuryl group and dibenzofuryl group are more preferable.

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 morpholic group and an azepinyl group. Didimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidini Ruvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl -4-Dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, Kinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolill group, phenylpyrrolill 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, Examples thereof include a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

Among the nitrogen-containing groups, an amino group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, and a dibenzylamino group. Group, pyrrolidinyl group, piperidinyl group, morpholic group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethyl Aminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl Group, tetramethyldurolidinyl 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, benzoimidazolyl group, oxazolyl group, Oxazoridinyl group, benzoxazolyl group and the like are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso -Propyl-4-dimethylaminophenyl group, duroridinyl group, tetramethylduroridinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferable.

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

Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofryl group, a thienotienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Adjacent substituents of R ^{1 to} R ⁶ (eg, 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 ) are relative to each other. It may be bonded to form a ring which may have a substituent. The ring formed in this case is composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which is fused to the indenyl ring portion and may have a substituent. A 5- to 8-membered ring is preferred. 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, and in this case, the structure in which the ring and the indenyl ring portion of the mother nucleus are combined is, for example, benzoinde. Nyl ring, tetrahydroindacenyl ring, tetrahydrobenzoindenyl ring (these may have a substituent), benzoindenyl ring, tetrahydroindacenyl ring (these may have a substituent). It may have).

Adjacent substituents of R ^{7 to} R ¹² (eg, R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ and R ¹² ) are relative to each other. It may be bonded to form a ring which may have a substituent. The ring formed in this case is composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which is fused to the indenyl ring portion and may have a substituent. A 5- to 8-membered ring is preferred. 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, and in this case, the structure in which the ring and the indenyl ring portion of the mother nucleus are combined is, for example, benzoinde. Nyl ring, tetrahydroindacenyl ring, tetrahydrobenzoindenyl ring, tetrahydrofluorenyl ring, fluorenyl ring (these may have a substituent), benzoindenyl ring, tetrahydroindasse Nyl rings (these may have substituents) are preferred.

R ¹³ and R ¹⁴ may combine with each other to form a ring containing Q. The ring formed in this case is preferably a saturated or unsaturated ring having a 3- to 8-membered ring which may have a substituent. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is preferably a 4- to 6-membered ring, and in this case, ^{as a structure in which R 13} and R ¹⁴ and Q are combined, for example, a substituted cyclobutane ring and a substituted cyclo Examples include a pentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletan) ring, a substituted silacyclopentane (sirolan) ring, a substituted silacyclohexane (silinan), and a substituted silafluorene ring, and a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclobutane ring. A silacyclopentane ring is preferred.

R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. It is a group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom.

R ² and R ⁵ 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, and more preferably having 1 to 20 carbon atoms. It is a hydrocarbon group, 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 more preferably a hydrocarbon group having 1 to 20 carbon atoms. ..

R ⁹ , R ¹² , R ¹³ and R ¹⁴ are independently, preferably hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, respectively. More preferably, it is 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 ^{R 7} , R ⁹ and R ^{12 , especially in R 7} , the oxygen-containing group, the nitrogen-containing group or the 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 is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group.
Q is a carbon atom or a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ independently have 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, and a nitrogen-containing group having 1 to 20 carbon atoms. Alternatively, it is a sulfur-containing group having 1 to 20 carbon atoms.
R ⁷ may have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a substituent containing at least one atom selected from nitrogen, oxygen, and sulfur in the heterocycle. A transition metal compound [A-1] which is an aromatic complex five-membered ring substituent can be mentioned.

As a more preferable embodiment of the transition metal compound [A-1],
In the general formula [1],
Q is a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20 or a nitrogen-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ are independently each of 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-2] is mentioned.

A more preferable embodiment of the transition metal compound [A-2] is a transition metal compound [A-3] ^{in which R 1} and R ^{6 are hydrogen atoms in the general formula [1].}
A more preferable embodiment of the transition metal compound [A-3] is a transition metal compound [A-4] ^{in which R 3} and R ^{4 are hydrogen atoms in the general formula [1].}

A more preferable embodiment of the transition metal compound [A-4] is a transition metal compound [A-5] ^{in which R 7} and R ^{8 are hydrogen atoms in the general formula [1].}
A more preferable embodiment of the transition metal compound [A-5] is a transition metal compound [A-6] ^{in which R 10} and R ^{11 are hydrogen atoms in the general formula [1].}

In a more preferable embodiment of the transition metal compound [A-6], ^{at least one of R 2} and R ⁵ in the general formula [1] is a hydrocarbon group having 1 to 20 carbon atoms (R ² and R). ^When only one of 5 is a hydrocarbon group having 1 to 20 carbon atoms, the other one is a hydrogen atom), more preferably R ² and R ⁵ are independently 1 to 20 carbon atoms, respectively. The transition metal compound [A-7] which is a hydrocarbon group of the above can be mentioned.

As a more preferable embodiment of the transition metal compound [A-7], ^{at least one of R 9} and R ¹² in the general formula [1] has a hydrocarbon group having 1 to 20 carbon atoms and 1 to 20 carbon atoms. It is a silicon-containing group, 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 ( ^{only one of R 9} and R ¹² is these). When it is a substituent, the other one is a hydrogen atom.) Transition metal compound [A-8] can be mentioned.

In the transition metal compound [A], a 5-membered ring (hereinafter referred to as a parent skeleton) containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur, which is one of the options of ^{R 7} , R ⁹ and R ^12. Examples of the complex ring-type aromatic group which may have a substituent, which is also referred to as “complex 5-membered ring”), include groups represented by the following general formulas [4a] to [4h]. Be done.

In the general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R ^d is an independent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which are the same or different. May be good.

