JP7223540B2 - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

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

Olefin polymers are molded by various molding methods and used for various purposes. For example, an extruded product of an ethylene polymer is used for films or sheets used for packaging foodstuffs, liquids, or daily necessities. The properties required for olefin polymers differ depending on the molding method or application. It is required to have processing performance such as small

Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branched structure, resulting in high melt tension and low neck-in. is served to However, the mechanical strength such as tensile strength, tear strength or impact strength of the molded body is low, and problems remain such as poor high-speed film forming processability in T-die molding.

On the other hand, ethylene-based polymers produced using Ziegler catalysts or metallocene catalysts, in contrast to LDPE, have high tensile strength, tear strength or impact strength due to their molecular structure, and therefore mechanical Although it is used in applications that require strength, it has the problem of low melt tension and poor moldability.

In order to solve these problems, a method for producing an ethylene-based polymer having long chain branches in the presence of a solid catalyst component consisting of two transition metal compounds and a solid carrier (Patent Documents 1, 2, etc.). is proposed.

Further, as a method for producing an ethylene-based polymer having long chain branches in the presence of a solid catalyst component consisting of one transition metal compound and a solid support, a bridged bis(1-indenyl) type compound is used as the transition metal compound. (Patent Document 3, etc.) and a method using a bridged cyclopentadienyl (1-indenyl) type compound (Patent Documents 4, 5, etc.) have been reported.

On the other hand, Patent Documents 6 to 9 and Non-Patent Document 1 report olefin polymerization using a transition metal compound having a 2-indenyl group as described later.

Japanese Patent Application Laid-Open No. 2006-233208 JP 2009-144148 A JP 2007-119716 A WO2015/152268 JP 2014-118550 A JP-A-11-315089 JP-A-11-292934 Japanese Patent Application Laid-Open No. 2001-220404 JP-A-2001-302687

Macromolecules, 2004, 37(7), 2342

When producing an ethylene-based polymer using a solid catalyst component composed of two transition metal compounds and a solid carrier described in Patent Documents 1 and 2, etc., one transition metal compound and a solid carrier are used. The method of controlling the polymer composition is complicated compared to the solid catalyst component consisting of This is because, in addition to the polymer composition (molecular weight, molecular weight distribution, density, etc.) derived from each individual transition metal compound, the polymer yield ratio derived from each transition metal compound is also a variable factor for the resulting polymer composition. This is because The ratio of polymer production derived from each transition metal compound can be controlled by the contact amount ratio of each transition metal compound brought into contact with the solid support. can fluctuate. In practice, when ethylene is introduced in the presence of a solid catalyst and slurry polymerization or gas phase polymerization is carried out batchwise or continuously, the composition of the resulting polymer may fluctuate, resulting in non-standard products. Therefore, from the viewpoint of simplification of the polymer composition control method, it is desired that only one type of transition metal compound is used in the solid catalyst component.

On the other hand, in the methods for producing an ethylene-based polymer having long chain branches in the presence of a solid catalyst component consisting of one type of transition metal compound and a solid carrier described in Patent Documents 3 to 5, ethylene There were problems such as a small amount of long chain branching in the system polymer or low catalytic activity.

The present invention has been made in view of the above problems in the prior art, and provides a transition metal compound that can be used as a component of an olefin polymerization catalyst, the transition metal compound being contained in the olefin polymerization catalyst. A transition metal compound capable of producing an ethylene-based polymer into which many long-chain branches are introduced with high catalytic activity even if only one type is used, and an olefin typified by an ethylene polymerization catalyst using the same. An object of the present invention is to provide a polymerization catalyst and a method for producing an olefin polymer represented by an ethylene-based polymer.

The present inventors have made intensive studies to solve the above problems, and found that the above problems were solved by using a bridged (2-indenyl) (1-indenyl) type compound having a specific substituent on the 1-indenyl ring. I discovered what I could do, and completed the present invention.

Olefin polymerization using a transition metal compound having a 2-indenyl group has been reported in Patent Documents 6-9 and Non-Patent Document 1. For example, Patent Document 6 discloses a method for producing an amorphous (co)polymer. Therefore, it is described that ethylene polymerization was performed in the presence of (2-indenyl)(1-indenyl)dimethylsilylzirconium dichloride (Example 11, etc.), and Non-Patent Document 1 describes [(2 -indenyl)(2-phenyl-1-indenyl)dimethylsilyl]zirconium dichloride, copolymerization of ethylene with propylene and ethylene with 1-hexene are described. However, these publications do not describe or suggest the production of transition metal compounds or long-chain branched ethylene polymers according to the present invention.

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

（一般式［１］中、Ｍは、周期表第４族遷移金属原子であり、
ｎは、遷移金属化合物［Ａ］が電気的に中性となるように選択される１～４の整数であり、
Ｘは、水素原子、ハロゲン原子、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子であり、前記アニオン配位子は、ハロゲン含有基、ケイ素含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基または共役ジエン系誘導体基であり、ｎが２以上の場合は、複数存在するＸで示される基は互いに同一でも異なっていてもよく、互いに結合して環を形成してもよく、
Ｑは、周期表第１４族原子であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立に、水素原子、炭素数１～４０の炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基または硫黄含有基であり、
Ｒ¹～Ｒ⁶のうちの隣接した置換基同士は、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｒ⁷～Ｒ¹¹のうちの隣接した置換基同士は、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｒ¹²～Ｒ¹⁶のうちの隣接した置換基同士は、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｒ⁹とＲ¹²またはＲ¹⁶とは、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｒ¹⁷およびＲ¹⁸は、互いに結合してＱを含む環を形成してもよく、この環は置換基を有していてもよい。）

(In the general formula [1], M is a Group 4 transition metal atom of the periodic table,
n is an integer from 1 to 4 selected so that the transition metal compound [A] is electrically neutral;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, the anionic ligand being a halogen-containing group, a silicon-containing group, an oxygen containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, aluminum-containing group or conjugated diene-based derivative group, and when n is 2 or more, multiple groups represented by X are the same may be different, and may be combined with each other to form a ring,
Q is a group 14 atom of the periodic table,
R1 ^{, R2 ,} R3, ^{R4 , R5} , R6, ^R7 , ^R8 , ^R9 , ^R10 , R11, ^{R12 , R13} , ^R14 , ^R15 , ^R16 , ^R17 and R ¹⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,
Adjacent substituents among R ¹ to R ⁶ may combine with each other to form a ring which may have a substituent,
Adjacent substituents among R ⁷ to R ¹¹ may combine with each other to form a ring which may have a substituent,
Adjacent substituents among R ¹² to R ¹⁶ may combine with each other to form a ring which may have a substituent,
R ⁹ and R ¹² or R ¹⁶ may combine with each other to form an optionally substituted ring,
R ¹⁷ and R ¹⁸ may combine with 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,
each 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 to R ⁶ and R ⁸ to R ¹⁸ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms,
R ⁷ 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, a nitrogen-containing group having 1 to 20 carbon atoms or a substituent; The transition metal compound [A] of the above [1] which is a thienyl group which may have.

[3]
In the general formula [1],
Q is a silicon atom,
R ¹ to R ¹⁸ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an amino group having 1 to 10 carbon atoms. The transition metal compound [A] of the above [2] which is a group.