The wavy lines in the general formulas [4a] to [4h] indicate the binding site with the indenyl ring.
Examples of the hydrocarbon groups having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms among those listed as examples of the above-mentioned hydrocarbon groups having 1 to 40 carbon atoms as ^{R 1 to} R ^{14 described above.} , And preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec- Butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Cyclooctenyl group, norbornyl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group , 2-Phenylethyl group, 3-Phenylpropyl group, Synamyl group, Phenyl group, Trill group, Xylyl group, Mesityl group, Cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-Tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group Groups and ferrocenyl groups are mentioned, and more preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group and allyl group. , Cyclopentyl group, Cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, trill group, xsilyl group, mesityl group, naphthyl group, biphenyl group, terphenyl group.

R ^ds are 5-8 members together with the atoms of the complex 5-membered ring moiety, which may have substituents, each independently ^{bonded to each other between adjacent R ds and fused to the complex 5-membered ring moiety.} Saturated or unsaturated hydrocarbon groups constituting the ring may be formed. The 5- to 8-membered ring is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. For example, a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzopyrazole ring and the like can be mentioned.

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

<< Example of Transition Metal Compound [A] >>
Specific examples of the transition metal compound [A] will be shown below, but the scope of the present invention is not particularly limited by this.

For convenience, the ligand structure of the transition metal compound [A] excluding the portion represented by MXn (metal moiety) is a 2-indenyl ring moiety, a 1-indenyl ring moiety, an indenyl ring moiety R ¹ , R ⁶ and R ^8. Substituents, indenyl ring moieties R ² , R ⁵ , R ⁹ , and R ¹² substituents, indenyl ring moieties R ³ , R ⁴ , R ¹⁰ , and R ¹¹ substituents, 1-indenyl ring moieties R ⁷ substituents, crosslinks Divide into 7 parts structure. Abbreviations 2- indenyl ring moiety alpha, abbreviations 1-indenyl ring moiety beta, the abbreviation of the indenyl ring moiety R ^1, R ⁶ and R ⁸ substituents gamma, indenyl ring moiety ^{R 2, R 5, R 9} , And R ¹² substituent abbreviation δ, indenyl ring moiety R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituent abbreviation ε, 1-indenyl ring moiety R ⁷ substituent abbreviation ζ, bridge moiety structure The abbreviation for each substituent is η, and the abbreviations for each substituent are shown in [Table 1] to [Table 7].

The wavy lines in the above [Table 1] to [Table 2] indicate the binding site with the crosslinked portion.

^{The R 1} , R ⁶ and R ⁸ substituents in [Table 3] may be the same or different from each other in the combination.

^{The R 2} , R ⁵ , R ⁹ , and R ¹² substituents in [Table 4] may be the same or different from each other in the combination. However, the R ² , R ⁵ and R ⁹ substituents are not δ-1.

^{The R 3} , R ⁴ , R ¹⁰ , and R ¹¹ substituents in [Table 5] may be the same or different from each other in the combination.

Specific examples of the metal portion MXn _{is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2, Ti (1,3-butadienyl), Ti (1,3-pentadienyl), Ti (2,4-hexadienyl), Ti _{(1,4-diphenyl-1,3-pentadienyl), Ti (CH 2 -Si (} Me ) ₃ ) ₂ , Ti (ОMe) ₂ , Ti (ОiPr) ₂ , Ti (NMe ₂ ) ₂ , Ti (ОMs) ₂ , Ti (ОTs) ₂ , Ti (ОTf) ₂ , ZrF ₂ , ZrCl ₂ , ZrBr _{2 , ZrI 2, Zr (Me)} 2, Zr (Bn) 2, Zr (Allyl) 2, Zr (CH 2 -tBu) 2, Zr (1,3- butadienyl), Zr (1,3-pentadienyl), Zr (2,4-hexadienyl), Zr _{(1,4-diphenyl-1,3-pentadienyl), Zr (CH 2 -Si (} Me) 3) 2, Zr (ОMe) 2, Zr (ОiPr) 2, Zr ( _{NMe 2) 2, Zr (ОMs} ) 2, Zr (ОTs) 2, Zr (ОTf) 2, HfF 2, HfCl 2, HfBr 2, HfI 2, Hf (Me) 2, Hf (Bn) 2, Hf (Allyl ) ₂ , Hf (CH _2- tBu) ₂ , Hf (1,3-butadienyl), Hf (1,3-pentadienyl), Hf (2,4-hexadienyl), Hf (1,4-diphenyl-1,3) -Pentadienyl), Hf (CH _2- Si (Me) ₃ ) ₂ , Hf (ОMe) ₂ , Hf (ОiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf ( ОTf) _{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, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and ОMs is a methanesulfonate. The group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

According to the above notation, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-5 in [Table 2], the indenyl ring moiety R ¹ , R ⁶ and R ⁸ Γ-1,2-indenyl ring moiety R ² and R ⁵ all substituents in [Table 3] δ-7, 2-indenyl ring moiety R ³ and R ^{4 in [Table 4]} The substituents are ε-1, 1-indenyl ring moiety R ^{7 in} [Table 5], and the substituents are ζ-30 in [Table 6], and the 1-indenyl ring moiety R ⁹ substituent is in [Table 4]. the δ-38,1- indenyl ring moiety R ¹² substituents [Table 4] in [delta]-3, cross-linking moiety is a combination of eta-20 in Table 7], MXn metal parts ZrCl ₂ In the case of, the compound represented by the following formula [5] is exemplified.

Also, 2-beta-1 indenyl ring moiety is alpha-1,1-indenyl ring moiety in Table 1 in [Table 2], both the indenyl ring moiety R ^1, R ⁶ and R ⁸ substituents are [Table 3] gamma-1 in, indenyl ring moiety R ^2, R ^5, R ⁹ and R ¹² δ-2 in both substituents [Table 4], the indenyl ring moiety R ^3, R ^4, R ¹⁰ And R ¹¹ substituents are ε-1 in [Table 5], 1-indenyl ring moiety R ⁷ substituents are ζ-2 in [Table 6], and crosslinked moieties are η-20 in [Table 7]. When the MXn of the metal portion is ZrCl ₂ , the compound represented by the following formula [6] is exemplified.

In addition, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1, 2-indenyl ring moiety in [Table 2], and the R ^{1 and R 6} substituents are all [ The γ-2,2-indenyl ring moiety R ² and R ⁵ substituents in [Table 3] are all in [Table 4], and the δ-2, 1-indenyl ring moiety R ⁷ substituents in [Table 6] are in [Table 6]. ζ-12, 1-indenyl ring moiety R ⁸ Substituent is γ-1, 1-indenyl ring moiety R ^{9 in} [Table 3] δ-42, 1-indenyl ring moiety R 9 Substituent is δ-42, 1-indenyl ring moiety R ¹⁰ Substituent is ε-1,1-indenyl ring moiety R in ^{[Table 5] 11 Substituent is ε-12 in} [Table 5], 1-indenyl ring moiety R 12 Substituent is in [Table 4] When δ-3 and the crosslinked portion are composed of a combination of η-31 in [Table 7] and MXn of the metal portion is HfMe ₂ , a compound represented by the following formula [7] is exemplified.

In addition, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1, 2-indenyl ring moiety in [Table 2], and the R ^{1 and R 6} substituents are all [ The γ-1,2-indenyl ring moiety R ² substituent in [Table 3] is δ-7 in [Table 4], and the indenyl ring moiety R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituents are all [Table 3]. The ε-1,2-indenyl ring moiety R ⁵ substituent in [5] is δ-2 in [Table 4], and the 1-indenyl ring moiety R ⁷ substituent is ζ-1,1- in [Table 6]. The indenyl ring moiety R ^{8 substituent is γ-9 in} [Table 3], the 1-indenyl ring moiety R 9 and R ¹² substituents are all δ-22 in [Table 4], and the crosslinked moiety is [Table 7]. When the MXn of the metal portion is Ti (1,3-pentadienyl), which is composed of the combination of η-4 in the medium, the compound represented by the following formula [8] is exemplified.

Further, the transition metal compound [A] has two surfaces (front surface and back surface) of an indenyl ring portion that is bonded to the central metal with the crosslinked portion interposed therebetween. Therefore, when the 2-indenyl ring moiety R ² and the R ⁵ substituent are not the same and there is no plane of symmetry in the 2-indenyl ring moiety, two types represented by the following general formula [9a] or [9b] are used as an example. Structural isomers are present.

^{Similarly, if the substituents R 2} and R ⁵ of the 2-indenyl ring moiety are the same but the substituents R ¹³ and R ^{14 of} the crosslinked moiety are not the same, the following general formula [10a] or [10b] is an example. ] There are two types of structural isomers.

Purification, fractionation, or selective production of structural isomers of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. As known production methods, in addition to those mentioned as the production method of the transition metal compound [A], Japanese Patent Application Laid-Open No. 10-109996, "Organometrics 1999, 18, 5347.", "Organometrics 2012, 31, 4340. , And the manufacturing method disclosed in Japanese Patent Publication No. 2011-502192.

Within the range 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, and structural isomers may be used. May be used alone, or a mixture of two or more structural isomers may be used. Further, one or more transition metal compounds other than the transition metal compound [A] may be used in combination as long as the effects of the present invention are not impaired. At this time, the transition metal compound [A] may have any of the above embodiments.

<< Production method of transition metal compound [A] >>
The transition metal compound [A] can be prepared by using a conventionally known method, for example, the method described in JP-A-2019-59933 [097] to [0115], or the method described in JP-A-2019-59724. ] the method according to ^{~ [0116], R 1 ~R} 14, Q, M, by read as synonymous with those described in X and n above general formula [1] can be produced.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization of the present invention contains the transition metal compound [A] of the present invention.
A typical example of the catalyst for olefin polymerization of the present invention is a catalyst for ethylene polymerization.

(Compound [B])
The catalyst for olefin polymerization of the present invention is preferably further [B-1] an organometallic compound, preferably an organometallic represented by the following general formulas (B-1a), (B-1b) or (B-1c). Compound (hereinafter also referred to as "component (B-1)"),
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In the general formula (B-1a), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, where X represents a halogen atom and m is 0. <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ... (B}} -1b)
[In the general formula (B-1b), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t … (B-1c)
[In the general formula (B-1c), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, and M ^b is derived from Mg, Zn and Cd. Selected, X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
[B-2] an organoaluminum oxy compound (hereinafter, also referred to as “component (B-2)”) and a compound that reacts with [B-3] transition metal compound (A) to form an ion pair (hereinafter, “component”). (B-3) ”), which includes at least one compound [B] (hereinafter, may be referred to as“ component (B) ”) selected from the group consisting of).

As the organometallic compound [B-1], the compound disclosed in JP-A-11-315109 or EP0874005A can be used without limitation.
The organic metal compound [B-1] is preferably represented by the general formula (B-1a), and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, and tri. Trialkylaluminum such as octylaluminum and tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkylaluminum sesquihalides such as aluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalide such as ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride , Dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum Examples thereof include alkylaluminum hydride such as hydride, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and dialkylaluminum alcoxyside such as diisobutylaluminum ethoxide.

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

Examples of the compound [B-3] that reacts with the transition metal compound (A) to form an ion pair include JP-A No. 1-501950, JP-A No. 1-502036, and JP-A-3-179005. , Luisic acid, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. Furthermore, heteropoly compounds and isopoly compounds can be used without limitation.