[4]
In the general formula [1],
The transition metal compound [A] of [3] above, wherein R ¹ , R ⁶ and R ¹¹ are hydrogen atoms.

[5]
An olefin polymerization catalyst comprising the transition metal compound [A] of any one of [1] to [4].

[6]
Furthermore, [B] [B-1] organometallic compound,
[B-2] The above [5] containing at least one compound selected from the group consisting of an organoaluminumoxy compound and [B-3] a compound that forms an ion pair by reacting with a transition metal compound [A] Catalyst for olefin polymerization.

[7]
A method for producing an olefin polymer, comprising the step of polymerizing an olefin in the presence of the olefin polymerization catalyst of the above [5] or [6].

[8]
The method for producing an olefin polymer according to [7] above, 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 to 20 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, even if the catalyst for olefin polymerization contains only one type of transition metal compound, ethylene into which many long-chain branches are introduced system polymers can be produced with high catalytic activity.

The transition metal compound and the like according to the present invention are described in more detail below.
[Transition metal compound [A]]
The transition metal compound [A] (hereinafter sometimes referred to as "component (A)") according to the present invention is represented by the following general formula (1).

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

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

When n is 2 or more, a plurality of X's may be the same or different, and may combine with each other to form a ring. Moreover, when there are a plurality of the rings, the rings may be the same or different.

The halogen atom includes fluorine, chlorine, bromine and iodine, 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- yl 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), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 ,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group (2,3-dimethylbut-2-yl group), linear or branched alkyl groups such as 4,4-dimethylpentyl group;
vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-diene-1 -yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group) , but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3- methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl a linear or branched alkenyl group or an unsaturated double bond-containing group such as
linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group);
benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6 - Aromatic-containing straight 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 2-adamantyl group;
Phenyl group, tolyl group (methylphenyl group), xylyl 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- Aromatic substituents such as a tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group and ferrocenyl group can be mentioned.

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

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

Among the halogen-containing groups, a pentafluorophenyl group is preferred.
Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris ( trimethylsilyl)silyl group, trimethylsilylmethyl group and the like.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferred.
Examples of the oxygen-containing group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group and 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 and periodate anion.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferred.
Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonafryl group (nonafluorobutanesulfonyl group), Mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), nonaflate group (nonafluorobutanesulfonate group).

Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferred.
Examples of the nitrogen-containing group include amino group, cyano group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, allylamino group, diallylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl groups, morpholyl groups, pyrrolyl groups, bistrifurylimide groups, and the like.

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

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl) ) borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, BR ₄ (each R independently represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like. shown.).

Examples of the aluminum-containing group include

（Ｍは、前記一般式（１）中のＭを表す。）
を形成可能な、ＡｌＲ₄（Ｒは水素、アルキル基、置換基を有してもよいアリール基またはハロゲン原子等を示す）で表される基が挙げられる。

(M represents M in the general formula (1).)
A group represented by AlR ₄ (R represents hydrogen, an alkyl group, an aryl group optionally having a substituent, a halogen atom, or the like) capable of forming

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 and cyclopentadienyl group, and metallocyclopentene groups.

Examples of neutral ligands capable of coordinating with a lone pair include ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, pyridine, picoline, lutidine, Heterocyclic compounds such as oxazoline, oxazole, thiazole, imidazole and thiophene, and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine are included.

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

《 ^R1 ～ ^R18 》
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R 8 , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ^{14 ,} R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group; be.

Examples of the hydrocarbon groups having 1 to 40 carbon atoms as R ¹ to R ¹⁸ include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples are the above examples of X. Specific examples of hydrocarbon groups are given.

The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding an aromatic hydrocarbon group) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include:
methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group , 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group , tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group ( 2-methylpentan-2-yl group), 3-methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 -dimethylbutyl group, thexyl group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexan-3-yl group, 2-methylpentan-3-yl group, heptane-4 -yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptane-4 -yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group and other linear or branched alkyl groups having 1 to 40 carbon atoms ;
vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3 -dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-ene- 1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, pent-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, pent-1-en-3-yl group, pent-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, pent-1 , 4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5- en-1-yl group, hex-4-en-1-yl group, hex-3-en-1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en- 1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl- pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-ene -2-yl group, 3-ethylpent-1-en-3-yl group, hex-3,5-dien-1-yl group, hex-2,4-dien-1-yl group, 4-methylpent-1 ,3-dien-1-yl group, 2,3-dimethyl-but-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadi linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms such as enyl)propan-2-yl group and 2-(cyclopentadienyl)ethyl group;
ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-buta- 1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, pent-4-yn-2-yl group, hex-1- yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, 2,2-dimethyl-but-3-yne -1-yl group, hex-4-yn-1-yl group, hex-5-yn-1-yl group, a linear or branched alkynyl group having 2 to 40 carbon atoms, or an unsaturated triple a bond-containing group;
benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl ) propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di -tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-2 -yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4- methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl) ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropy group, cinnamyl group (3-phenylallyl group), neophyll group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group , cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl ) propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2-(tetrahydro-1-indacenyl) ethyl group, 2-(1-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 pentadienyl 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]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo [2.2.2] octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl) , 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl) ), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. having 3 to 40 carbon atoms cyclic saturated and unsaturated hydrocarbon groups of;
phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, duryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl)phenyl group, (but-2-en-1-yl)phenyl group, methallylphenyl group , prenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. Examples 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, 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 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group, 3-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl Groups 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 are preferred. -2-yl group and 2,4,4-trimethylpentan-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, but-3-en-1-yl group, crotyl group, methallyl group, pent-4-en-1-yl group, prenyl group, pent-1,4-dien-3-yl group, hex-5-en-1-yl group, 2-methylpent-4-en-2- yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group and the like are preferred, and vinyl group, allyl group, but-3-en-1-yl group, penta -4-en-1-yl group, prenyl group and hex-5-en-1-yl group are more preferred.

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

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 group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group , 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3 ,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyll group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2-(1-indenyl) ethyl group, 2-(9-fluorenyl) propan-2-yl group, (9- fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group and the like are preferred, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group and 3-phenylpropyl group. , a cinnamyl group is more preferred.

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-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]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group and the like are preferred, cyclopentyl group, A cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group are more preferred.

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

Examples of the halogen-containing group include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoromethyl group, 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 group, and the like.

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

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

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 preferred, 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 methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group and methallyloxy group. , prenyloxy 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 group 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, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyrani furoryl group, benzofuryl group, dibenzofuryl group and the like.

Among the oxygen-containing groups, alkoxy groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) are preferred, and specific examples include methoxy, ethoxy, iso-propoxy, allyloxy, n-butoxy, and 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, furyl group, methylfuryl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group and the like are preferred, methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl- A 4-methoxyphenyl group, a furyl group, a methylfuryl group, a benzofuryl group, and a dibenzofuryl group are more preferred.

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

Among the above nitrogen-containing groups, amino groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) are preferred, and specific examples are amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group and dibenzylamino. group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethyl amino allyl group, pyrrolidinyl allyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group , an iso-quinolyl group, a tetrahydro-iso-quinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, An oxazolidinyl group, a benzoxazolyl group, and the like are preferred, and an amino group, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, and a 3,5-di-iso -Propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferable.