In the olefin polymerization catalyst according to the present invention, when an organic aluminum oxy compound [B-2] such as methylaluminoxane is used in combination as a co-catalyst component, it not only exhibits extremely high catalytic activity for olefins such as ethylene, but also is a solid. Since a solid carrier component containing a co-catalyst component can be easily prepared by reacting with active hydrogen in the state carrier, it is preferable to use the organic aluminum oxy compound [B-2] as the component (B).

(Solid support [S])
The catalyst for olefin polymerization of the present invention preferably contains a solid support [S] (hereinafter, may be referred to as “carrier [S]” or “component (S)”).

The solid support [S] is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2, and the} like, or a composite or mixture containing these. It can also be used, for example natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TIO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TiO _2- MgO or the like can be used. Of these, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , Mg _{CO 3} , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Although the properties of the porous oxide differ 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, and a specific surface area of 50 to 1000 m ^2. It is in the range of / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of ^{0.3 to 3.0 cm 3 / g.} Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane having a structure represented by the following general formula (Sa) or (Sb), a repeating unit represented by the following general formula (Sc), and the following general formula ( Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit represented by Sd) as a structure.

In the general formulas (S-a) to (S-d), R ^e is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group and an ethyl group. Group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group , Octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, trill group, ethylphenyl group and other hydrocarbon groups can be exemplified, and methyl group, ethyl group and isobutyl group are preferable, and methyl group is particularly preferable. preferable. Further, ^{a part of R e} may be replaced with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on ^{R e.} A straight line in (Sc) and (Sd) in which one is not connected to an atom indicates a bond with another atom (not shown).

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

Unlike the conventionally known carrier for an olefin polymerization catalyst, the solid aluminoxane compound does not contain an inorganic solid component such as silica or alumina or an organic polymer component such as polyethylene or polystyrene, and is solidified with an alkylaluminum compound as a main component. It is a thing. "Solid" means that the aluminoxane component remains substantially solid in the reaction environment in which it is used. More specifically, as described later, when the transition metal compound [A] is brought into contact with the aluminoxane component to prepare an olefin polymerization catalyst (eg, an ethylene polymerization catalyst), and the prepared olefin polymerization catalyst When the polymerization of an olefin (eg, ethylene) (for example, suspension polymerization) is carried out using the above, the aluminoxane component maintains a substantially solid state.

The simplest method is to visually confirm whether or not the aluminoxane component is in a solid state, but it is often difficult to visually confirm, for example, during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after the polymerization and the state of adhesion to the reactor. On the contrary, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the aluminoxane component is eluted in the polymerization environment, the gist of the present invention is not deviated. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of abundance of the amorphous polymer, but the polymer bulk density is preferable from the viewpoint of quantification. The bulk density is usually 0.01 to 0.9, preferably in the range of 0.05 to 0.6, more preferably 0.1 to 0.5.

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

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

As the solid aluminoxane compound, known solid aluminoxane can be used endlessly, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. As known manufacturing methods, for example, JP-A-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. Examples thereof include the production methods described in Japanese Patent Application Laid-Open No. −38410, Japanese Patent Application Laid-Open No. 2000-95810, and International Publication No. 2010/55652.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. First, the particle size of each particle is calculated by the following formula after measuring the length of the particle image sandwiched between two parallel lines in the horizontal direction and the vertical direction.

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

Weight average particle size = Σnd ⁴ / Σnd ³
(N; number of particles, d; particle size)
The solid aluminoxane compound preferably 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, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The obtained inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, an ionic crystalline compound having a layered crystal structure such _{as hexagonal fine packing type, antimony type, CdCl 2} type and CdI _{2 type can be exemplified.}

Furthermore, as clays and clay minerals, kaolin, bentonite, wood section clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, rhokuday stone group, parigolskite, kaolinite, nacrite, dicite, etc. Halloysite etc.
The ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples include crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ and H _{2 O.}

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method and having a radius of 20 Å or more. Is particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.

When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat the clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as _{TiCl 4} , ZrCl _4, and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions And so on. These compounds are used alone or in combination of two or more. Further, when these compounds are intercalated _{, metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , and Ge (OR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as _{SiO 2 can coexist.} In addition, examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, one type may be used alone, or two or more types may be used in combination.

Of these, preferred are clays or clay minerals, with particular preference being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound 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. Specifically, a polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. The polymers produced as, and their variants can be exemplified.

<Usage and order of addition of each component>
The catalyst for olefin polymerization according to the present invention can be prepared by mixing and contacting the component (A), optionally the component (S), and optionally the component (B) in an inert hydrocarbon.

As a method of contacting each component, paying attention to the order of contact, for example,
(I) Method of contacting component (B) with component (A) (ii) Method of contacting component (A) with component (S) (iii) Contacting component (S) with component (B), then component Method of contacting (A) (iv) Method of contacting component (B) with component (A) and then contacting component (S) (v) Contacting component (S) with component (B), then component A method of contacting a mixture of (A) and component (B),
(Vi) Examples thereof include a method in which the component (B) is brought into contact with the component (S), the component (B) is further brought into contact with the component (S), and then a mixture of the component (A) and the component (B) is brought into contact with the component (S). When a plurality of types of the component (B) are used, the components (B) may be the same or different from each other. Of the above methods, (i), (ii), (iii) and (iv) are preferable.

In each of the methods showing the contact sequence form, in the step including the contact between the component (S) and the component (B) and the step including the contact between the component (S) and the component (A), the component (G) is used. By coexisting with the above, fouling during the polymerization reaction is suppressed, and the particle properties of the produced polymer are improved. As the component (G), a compound having a polar functional group can be used, a nonionic (nonionic) surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, and a polyalkylene oxide alkyl ether are used. , Alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, N-acylamino acid are more preferable. One of these may be used, or two or more thereof may be used in combination.