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

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

Adjacent substituents among R ¹ to R ^{6 (} e.g., R ¹ and R ² , R ² and R ³ , R ³ and R 4 , R ⁴ and R ⁵ , and R ⁵ and R ⁶ ) are They may combine to form a ring which may have a substituent. The ring formed in this case consists of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon, optionally having a substituent, condensed to the indenyl ring portion. A 5- to 8-membered ring is preferred. In addition, when multiple rings exist, these may mutually be the same or different. 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. A denyl ring, a substituted tetrahydroindacene ring, and a substituted cyclopentatetrahydronaphthalene can be mentioned, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

Adjacent substituents among R ⁷ to R ¹¹ (eg, R ⁷ and R ⁸ , R ⁹ and R ¹⁰ and R ¹⁰ and R ¹¹ ) may be bonded to each other to have a substituent A ring may be formed. The ring formed in this case consists of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon, optionally having a substituent, condensed to the indenyl ring portion. A 5- to 8-membered ring is preferred. In addition, when multiple rings exist, these may mutually be the same or different. Although not particularly limited as long as the effect of the present invention is exhibited, the ring is more preferably a 5- or 6-membered ring. A denyl ring, a substituted tetrahydroindacene ring, a substituted cyclopentatetrahydronaphthalene, a substituted tetrahydrofluorene ring, and a substituted fluorene ring can be mentioned, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

Adjacent substituents among R ¹² to R ¹⁶ (e.g., R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁶ ) are bonded together to form a substituent may form a ring which may have The ring formed in this case consists of a saturated hydrocarbon (excluding the hydrocarbon of the benzene ring portion) or an unsaturated hydrocarbon, optionally having a substituent, condensed to the benzene ring portion. A 5- to 8-membered ring is preferred. In addition, when multiple rings exist, these may mutually be the same or different. 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. , anthracene ring, phenanthrene ring, tetrahydronaphthalene ring, octahydroanthracene ring, dihydroindene ring and hexahydroindacene ring are preferred.

R ⁹ and R ¹² or R ¹⁶ and (eg R ⁹ and R ¹² , R ⁹ and R ¹⁶ ) may combine with each other to form an optionally substituted ring. The ring formed in this case is an optionally substituted saturated hydrocarbon (excluding hydrocarbons of the indenyl ring portion and the benzene ring portion), which is fused to the indenyl ring portion and the benzene ring portion. .) or a 5- to 6-membered ring composed of an unsaturated hydrocarbon is preferred. Although not particularly limited as long as the effect of the present invention is exhibited, the ring is more preferably a 6-membered ring. A cyclopentaphenanthrene ring, a dihydrocyclopentaphenanthrene ring, and a cyclopentafluorene ring are preferred.

R ¹⁷ and R ¹⁸ may combine with each other to form a ring containing Q. The ring formed in this case is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although not particularly limited as long as the effect of the present invention is exhibited, the ring is preferably a ^4- to ⁶ -membered ring. Pentane ring, substituted fluorene ring, substituted silacyclobutane (silethane) ring, substituted silacyclopentane (silolane) ring, substituted silacyclohexane (silinane), substituted silafluorene ring, substituted cyclopentane ring, substituted silacyclobutane ring, substituted A silacyclopentane ring is preferred.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom. be.

R ² to R ⁵ and R ⁷ to R ¹⁸ are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group; More preferably, it is a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a silicon-containing group with 1 to 20 carbon atoms, an oxygen-containing group with 1 to 20 carbon atoms or a nitrogen-containing group with 1 to 20 carbon atoms. At least one of R ⁷ and R ¹¹ , especially R ⁷ , the oxygen-containing group, nitrogen-containing group or sulfur-containing group may be a heterocyclic aromatic group described later.

<<Preferred Embodiment of Transition Metal Compound [A]>>
A preferred embodiment of the transition metal compound [A] is
In the general formula [1],
M is a zirconium atom or a hafnium atom,
each 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 to R ⁶ and R ⁸ to R ¹⁸ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms ( an alkoxy group) or a nitrogen-containing group having 1 to 20 carbon atoms (eg, an amino group),
R ⁷ 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 (e.g., an alkoxy group, even if it has a substituent furyl group), a nitrogen-containing group having 1 to 20 carbon atoms (eg, amino group) or a thienyl group optionally having a substituent [A-1]
A more preferred embodiment is
In the general formula [1],
Q is a silicon atom,
R ¹ to R ¹⁸ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an amino group having 1 to 10 carbon atoms. a group, which may be the same or different transition metal compounds [A-2]
is mentioned.

A more preferred embodiment of the transition metal compound [A-2] is a transition metal compound [A-3] in which R ¹ , R ⁶ and R ¹¹ in the general formula [1] are hydrogen atoms.
In the transition metal compound [A ^- 1], a five-membered ring ⁽ hereinafter " (Also referred to as "hetero 5-membered ring".) Examples of the optionally substituted heterocyclic aromatic group include groups represented by the following general formulas [4a] to [4h] .

前記一般式［４ａ］～［４ｈ］中、Ｃｈは酸素原子あるいは硫黄原子であり、Ｒ^dはそれぞれ独立に、水素原子または炭素数１～２０の炭化水素基であり、それぞれ同一でも異なっていてもよい。

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

The wavy lines in the general formulas [4a] to [4h] indicate bonding sites with the indenyl ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms among the examples of the hydrocarbon group having 1 to 40 carbon atoms as R ¹ to R ¹⁸ described above. are 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]octan-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, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group , cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group and terphenyl group.

Each R ^d is independently bonded to each other and condensed to the 5-membered heterocyclic ring moiety, optionally having a substituent, and 5 to 8-membered together with the atoms of ^the 5-membered heterocyclic moiety A saturated or unsaturated hydrocarbon group constituting a 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, benzofuran ring, benzothiophene ring, indole ring, carbazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzopyrazole ring and the like.

Among the heterocyclic aromatic groups represented by general formulas [4a] to [4h], the heterocyclic aromatic groups represented by general formula [4a] are preferred.
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] are shown below, but the scope of the present invention is not particularly limited by these.

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

なお、前記［表１］～［表２］中の波線は架橋部分との結合部位を示す。

The wavy lines in [Table 1] to [Table 2] indicate the bonding sites with the crosslinked portions.

前記［表３］中のＲ¹、Ｒ⁶およびＲ⁸置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ¹ , R ⁶ and R ⁸ substituents in [Table 3] may be the same or different in combination.

前記［表４］中のＲ²、Ｒ⁵およびＲ¹¹置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ² , R ⁵ and R ¹¹ substituents in [Table 4] may be the same or different in combination.

前記［表５］中のＲ³、Ｒ⁴、Ｒ⁹およびＲ¹⁰置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ³ , R ⁴ , R ⁹ and R ¹⁰ substituents in [Table 5] may be the same or different in combination.

Specific examples of the metal portion MXn include 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(OMe) ₂ , Ti(OiPr) ₂ , Ti( _NMe2 ) ₂ , Ti(OMs) ₂ , Ti(OTs) ₂ , Ti(OTf) ₂ , _ZrF2 , _ZrCl2 , _ZrBr2 , 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(OMe) ₂ , Zr(OiPr) ₂ , Zr( _NMe2 ) ₂ , Zr(OMs) ₂ , Zr(OTs) ₂ , Zr(OTf) ₂ , HfF2 _{, HfCl2} , HfBr2, _{HfI2 ,} Hf(Me) ₂ , Hf(Bn) ₂ , Hf(Allyl ) ₂ , Hf(CH ₂ -tBu) ₂ , Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3 -pentadienyl), Hf( _CH2 -Si(Me) ₃ ) ₂ , Hf(OMe) ₂ , Hf(OiPr) ₂ , Hf( _NMe2 )2, Hf(OMs) ₂ , Hf(OTs) _{2 ,} Hf( OTf) ₂ and the like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, _NMe2 is a dimethylamino group, and OMs is methanesulfonate. OTs is the p-toluenesulfonate group and OTf is the 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-3 in [Table 2], and the indenyl ring moieties R ¹ , R ⁶ and R ⁸ All substituents are γ-1,2-indenyl ring moieties R ² and R ⁵ in [Table 3] All substituents are δ-1,2-indenyl ring moieties R ³ and R ⁴ in [Table 4] All of the substituents are the ε-1,1-indenyl ring portion R ⁷ substituent in [Table 5] and the ζ-30,1-indenyl ring 4-position portion Ar substituent in [Table 6]. η-28 in the 1-indenyl ring portion R ¹¹ substituent is δ-3 in [Table 4], the bridging portion is a combination of θ-20 in [Table 8], and the metal portion MXn is ZrCl In the case of ₂ , the compound represented by the following formula [5] is exemplified.

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

Further, the 2-indenyl ring moiety in [Table 1] is ^the α-3,1-indenyl ring moiety in [Table 2] and the β-1,2-indenyl ring moiety in [Table ² ] γ-2, indenyl ring moieties R ² , R ⁵ and R ¹¹ substituents in [Table 3] are all the δ-1,1-indenyl ring moieties R ⁷ substituents in [Table 4] The ζ-12,1-indenyl ring portion R ⁸ substituent in [Table 3] is the γ-1,1-indenyl ring 4-position portion Ar substituent in [Table 7] η-50,1-indenyl ring The ε- ³ , 1-indenyl ring moiety R ¹⁰ substituent in [Table 5] is the ε-12, 1-indenyl ring moiety R ¹¹ substituent in [Table 4]. δ-1 in [Table 8], the cross-linking portion is composed of a combination of θ-31 in [Table 8], and MXn of the metal portion is HfMe ₂ , the compound represented by the following formula [7] is exemplified. .

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

In addition, in the transition metal compound [A], there are two planes of the indenyl ring portion that binds to the central metal across the bridge portion (front side and back side). Therefore, when the 2-indenyl ring moiety does not have a plane of symmetry, there are two structural isomers represented by the following general formulas [9a] and [9b].

同様に、架橋部分の置換基Ｒ¹⁷とＲ¹⁸が同一でない場合にも、一例として下記一般式［１０ａ］あるいは［１０ｂ］で示される２種類の構造異性体が存在する。

Similarly, even when the substituents R ¹⁷ and R ¹⁸ of the crosslinked portion are not the same, there are two types of structural isomers represented by the following general formulas [10a] and [10b].

Ar in [9a], [9b], [10a] and [10b] represents an aromatic substituent. Purification and fractionation of these structural isomer mixtures, or selective production of structural isomers is possible by known methods, and the production method is not particularly limited. As known production methods, in addition to the production method of the transition metal compound [A], JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340." ”, and the manufacturing method disclosed in Japanese Patent Application Laid-Open 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. As described above, according to the present invention, an ethylene polymer into which many long-chain branches are introduced is produced with high catalytic activity by using only the transition metal compound [A] as the transition metal compound constituting the catalyst for olefin polymerization. However, one or more transition metal compounds other than the transition metal compound [A] may be used in combination as the transition metal compound within a range in which this effect is not impaired. At this time, the transition metal compound [A] may be in any of the above modes.

<<Method for producing transition metal compound [A]>>
The transition metal compound [A] can be produced using a conventionally known method, and representative synthetic route examples are shown below, but the production method is not particularly limited. In the following [Formulas 1] to [Formulas 5], R ¹ to R ¹⁸ , Q, M, X and n have the same meanings as those described in the general formula [1].

The starting substituted indene compound can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, "Organometallics 1994, 13, 954.", "Organometallics 2006, 25, 1217." WO2009/080216, "Organometallics 2011, 30, 5744." Disclosed in JP 2012-012307, JP 2012-121882, JP 2014-196319, JP 2014-513735, JP 2015-063495, JP 2016-501952, etc. manufacturing method.

Among the above substituted indene compounds, the 2-position unsubstituted one can be brominated at the 2-position by the following known method, and the production method is not particularly limited.

In the above [Formula 1], NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid or its monohydrate. An indene compound has 5-membered ring partial double bond positional isomers, and a mixture of these isomers may be used. Examples of known production methods include the production methods disclosed in JP-A-2014-111568 and the like, in addition to JP-A-2012-121882 and JP-A-2015-063495.

From the 2-brominated indene compound and the 4-brominated indene compound, the corresponding coupling products can be produced by a known method such as the following palladium-catalyzed Suzuki-Miyaura coupling reaction, The manufacturing method is not particularly limited.

前記同様に、インデン化合物５員環部分二重結合位置異性体が存在するが、それら異性体の混合物を用いてもよい。

As mentioned above, there are 5-membered ring partial double bond positional isomers of indene compounds, and mixtures of these isomers may also be used.

Instead of the boronic acid, other boron compounds such as various boronic esters and boroxines may be used, and the reaction mixture of the halogen compound and the metal reagent, then the boron compound may be used without isolation and purification, A nickel or iron catalyst may be used instead of the palladium catalyst. Examples of known production methods include those disclosed in JP-A-2014-196274 in addition to those described above.

Also, instead of Suzuki-Miyaura coupling with boron compounds, Negishi coupling with organozinc reagents, Mizoroki-Heck reaction with alkene compounds, Hiyama coupling with organosilicon compounds, Sonogashira-Hagiwara coupling with terminal alkyne compounds, Migita-Kosugi-Stille coupling with organotin compounds, Kumada-Tamao-Corriu coupling with organomagnesium compounds, Buchwald-Hartwig coupling, Goldberg amination reaction or Ullmann ether synthesis reactions may also be used. Examples of known production methods include those disclosed in JP-A-8-183814, JP-A-2005-529865, JP-A-2006-509046, and the like, in addition to those described above.

The coupling product may be produced by a known method such as a direct coupling reaction with a palladium catalyst using the 2-unsubstituted indene compound and the aromatic halide.

In the above [Formula 3], Ar represents an aromatic substituent, and a mixture of 5-membered ring partial double bond positional isomers of indene compounds may be used. Known production methods include, for example, JP-A-2000-512661 and JP-A-2014-201519.

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

In the above [Formula 4], in the precursor compound (ligand) synthesis, the organomagnesium reagent prepared from the 2-brominated substituted indene compound and the organolithium reagent prepared from the substituted 1-indene compound are stepwise is preferably reacted with a chloride containing Q in any order. After the reaction with the organometallic reagent in the first step, the by-product inorganic compound may be removed under an inert atmosphere, and the reaction product is isolated by distillation, crystallization or washing before use. good too. During the reaction with the organometallic reagent in the second stage, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropylene urea) or HMPA (hexamethylphosphoric acid triamide), etc. , preferably 0.1 to 5.0 equivalents, more preferably 1.0 equivalents of DMI, relative to the organometallic reagent. In the substituted indene compound and the precursor compound (ligand), there are 5-membered ring partial double bond positional isomers of the indene compound, and a mixture of these isomers may be used.