Examples of the solvent used for preparing the olefin polymerization catalyst according to the present invention include an inert hydrocarbon solvent, and specifically, fats such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Group hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, etc. The olefin itself can be used as a solvent depending on the type of the olefin to be polymerized.

In the contact between the component (B) and the component (S), the reaction site in the component (B) and the reaction site in the component (S) are chemically bonded to each other, and the component (B) and the component (S) are chemically bonded. ) Is formed. The contact time between the component (B) and the 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. It is done in. When the initial contact between the component (B) and the component (S) is abruptly performed, the component (S) collapses due to the reaction heat generation and the reaction energy, and the morphology of the obtained solid catalyst component deteriorates, which is used for polymerization. If so, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between the component (B) and the component (S), the reaction is brought into contact at a lower temperature for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled to react at a rate at which the initial contact temperature can be maintained. Is preferable. The same applies to the case where the component (B) and the component (S) are brought into contact with each other and the component (B) is further brought into contact with each other. The contact weight ratio between the component (B) and the component (S) (weight of the component (B) / weight of the component (S)) can be arbitrarily selected, but the higher the contact weight ratio, the more components (A). ) Can be brought into contact with each other, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of the component (B) to the component (S) [= weight of the component (B) / weight of the component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2. It is 0.0.
When the contact material between the component (B) and the component (S) and the component (A) are brought into contact with each other, the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature. Is usually in the range of −50 to 200 ° C., preferably −50 to 100 ° C.

The molar ratio [(B-1) / M] of the component (B-1) to all the transition metal atoms (M) in the component (A) is usually 0.01 to 100, It is used in an amount such that it is 000, preferably 0.05 to 50,000.

The molar ratio [(B-2) / M] of the component (B-2) to the total transition metal atom (M) in the component (A) of the component (B-2) (aluminum atom equivalent) is usually 10. It is used in an amount of up to 500,000, preferably 200,000 to 100,000.

The molar ratio [(B-3) / M] of the component (B-3) to all the transition metal atoms (M) in the component (A) is usually 1 to 10, preferably 1. It is used in an amount such that it becomes 1 to 5. The ratio of the component (B) to all the transition metal atoms (M) in the component (A) can be determined by inductively coupled plasma emission spectrometry (ICP analysis).

The olefin polymerization catalyst according to the present invention can be used as it is for olefin polymerization, 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 (eg, ethylene) or the like in an inert hydrocarbon solvent in the presence of the catalyst for olefin polymerization according to the present invention. It can be carried out by either a semi-continuous method or a continuous method, and can be carried out under reduced pressure, normal pressure or pressurized. Further, it is desirable that the prepolymerized solid catalyst component is produced in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid catalyst component.

The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent is separated from the suspension, then suspended again in the inert hydrocarbon, and an olefin (eg, ethylene) is introduced into the obtained suspension. Alternatively, an olefin (eg, ethylene) may be introduced after drying.

The prepolymerization temperature is -20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. For the prepolymerization, an olefin containing ethylene as a main component is preferably used.

As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. Further, the component (B) is used as needed, and the organoaluminum compound [B-1a] represented by the general formula (B-1a) is particularly preferably used. When the component (B) is used, the component (B) is the molar ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the transition metal compound [A]. ) Is used in an amount of 0.1 to 10000, preferably 0.5 to 5000.

The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is usually 1 to 1000 g / liter, more preferably 10 to 500 g / liter in terms of the olefin polymerization catalyst / polymerization volume ratio. At the time of prepolymerization, the above-mentioned component (G) may coexist for the purpose of suppressing fouling or improving the particle properties.

Further, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot seating during polymerization, and suppressing the generation of polymer lumps, the component (G) is brought into contact with the prepolymerized solid catalyst component once generated by prepolymerization. May be good.

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

The mixed contact between the olefin polymerization catalyst according to the present invention and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same as described above.
In the method for producing an olefin polymer according to the present invention, a dried prepolymerized solid catalyst component (hereinafter, also referred to as “dry prepolymerized catalyst”) can be used as the catalyst for olefin polymerization. The prepolymerized solid catalyst component is usually dried after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

The prepolymerized solid catalyst component is dried by keeping the prepolymerized solid catalyst component at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of an inert gas. The amount of the volatile component of the obtained dry prepolymerization catalyst is preferably 2.0% by weight or less, preferably 1.0% by weight or less. The smaller the amount of the volatile component of the dry prepolymerization catalyst, the better, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 1 to 48 hours, although it depends on the drying temperature.

Since the dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dry prepolymerization catalyst is used, stable polymerization can be performed because it is not necessary to accompany the solvent used for suspension in the gas phase polymerization system.

[Method for producing olefin polymer]
The method for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the catalyst for olefin polymerization 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 this method, ethylene is polymerized in the presence of the olefin polymerization catalyst of the present invention, or ethylene and ethylene are used. It polymerizes with an olefin having 3 or more and 20 or less carbon atoms.

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

Examples of the polymerization method include a liquid phase polymerization method such as solution polymerization and suspension polymerization and a vapor phase polymerization method, and the suspension polymerization method and the vapor phase polymerization method are preferable.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Such as alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.

When polymerizing an olefin (eg, ethylene) using the catalyst for olefin polymerization according to the present invention, the component (A) is usually 1 × 10 ^-12 to 1 × 10 ^-1 mol, preferably 1 × 10 -12 to 1 × 10 -1 mol, per 1 liter of reaction volume. Is used in an amount such that it is 1 × 10 ^-8 to 1 × 10 ^{−2 mol.} Further, the component (B) is used, and preferably the compound represented by the general formula (B-1a) or the component (B-2) is used.