As known methods for producing the transition metal compound [A] and the precursor compound (ligand), for example, in addition to those shown above, JP-A-11-315089, JP-A-2001-302687, JP-A-2001 -220404, "Polymer Papers 2002, 59, 243.", JP-A-2003-522194, "Macromolecules 2004, 37, 2342.", JP-A-2007-320935, JP-A-2011-126813 publications and the like.

When Q is a carbon atom, it can be produced by the following methods, and the production method is not particularly limited.

In the above [Formula 5], base is a basic substance capable of generating an indenyl anion, for example, sodium hydride, n-butyllithium, organometallic compounds such as Grignard reagent, sodium hydroxide, potassium hydroxide and organic bases such as diethylamine and pyrrolidine, but are not particularly limited. A fulvene compound can be synthesized by a known method from a substituted 1-indene compound and a carbonyl compound in the presence of a basic substance. ) can be manufactured. In the substituted indene compound and the precursor compound (ligand), there are 5-membered ring partial double bond positional isomers of the indene compound, and a mixture of these isomers may be used.

Known methods for producing the transition metal compound [A] and the precursor compound (ligand) include, in addition to those shown above, "Macromolecules 2003, 36, 9325." and "Organometallics 2004, 23, 5332." , "Eur.J.Inorg.Chem. 2005, 1003.", "Eur.J.Inorg.Chem. 2009, 1759.", and the like.

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

(Compound [B])
The olefin polymerization catalyst of the present invention preferably further comprises
[B-1] an organometallic compound, preferably an organometallic compound represented by the following general formula (B-1a), (B-1b) or (B-1c) (hereinafter also referred to as "component (B-1)" ),
R.^a _mAl(OR^b)_nH._pX_q … (B-1a)
[In general formula (B-1a), R^aand R^brepresents a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different, X represents a halogen atom, m is 0<m≦3, n is 0≦n<3, p is 0≤p<3, q is a number satisfying 0≤q<3, and m+n+p+q=3. ]
M.^aAlR^a _Four … (B-1b)
[In general formula (B-1b), M^arepresents Li, Na or K, and R^arepresents a hydrocarbon group having 1 to 15 carbon atoms. ]
R.^a _rM.^bR.^b _s X_t … (B-1c)
[In general formula (B-1c), R^aand R^brepresents a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different, and M^bis selected from Mg, Zn and Cd, 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 organoaluminumoxy compound (hereinafter also referred to as "component (B-2)"), and
[B-3] A compound that forms an ion pair by reacting with the transition metal compound (A) (hereinafter also referred to as "component (B-3)")
At least one compound [B] selected from the group consisting of (hereinafter sometimes referred to as "component (B)") is included.

As the organometallic compound [B-1], compounds disclosed in JP-A-11-315109 and EP0874005A by the present applicant can be used without limitation.
The organometallic compound [B-1] is preferably represented by the general formula (B-1a), and specifically includes trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tri Trialkylaluminums such as octylaluminum and tri-2-ethylhexylaluminum, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkyl aluminum sesquihalides such as aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, dimethyl aluminum hydride, diethyl aluminum hydride , dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminum Examples include alkylaluminum hydrides such as hydride, dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide and diisobutylaluminum ethoxide.

These are used individually by 1 type or in combination of 2 or more types.
As the organoaluminumoxy compound [B-2], an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an organoaluminumoxy compound prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminumoxy compounds may be used singly 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-1-501950, JP-A-1-502036, JP-A-3-179005, Lewis acids, 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, and further can use heteropolycompounds and isopolycompounds without limitation.

The olefin polymerization catalyst according to the present invention not only exhibits extremely high catalytic activity for olefins such as ethylene, but also exhibits a solid It is preferable to use the organoaluminum oxy compound [B-2] as the component (B) because the solid carrier component containing the co-catalyst component can be easily prepared by reacting with the active hydrogen in the solid carrier.

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

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

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 composites or mixtures containing these. can also be used, for example natural or synthetic zeolites, 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 and the like can be used. Among these, the porous oxide is preferably composed mainly of SiO ₂ and/or Al ₂ O ₃ .

Said porous oxide contains a small amount of _Na2CO3 , _{K2CO3 , CaCO3} , _MgCO3 , _{Na2SO4 , Al2} ( _SO4 ) _{3 , BaSO4} , _KNO3 , Mg( _NO3 ) _2. , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components.

Although the properties of the porous oxide differ depending on the type and manufacturing 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 .} /g, preferably in the range of 100 to 700 m ² /g, with a pore volume in the range of 0.3 to 3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.

The solid aluminoxane compound includes an aluminoxane having a structure represented by the following general formula (Sa) or (Sb), and a repeating unit represented by the following general formula (Sc) and the following general formula ( aluminoxanes selected from at least one kind of aluminoxanes having a repeating unit represented by Sd) as a structure.

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

In the general formulas (Sa) and (Sb), r represents an integer of 2-500, preferably 6-300, particularly preferably 10-100. In the general formulas (Sc) and (Sd), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane remains substantially solid under the reaction environment employed.

The solid aluminoxane compound, unlike conventionally known carriers for olefin polymerization catalysts, does not contain inorganic solid components such as silica and alumina, organic polymer components such as polyethylene and polystyrene, and is solidified with an alkylaluminum compound as the main component. It is. By "solid state" is meant that the aluminoxane component remains substantially solid under the reaction environment in which it is used. More specifically, when preparing an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) by contacting the transition metal compound [A] with an aluminoxane component as described later, and the prepared olefin polymerization catalyst is used to polymerize an olefin (eg, ethylene) (eg, suspension polymerization), the aluminoxane component remains substantially solid.

Visual confirmation is the simplest method for determining whether the aluminoxane component is in a solid state or not. However, visual confirmation is often difficult, for example, during polymerization. In that case, it is possible to determine, for example, from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. Conversely, if the polymer powder has good properties and little adhesion to the reactor, even if some of the aluminoxane component is eluted under the polymerization environment, it does not depart from the gist of the present invention. Indices for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymer. Polymer bulk density is preferable from the viewpoint of quantification. The bulk density is generally 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.

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

The dissolution ratio was obtained by adding 2 g of the 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. , is determined by measuring the aluminum concentration in this filtrate. The dissolution rate is therefore determined as the proportion of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

As the solid aluminoxane compound, known solid aluminoxane can be used without limit, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. Examples of known production methods include JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. -38410, JP-A-2000-95810, International Publication No. 2010/55652, and the like.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01-50000 μm, preferably 1-1000 μm, particularly preferably 1-200 μm. The average particle size of the solid aluminoxane compound is obtained by observing particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight average. First, the particle size of each particle is obtained by the following formula, measuring the length of a particle image sandwiched between two parallel lines in the horizontal and vertical directions.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound is determined by the following formula using the particle size determined above.
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 inorganic halide may be used as it is obtained, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used.