When polymerizing an olefin (eg, ethylene), the lower limit of the polymerization temperature is 0 ° C., preferably 40 ° C., particularly preferably 60 ° C. The higher the temperature, the more advantageous in terms of heat removal and the like in production on an industrial scale. 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 by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.
The molecular weight of the olefin polymer obtained by the method for producing an olefin polymer according to the present invention can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the above-mentioned component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

When the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, the monomer supplied to the polymerization reaction is ethylene alone or ethylene and an olefin having 3 or more and 20 or less carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-. Α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8 -Dimethano-1,2,3,4,4a, 5,8,8a-Cyclic olefins such as octahydronaphthalene can be mentioned.

Further, a small amount of styrene, vinylcyclohexane, diene or acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc., as long as the effects of the present invention are not impaired. A polar monomer such as methacrylic acid may be supplied.

According to the method for producing an olefin polymer according to the present invention, the transition metal compound [A] has a double bond at the terminal because β-agostic interaction with the growth polymer chain facilitates β-hydrogen desorption. By generating macromers and introducing a specific substituent into the transition metal compound [A], it becomes possible to efficiently incorporate the produced macromers, so that many long-chain branches are introduced and the molecular weight is improved. It is presumed that the resulting olefin polymer can be produced, and that the efficient uptake of the produced macromer reduces the remaining amount of macromer, and at the same time narrows the molecular weight distribution.

[Olefin polymer]
The olefin polymer produced by the present invention (eg, an ethylene polymer) includes a weather resistance stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as long as the object of the present invention is not impaired. , Antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants and the like may be added as necessary.

The olefin polymer produced by the present invention (eg, ethylene-based polymer) can be processed by general film molding, blow molding, injection molding and extrusion molding.
Molds obtained by processing the olefin polymer produced by the present invention (eg, ethylene-based polymer) include films, blow infusion bags, blow bottles, gasoline tanks, extrusion-molded tubes, pipes, and tears. Examples include injection molded products such as caps and daily miscellaneous goods, fibers, and large molded products produced by rotary molding.

The film obtained by processing the olefin polymer (eg, ethylene-based polymer) produced by the present invention is a water packaging bag, a liquid soup packaging bag, a liquid paper container, a lami raw fabric, or a specially shaped liquid packaging bag ( It is suitable for various packaging films such as standing pouches), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging, protective films, infusion bags, agricultural materials, etc., and nylon. , It can also be used as a multilayer film by bonding with a base material such as polyester.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
[Measurement of various physical properties]
The method for measuring the physical characteristics of the ethylene polymer is shown below.

<Melt flow rate (MFR)>
The measurement was carried out under the conditions of 190 ° C. and a 2.16 kg load (kgf).
<Density (D)>
The strands obtained during the MFR measurement were heat-treated at 100 ° C. for 30 minutes, left at room temperature for 1 hour, and then 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 performed as follows using an Agilent GPC-viscosity detector (GPC-VISCO) PL-GPC220.

Two Agilent PLgel Olexis are used for the analysis column, a differential refractometer and a 3-capillary viscometer are used for the detector, the column temperature is 145 ° C., o-dichlorobenzene is used as the mobile phase, and the flow velocity is 1.0 ml. The sample concentration was 0.1% by weight. As the standard polystyrene, one manufactured by Tosoh Co., Ltd. was used. In the molecular weight calculation, the measured viscosity is calculated from the viscometer and the refraction meter, and the number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), and the molecular weight distribution (Mw / Mn, Mz) are calculated from the measured universal calibration. / Mw) was calculated.

<Synthesis of transition metal compound (A)>
[Synthesis Example 1-1]
0.97 g (40.0 mmol) of magnesium pieces was charged into a 200 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. Further, a 15 mL diluted solution of 2-bromo-4,7-dimethyl-1H-indene (2.68 g (12.0 mmol)) synthesized by the method of Example 1 of International Publication No. 2016/188999 was added dropwise (1.0 mL). After the addition, the mixture was heated under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the residue was dropped), and after the completion of the addition, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 7.17 mL (60.0 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 10 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 1a.

In a 100 mL reactor sufficiently dried and substituted with argon, 1.44 g (10.0 mmol) of 4,7-dimethyl-1H-indene and 15 mL of tetrahydrofuran were charged, and 6.60 mL of n-butyllithium solution (hexane solution, 1. 59M (10.5 mmol) was added, and the mixture was stirred at room temperature for 2 hours to obtain a solution 1b.

The solution 1b was added dropwise to the solution 1a cooled to −78 ° C., and stirring was continued for 15 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off and the obtained residue is purified by silica gel column chromatography. The target product represented by the following formula (A-1L) (hereinafter referred to as "compound (A-1L)"). ) Was obtained as an isomer mixture of 3.01 g (yield 87%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.12-6.86 (6H, m, Ar-H & C = CH-C), 6.64-6.62 (1H, dd, J = 5.1 and 1.6Hz) , C = CH-C), 3.85 (1H, s, Si-CH), 3.20 (2H, s, Ar-CH _2- C), 2.41-2.40 (6H, s,- CH ₃ ), 2.31 (3H, s, -CH ₃ ), 2.25 (3H, s, -CH ₃ ), 0.16 (3H, s, Si-CH ₃ ), 0.09 (3H, 3H, s, Si-CH ₃ ) ppm