Examples of clays, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, _CdCl2 type, and _CdI2 type.

Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, halloy sites, etc.
Examples of the ion-exchange layered compound include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ ·3H ₂ O, α-Ti(HPO ₄ ). ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ-Ti(HPO ₄ ) ₂ , γ-Ti( _NH4PO4 ) _2.H2O and other polyvalent metal crystalline _acid salts _.

Such a clay, clay mineral, or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc/g or more, more preferably 0.3 to 5 cc/g, with a radius of 20 Å or more measured by mercury porosimetry. is particularly preferred. Here, the pore volume is measured in the pore radius range of 20 to 30000 Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume of 20 Å or more and a pore volume of less than 0.1 cc/g is used, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat the clay and clay mineral. Any chemical treatment can be used, such as surface treatment for removing impurities adhering to the surface, treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment. The acid treatment removes surface impurities and also elutes cations such as Al, Fe and Mg in the crystal structure to increase the surface area. Alkaline treatment destroys the crystalline structure of the clay, resulting in changes in the clay structure. Also, in salt treatment and organic matter treatment, ionic complexes, molecular complexes, organic derivatives, etc. are formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of a layered compound is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [ _Al13O4 (OH) ₂₄ ] ⁷⁺ , [ _Zr4 (OH _{) 14} ] ²⁺ , [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ etc. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ (R represents a hydrocarbon group) are hydrolyzed. The resulting polymer, a colloidal inorganic compound such as SiO _{2 ,} etc., can also coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are obtained, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, one type may be used alone, or two or more types may be used in combination.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.
Examples of organic compounds that can be used as the carrier [S] include granular or particulate solids having a particle size in the range of 1 to 300 μm. Specifically, polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene as main components. Polymers produced as and modified products thereof can be exemplified.

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

As a method of contacting each component, focusing on the order of contact, for example,
(i) Method of contacting component (A) with component (B) (ii) Method of contacting component (A) with component (S) (iii) Contacting component (B) with component (S), then component Method of contacting (A) (iv) Method of contacting component (A) with component (B) followed by component (S) Method (v) Contacting component (S) with component (B) followed by component a method of contacting a mixture of (A) and component (B);
(vi) A method of contacting component (B) with component (S), further contacting component (B), and then contacting a mixture of component (A) and component (B). When multiple types of components (B) are used, the components (B) may be the same or different. Of the above methods, (i), (ii), (iii) and (iv) are preferred.

In each of the methods showing the contact order form, in the step involving contacting component (S) with component (B) and in the step involving contacting component (S) with component (A), component (G) coexistence suppresses fouling during the polymerization reaction and improves the particle properties of the resulting polymer. As the component (G), a compound having a polar functional group can be used, preferably a nonionic (nonionic) surfactant, polyalkylene oxide block, higher aliphatic amide, polyalkylene oxide, polyalkylene oxide alkyl ether , alkyldiethanolamines, polyoxyalkylenealkylamines, glycerin fatty acid esters, and N-acylamino acids are more preferable. These may be used alone or in combination of two or more.

Examples of the solvent used for preparing the olefin polymerization catalyst according to the present invention include inert hydrocarbon solvents. alicyclic hydrocarbons such as group hydrocarbons, cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. Depending on the type of olefin to be polymerized, the olefin itself can also be used as a solvent.

In the contact between component (B) and component (S), the reactive sites in component (B) and the reactive sites in component (S) are chemically bonded by reaction, and component (B) and component (S ) is formed. The contact time between component (B) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. is done in When component (B) and component (S) are rapidly brought into initial contact with each other, component (S) collapses due to the reaction heat and reaction energy, and the morphology of the obtained solid catalyst component deteriorates. Continuous operation is often difficult due to poor polymer morphology. Therefore, at the initial stage of contact between the component (B) and the component (S), the contact is made at a lower temperature for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled and the reaction is made at a rate that can maintain the initial contact temperature. is preferred. The same applies when the component (B) and the component (S) are brought into contact with each other and then the component (B) is brought into contact with the component (B). The contact weight ratio between component (B) and component (S) (weight of component (B)/weight of component (S)) can be arbitrarily selected, but the higher the contact weight ratio, the more component (A ) can be contacted, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of component (B) to component (S) [=weight of component (B)/weight of component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2. .0.
When the component (A) is contacted with the contact product of the component (B) and the component (S), 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.

In component (B-1), the molar ratio [(B-1)/M] of component (B-1) to all transition metal atoms (M) in component (A) is usually 0.01 to 100, 000, preferably 0.05 to 50,000.

In component (B-2), the molar ratio [(B-2)/M] of component (B-2) (in terms of aluminum atoms) to all transition metal atoms (M) in component (A) is usually 10. -500,000, preferably from 20 to 100,000.

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

In the olefin polymerization, the olefin polymerization catalyst of the present invention can be used as it is, but it is also possible to prepolymerize the olefin with this olefin polymerization catalyst to form a prepolymerized solid catalyst component before use.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin (e.g., ethylene) or the like in the presence of the olefin polymerization catalyst of the present invention, usually in an inert hydrocarbon solvent. It can be carried out in either a semi-continuous method or a continuous method, and can be performed under reduced pressure, normal pressure, or increased pressure. Further, it is desirable that the prepolymerization produces 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g of the prepolymerized solid catalyst component per 1 g of the solid catalyst component.

After the prepolymerized solid catalyst component produced in the inert hydrocarbon solvent is separated from the suspension, it is suspended again in the inert hydrocarbon, and an olefin (e.g. ethylene) is introduced into the resulting suspension. or the 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 about 0.5 to 100 hours, preferably 1 to 50 hours. An olefin based on ethylene is preferably used for the prepolymerization.

As the form of the solid catalyst component used for prepolymerization, those already mentioned can be used without limitation. In addition, component (B) is used as necessary, and an organoaluminum compound [B-1a] represented by general formula (B-1a) is particularly preferably used. When component (B) is used, component (B) is the molar ratio (Al/M ) is used in an amount of 0.1 to 10,000, preferably 0.5 to 5,000.

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

In addition, for the purpose of improving the fluidity of the prepolymerized solid catalyst component and suppressing the occurrence of heat spots, sheeting and polymer lumps during polymerization, the component (G) is brought into contact with the prepolymerized solid catalyst component once generated by the prepolymerization. good too.

The temperature at which the component (G) is contacted 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 and the component (G) are brought into contact with each other, the component (G) is added in an amount of 0.1 to 20 parts by weight, preferably 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 those mentioned 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 "dried prepolymerized catalyst") can be used as the olefin polymerization catalyst. Drying of the prepolymerized solid catalyst component is usually carried out after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

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

Since the dried prepolymerized catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dry prepolymerized catalyst is used, the solvent used for suspension does not have to be entrained in the gas phase polymerization system, so that the polymerization can be stably carried out.

[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 olefin polymerization catalyst of the present invention.

A preferred embodiment of the method for producing an olefin polymer of the present invention includes a method for producing an ethylene polymer. In this method, ethylene is polymerized or mixed with ethylene in the presence of the olefin polymerization catalyst of the present invention. It polymerizes with an olefin having 3 to 20 carbon atoms.

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

Examples of the polymerization method include liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods, with suspension polymerization methods and gas phase polymerization methods being preferred.
Specific examples of inert hydrocarbon media used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures thereof.

When olefin (eg, ethylene) is polymerized using the olefin polymerization catalyst according to the present invention, component (A) is usually 1×10 ⁻¹² to 1×10 ^{−1 mol, preferably 1×10 −1} mol per liter of reaction volume. is used in an amount of 1×10 ⁻⁸ to 1×10 ⁻² mol. In addition, component (B) is used, and preferably a compound represented by general formula (B-1a) or 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. A higher temperature is 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 kg/cm ² , preferably normal pressure to 50 kg/cm ² .

The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with 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 exist in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

When the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, the monomer supplied to the polymerization reaction is ethylene alone, or ethylene and an olefin having 3 to 20 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-octahydronaphthalene and other cyclic olefins may be mentioned.

Furthermore, a small amount of styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, A polar monomer such as methacrylic acid may be supplied.

According to the method for producing an olefin polymer according to the present invention, an ethylene-based polymer having many long-chain branches can be produced with high catalytic activity using one transition metal compound. In the method for producing the olefin polymer of the present invention, the present inventors have found that the transition metal compound (A) is a macromonomer having a terminal vinyl as a mechanism for introducing long-chain branching into the ethylene-based polymer. It is presumed that it plays both the role of generating and the role of copolymerizing the macromonomer competitively with the polymerization of ethylene and α-olefin. In addition, by using the transition metal compound [A] in contact with the optional component carrier [S], it is possible to increase the macromonomer concentration near the reaction point of the transition metal compound (A), so that more It is believed that it is possible to produce an ethylene-based polymer into which long-chain branches have been introduced.

[Olefin polymer]
The ethylene polymer produced by the method for producing an olefin polymer according to the present invention has many long-chain branches of appropriate length, and preferably satisfies the following requirements (1) to (4).
(1) Melt flow rate (MFR) at 190° C. under a load of 2.16 kg is 0.1 g/10 min or more and 50 g/10 min or less, preferably 0.5 g/10 min or more and 30 g/10 min or less;
(2) Density is 875 kg/m ³ or more and 965 kg/m ³ or less, preferably 885 kg/m ³ or more and 945 kg/m ³ or less;
(3) The ratio of the zero-shear viscosity [η ₀ (P)] at 200° C. to the 6.8th power of the weight average molecular weight (Mw ^6.8 ) measured by the GPC-viscosity detector method (GPC-VISCO), η ₀ /Mw ^6.8 is 0.03×10 ⁻³⁰ or more and 7.5×10 ⁻³⁰ or less, preferably 0.03×10 ⁻³⁰ or more and 5.0×10 ⁻³⁰ or less;
(4) Intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) to the power of 0.776 (Mw ^0.776 ), [η]/Mw ^0.776 is 0.90×10 ⁻⁴ or more and 1.65×10 ⁻⁴ or less, preferably 0.90×10 ⁻⁴ or more and 1.55×10 ⁻⁴ or less.

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

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

Both of the requirements (3) and (4) are known indicators of long chain branching, and their significance is described in, for example, JP-A-2006-233207, WO2006/080578, WO2006/080578, 2013/099927 etc. can be referred.

Olefin polymers (eg, ethylene-based polymers) produced by the present invention may be pelletized.
The olefin polymer (e.g., ethylene polymer) produced by the present invention contains a weather stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent, as long as the objects of the present invention are not impaired. , anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants and the like may be blended as necessary.

The olefin polymer (eg, ethylene-based polymer) produced by the present invention can be processed by general film molding, blow molding, injection molding and extrusion molding.
Molded articles obtained by processing the olefin polymer (e.g., ethylene-based polymer) produced by the present invention include films, blow infusion bags, blow bottles, gasoline tanks, extruded tubes, pipes, and torn pieces. Injection molded products such as caps and daily necessities, textiles, and large-sized molded products by rotational molding.

Films obtained by processing olefin polymers (e.g., ethylene-based polymers) produced by the present invention include water packaging bags, liquid soup packaging bags, liquid paper containers, laminated original fabrics, special-shaped liquid packaging bags ( Standing pouches, etc.), standard bags, heavy duty bags, wrap films, sugar bags, oil packaging bags, various packaging films such as food packaging, protective films, infusion bags, agricultural materials, etc. It can also be used as a multi-layer film by bonding it to a base material such as polyester.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples.
[Measurement of various physical properties]
Methods for measuring physical properties of ethylene-based polymers are shown below.
<Melt flow rate (MFR)>
Measured under the conditions of 190° C. and 2.16 kg load (kgf).

<Density (D)>
The strand obtained in the MFR measurement was heat-treated at 100° C. for 30 minutes, left at room temperature for 1 hour, and then measured by the density gradient tube method.

<Melt tension (MT)>
The melt tension (MT) (unit: g) at 190° C. was determined by measuring the stress when drawing at a constant speed. For the measurement, a capillary rheometer: Capilograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The conditions are resin temperature 190°C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm/min, winding speed 24 m/min (if the molten filament breaks, reduce the winding speed by 5 m/min) ), a nozzle diameter of 2.095 mm, and a nozzle length of 8 mm.

<Shear viscosity (η ^* )>
The shear viscosity [η ^* (1.0)] (P) at 200°C and an angular velocity of 1.0 rad/sec was measured by the following method.

The shear viscosity (η ^* ) was measured by angular velocity [ω (rad/sec)] dispersion of the shear viscosity (η ^* ) at a measurement temperature of 200°C within the range of 0.01≤ω≤100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a parallel plate of 25 mmφ was used as a sample holder, and the thickness of the sample was set to about 2.0 mm. The measurement points were five points per one digit of ω. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and the torque would not be over.

The samples used for shear viscosity measurement were preheated at 190°C, preheated for 5 minutes, heated at 190°C, heated for 2 minutes, heated at a pressure of 100 kgf/cm ² , and cooled at a cooling temperature of 20 using a press molding machine manufactured by Shindo Kinzoku Kogyo Co., Ltd. C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf/ ^cm.sup.2 .

<Zero shear viscosity (η ₀ )>
The zero shear viscosity (η ₀ ) (P) at 200°C was obtained by the following method.
At a measurement temperature of 200° C., the angular velocity ω (rad/sec) dispersion of shear viscosity (η ^* ) was measured in the range of 0.01≦ω≦100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a parallel plate of 25 mmφ was used as a sample holder, and the thickness of the sample was set to about 2.0 mm. The measurement points were five points per one digit of ω. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and torque over would not occur.

The samples used for shear viscosity measurement were preheated at 190°C, preheated for 5 minutes, heated at 190°C, heated for 2 minutes, heated at a pressure of 100 kgf/cm ² , and cooled at a cooling temperature of 20 using a press molding machine manufactured by Shindo Kinzoku Kogyo Co., Ltd. C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf/ ^cm.sup.2 .

The zero shear viscosity (η ₀ ) was calculated by fitting the Carreau model of the following formula to the actually measured rheology curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] by the nonlinear least squares method.
η ^* = η ₀ [1 + (λω) ^a ] ^(n-1)/a
[λ is a parameter with the dimension of time, n represents the power law index of the material. Fitting by the nonlinear least squares method was performed so that d in the following equation was minimized.

〔η_exp（ω）は実測のせん断粘度を表し、η_calc（ω）はＣａｒｒｅａｕモデルより算出したせん断粘度を表す。〕

[η _exp (ω) represents the measured shear viscosity, and η _calc (ω) represents the shear viscosity calculated from the Carreau model. ]

<Intrinsic viscosity [η]>
About 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice, and the value of η _sp /C when the concentration (C) was extrapolated to 0 as shown in the following formula was determined as the intrinsic viscosity [η] (unit: dl/g).
[η]=lim(η _sp /C) (C→0)

<Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw/Mn, Mz/Mw)>
Using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent, measurements were made as follows.

Two Agilent PLgel Olexis were used as analytical columns, a differential refractometer and three capillary viscometers were used as detectors, the column temperature was 145° C., o-dichlorobenzene was used as the mobile phase, and the flow rate was 1.0 ml. /min, and the sample concentration was 0.1% by weight. As standard polystyrene, one manufactured by Tosoh Corporation was used. For molecular weight calculation, the measured viscosity is calculated from the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw/Mn, Mz /Mw) was determined.

<Synthesis of transition metal compound (A)>
[Synthesis Example 1-1]
0.98 g (40.3 mmol) of magnesium pieces were placed in a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A tetrahydrofuran 10 mL diluted solution of 1.95 g (10.0 mmol) of 2-bromoindene was added dropwise (after adding 1.0 mL, heating under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 6.00 mL (50.2 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 19 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 20 mL of tetrahydrofuran and 1.00 mL (10.6 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 2.65 g (10.0 mmol) of 7-(4-trimethylsilylphenyl)indene synthesized by the method described in WO2012/133717 and 15 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and replaced with argon, and n-butyl 6.45 mL of lithium solution (hexane solution, 1.55 M, 10.0 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 3 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to give the desired product represented by the following formula (A-1L) (hereinafter referred to as compound (A-1L)). was obtained as an isomeric mixture of 2.12 g (48% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.72-7.04 (13H, m, Ar-H&C=CH-C), 7.00-6.60 (1H, m, C=CH-C), 3.94-3.10 (3H, m, Si--CH & C--CH ₂ --C), 0.65-0.10 (15H, m, Si--CH ₃ ) ppm

[Example 1A]
0.88 g (2.01 mmol) of the compound (A-1L) obtained in Synthesis Example 1-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were placed in a 100 mL reactor sufficiently dried and purged with argon, and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. After distilling off the solvent of the reaction liquid, 20 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0° C., 0.46 g (1.99 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, diethyl ether and n-hexane were added to adjust the suspension, insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to give the following formula (A -1) yellow powdery compound dimethylsilylene (2-indenyl) (4-(4-trimethylsilylphenyl)-1-indenyl) zirconium dichloride (hereinafter referred to as compound (A-1)) 0.24 g ( Yield 20%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.68-7.57 (2H, m, Ar-H), 7.54 (4H, s, Ar-H), 7.43-7.34 (2H, m, Ar-H), 7.31-7.17 (3H, m, Ar-H), 7.15 (1H, dd, J = 3.4 and 0.9 Hz, Ind-H), 6.23 (1H , d, J=3.4 Hz, Ind-H), 6.12 (2H, s, Ind-H), 1.13 (3H, s, Si—CH ₃ ), 0.91 (3H, s, Si —CH ₃ ), 0.26 (9H, s, Si—CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 596

[Synthesis Example 2-1]
1.45 g (63.5 mmol) of magnesium pieces were charged into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. 2-Bromoindene 2.93 g (15.0 mmol) diluted solution of 2.93 g (15.0 mmol) of tetrahydrofuran in 10 mL was added dropwise (after adding 1.0 mL, heated under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 20 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 7-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indene synthesized by the method described in JP-A-2017-145240 was placed in a 100 mL reactor that was sufficiently dried and replaced with argon5. 03 g (15.0 mmol) and 15 mL of tetrahydrofuran were charged, 9.70 mL of n-butyllithium solution (hexane solution, 1.55 M, 15.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 19 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-2L) (hereinafter referred to as compound (A-2L)). was obtained as an isomeric mixture of 5.08 g (67% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.50-7.30 (5H, m, Ar-H), 7.30-7.15 (4H, m, Ar-H), 7.15-7. 03 (2H, m, C═CH—C), 6.98-6.46 (1H, s, C═CH—C), 3.90-3.65 (4H, s, —OCH ₃ &Si—CH ), 3.60-2.90 (2H, m, Ar—CH ₂ —C), 1.44 (18H, s, —C(CH ₃ ) ₃ ), 0.25 (3H, s, Si—CH ₃ ), 0.21 (3H, s, Si—CH ₃ ) ppm

[Example 2A]
1.02 g (2.01 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 sufficiently dried and purged with argon and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. This 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 20 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to give the following formula (A-2) Dimethylsilylene (2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indenyl)zirconium dichloride (hereinafter referred to as compound (A-2) ) was obtained (yield 48%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.77-7.55 (2H, m, Ar-H), 7.46-7.32 (4H, m, Ar-H), 7.30-7. 17 (3H, m, Ar-H), 7.10 (1H, d, J = 3.3 Hz, Ind-H), 6.21 (1H, d, J = 3.4 Hz, Ind-H), 6 .13 (1H, t, J=3.3 Hz, Ind-H), 3.70 (3H, s, -OCH ₃ ), 1.41 (18H, s, -C(CH ₃ ) ₃ ), 1. 13 (3H, s, Si--CH ₃ ), 0.90 (3H, s, Si--CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 666

[Synthesis Example 3-1]
0.96 g (39.6 mmol) of magnesium pieces were introduced into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A tetrahydrofuran 10 mL diluted solution of 1.96 g (10.0 mmol) of 2-bromoindene was added dropwise (after adding 1.0 mL, heating under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 6.00 mL (50.2 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 20 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.00 mL (10.6 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 7-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1 synthesized by the method described in JP-A-2017-145240 was placed in a 100 mL reactor that was sufficiently dried and replaced with argon. -Indene 3.49 g (10.0 mmol) and tetrahydrofuran 10 mL were charged, n-butyllithium solution 6.45 mL (hexane solution, 1.55 M, 10.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 17 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-3L) (hereinafter referred to as compound (A-3L)). was obtained as an isomeric mixture of 3.33 g (64% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.50-7.02 (10H, m, Ar-H&C=CH-C), 6.68 (1H, s, C=CH-C), 3.73 ( 3H, s, —OCH ₃ ), 3.61 (1H, s, Si—CH), 3.42-3.10 (2H, m, Ar—CH ₂ —C), 2.12 (3H, s, —CH ₃ ), 1.43 (18H, s, —C(CH ₃ ) ₃ ), 0.31 (3H, s, Si—CH ₃ ), 0.24 (3H, s, Si—CH ₃ ) ppm

[Example 3A]
1.04 g (2.00 mmol) of the compound (A-3L) obtained in Synthesis Example 3-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. This solution was cooled to 0° C., 0.47 g (2.02 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 20 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to give the following formula (A-3) Dimethylsilylene (2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1-indenyl)zirconium dichloride (hereinafter referred to as compound ( A-3)) was obtained (1.01 g, yield 73%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.73-7.57 (2H, m, Ar-H), 7.45-7