[Example 1A]
0.69 g (2.00 mmol) of the compound (A-1L) obtained in Synthesis Example 1-1, 20 mL of toluene and 0.3 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. To this solution, 2.52 mL of an n-butyllithium solution (hexane solution, 1.59 M, 4.00 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. The solution was cooled to 0 ° C., 0.47 g (2.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, the suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (A-1). (Dimethylsilylene (4,7-dimethyl-2-indenyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, hereinafter referred to as "transition metal compound (A-1)") Was obtained in an amount of 0.45 g (yield 44%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.11-7.10 (1H, d, J = 3.5, Ind-H), 6.99-6.86 (4H, m, Ar-H), 6.42-6.41 (1H, d, J = 3.5, Ind-H), 6.08-6.07 (1H, d, J = 2.5, Ind-H), 5.98- 5.97 (1H, d, J = 2.5Hz, Ind-H), 2.56 (3H, s, -CH ₃ ), 2.43 (3H, s, -CH ₃ ), 2.39 (3H) , S, -CH ₃ ), 2.28 (3H, s, -CH ₃ ), 1.09 (3H, s, Si-CH ₃ ), 0.96 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 502

[Synthesis Example 2-1]
1.36 g (56.0 mmol) of magnesium pieces were charged into a 200 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. Further, a 20 mL diluted solution of 2-bromo-4,7-dimethyl-1H-indene (3.13 g (14.0 mmol)) synthesized by the method of Example 1 of WO 2016/188999 was added dropwise (1. After adding 0 mL, the mixture was heated under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the residue was dropped), and after the completion of the addition, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 8.41 mL (70.0 mmol) of dimethylsilyl dichloride in 15 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 10 mL of tetrahydrofuran and 1.51 mL (14.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain a solution 2a.

4. 7- (3,5-di-tert-butyl-4-methoxyphenyl) -1H-inden synthesized by the method described in JP-A-2017-145240 in a 100 mL reactor that has been sufficiently dried and substituted with argon. 69 g (14.0 mmol) and 15 mL of tetrahydrofuran were charged, 9.2 mL of n-butyllithium solution (hexane solution, 1.55 M, 14.7 mmol) was added, and the mixture was stirred at room temperature for 2 hours to obtain solution 2b.

This solution 2b was added dropwise to the 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, the soluble component was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off and the obtained residue is purified by silica gel column chromatography. The target product represented by the following formula (A-2L) (hereinafter referred to as "compound (A-2L)"). ) Was obtained as an isomer mixture of 3.83 g (yield 51%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.48-6.69 (10H, m, Ar-H & C = CH-C), 3.80 (1H, s, Si-CH), 3.74 (3H, 3H, s, -OCH ₃ ), 3.27-3.03 (2H, m, Ar-CH _2- C), 2.41 (3H, s, -CH ₃ ), 2.29 (3H, s, -CH) ₃ ), 1.49-1.39 (18H, s, -C (CH ₃ ) ₃ ), 0.26 (3H, s, Si-CH ₃ ), 0.21 (3H, s, Si-CH ₃₎ ) Ppm

[Example 2A]
1.07 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 into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 2.58 mL of an 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 an oil bath at 40 ° C. The solution was cooled to 0 ° C., 0.47 g (2.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, the suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (A-2). Compound in the form of a yellow powder represented by (dimethylsilylene (4,7-dimethyl-2-indenyl) (4- (3,5-di-tert-butyl-4-methoxyphenyl) -1-indenyl) zirconium dichloride, hereinafter "Transition metal compound (A-2)") was obtained in an amount of 0.60 g (yield 43%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.61-7.58 (1H, d, J = 4.4 Hz, Ar-H), 7.47-7.45 (2H, m, Ar-H), 7.36-7.34 (1H, d, J = 7.0Hz, Ar-H), 7.26-7.21 (1H, m, Ar-H), 7.10 (1H, d, J = 3.3Hz, Ind-H), 6.93-6.90 (2H, m, Ar-H, Ind-H), 6.19-6.18 (1H, d, J = 3.3Hz, Ind- H), 6.13-6.12 (1H, d, J = 3.3Hz, Ind-H), 6.06-6.05 (1H, d, J = 3.3Hz, Ind-H), 3 .70 (3H, s, -OCH ₃ ), 2.53 (1H, s, -CH ₃ ), -2.20 (1H, s, -CH ₃ ), 1.41 (18H, s, -C ( CH ₃ ) ₃ ), 1.15 (3H, s, Si-CH ₃ ), 0.92 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 694

[Reference Example 1A]
According to the method of Synthesis Example 7-2 of JP-A-2019-059933, a yellow powdery compound represented by the following formula (A-3) (dimethylsilylene (2-indenyl) (4,7-dimethyl-1-indenyl). ) Zirconium dichloride, hereinafter referred to as "transition metal compound (A-3)") was synthesized.

[Reference Example 2A]
According to the method of Example 2A of JP-A-2019-059723, a yellow powdery compound represented by the following formula (A-4) (dimethylsilylene (2-indenyl) (4- (3,5-di-tert-)). Butyl-4-methoxyphenyl) -1-indenyl) zirconium dichloride, hereinafter referred to as "transition metal compound (A-4)") was synthesized.

[Example 1]
<Preparation of solid catalyst component (X-1)>
Using a reactor with a stirrer with an internal volume of 270 L, as a solid carrier [S] under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative 50% particle size of volume distribution by laser photodiffraction scattering method: 70 μm, specific surface area) Surface area: 340 m ² / g, pore volume: 1.3 cm ³ / g, dried at 250 ° C. for 10 hours, hereinafter referred to as "solid support [S-1]") After suspending 10 kg in 77 L of toluene. , 0-5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) as a component (B) was added dropwise over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C. Then, these were brought into contact at 0 to 5 ° C. for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and the contact was continued at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the residue was washed twice with toluene to prepare a total amount of 115 liters of toluene slurry. When a part of the obtained slurry was collected and analyzed, the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L.

Next, 30 mL of toluene and 1.63 mL of the above-mentioned toluene slurry (solid content weight 0.2 g) were charged into a reactor with a stirrer having an internal volume of 200 mL sufficiently nitrogen-substituted under a nitrogen atmosphere. Next, 5.0 μmol of the toluene solution of the transition metal compound (A-1) obtained in Example 1A was added as Zr, and these were brought into contact with each other at an in-system temperature of 20 to 25 ° C. for 1 hour, and then the supernatant was decanted. And then washed twice with hexane. As a result, a slurry of the solid catalyst component (X-1) having a total volume of 40 mL was prepared.

<Manufacturing of ethylene polymer>
After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, ethylene was circulated and the inside of the reactor was saturated 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 the state of a slurry were charged as a solid content, and then at 80 ° C. and 0 in ethylene. The temperature was raised to .8 MPaG, the pressure was increased, and the 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 148.0 g of an ethylene polymer. The catalytic activity was 14,800 g-PE / g-solid catalytic component.

[Example 2]
<Preparation of solid catalyst component (X-2)>
The 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 2-1 was used instead of the transition metal compound (A-1). ) Was prepared.

<Manufacturing of ethylene polymer>
<Production of Ethylene Polymer> of Example 1 except that 20.0 mg of the solid catalyst component (X-2) in a slurry state was charged as a solid content in place of the solid catalyst component (X-1). The same operation as in the above was carried out to obtain 89.3 g of an ethylene polymer. The catalytic activity was 2,980 g-PE / g-solid catalytic component. The results are shown in Table 1.

[Comparative Example 1]
<Preparation of solid catalyst component (X-3)>
The 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). A slurry was prepared.

<Manufacturing of ethylene polymer>
Same as <Production of Ethylene Polymer> in Example 1 except that 250 mg of the solid catalyst component (X-3) in a slurry state was charged as a solid content in place of the solid catalyst component (X-1). To obtain 80.0 g of an ethylene-based polymer. The catalytic activity was 2,670 g-PE / g-solid catalytic component. The results are shown in Table 1.

[Comparative Example 2]
<Preparation of solid catalyst component (X-4)>
The solid catalyst component (X-4) was prepared in the same manner as in Example 1 except that the transition metal compound (A-4) obtained in Comparative Example 2A was used instead of the transition metal compound (A-1). A slurry was prepared.

<Manufacturing of ethylene polymer>
Same as <Production of Ethylene Polymer> in Example 1 except that 250 mg of the solid catalyst component (X-4) in a slurry state was charged as a solid content in place 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 catalytic component. The results are shown in Table 1.

Examples 1 and 2 using the transition metal compound [A] of the present invention (crosslinked (2-indenyl) (1-indenyl) type compound having a substituent at a specific position on the 2-indenyl ring) have the above-mentioned substituents. The MFR of the obtained ethylene-based polymer decreased, that is, the molecular weight increased, as compared with Comparative Examples 1 and 2 using the crosslinked (2-indenyl) (1-indenyl) type compound having no.

Further, in Examples 1 and 2, the molecular weight distribution of the obtained ethylene polymer was narrower than that in Comparative Examples 1 and 2.

Claims (12)

The transition metal compound [A] represented by the following general formula [1].

(In the general formula [1], M is a Group 4 transition metal atom in 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 neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a 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-based derivative group. But they may be different, they may combine with each other to form a ring,
Q is a Group 14 atom of the periodic table,
R ¹ , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen atoms and 1 to 40 carbon atoms. A hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.
R ² and R ⁵ are independently hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, respectively.
Adjacent substituents of R ^{1 to} R ⁶ may be bonded to each other to form a ring which may have a substituent.
Adjacent substituents of R ^{7 to} R ¹² may be bonded to each other to form a ring which may have a substituent.
R ¹³ and R ¹⁴ may be bonded to each other to form a ring containing Q, and this ring may have a substituent. ) In the general formula [1],
M is a zirconium atom or a hafnium atom,
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group.
Q is a carbon atom or a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ independently have 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, and a nitrogen-containing group having 1 to 20 carbon atoms. Alternatively, it is a sulfur-containing group having 1 to 20 carbon atoms.
R ⁷ may have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a substituent containing at least one atom selected from nitrogen, oxygen, and sulfur in the heterocycle. The transition metal compound [A] according to claim 1, which is an aromatic complex five-membered ring substituent. In the general formula [1],
Q is a silicon atom,
R ¹ , R ³ , R ⁴ , R ⁶ and R ^{8 to} R ¹⁴ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is an oxygen-containing group of 20 or a nitrogen-containing group having 1 to 20 carbon atoms.
R ² and R ⁵ are independently each of 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 claim 2. The transition metal compound [A] according to claim 3, wherein ^{R 1} and R ⁶ are hydrogen atoms in the general formula [1]. The transition metal compound [A] according to claim 4, wherein ^{R 3} and R ⁴ are hydrogen atoms in the general formula [1]. The transition metal compound [A] according to claim 5, wherein ^{R 7} and R ⁸ are hydrogen atoms in the general formula [1]. The transition metal compound [A] according to claim 6, wherein ^{R 10} and R ¹¹ are hydrogen atoms in the general formula [1]. The transition metal compound [A] according to claim 7, wherein in the general formula [1], ^{at least one of R 2} and R ^{5 is a hydrocarbon group having 1 to 20 carbon atoms.} A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of claims 1 to 8. Furthermore, [B] [B-1] organometallic compounds,
The ninth aspect of claim 9 comprises at least one compound selected from the group consisting of the [B-2] organic aluminum oxy compound and the [B-3] transition metal compound [A] to form an ion pair. Olefin polymerization catalyst. A method for producing an olefin polymer, which comprises a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 9 or 10. The method for producing an olefin polymer according to claim 11, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms.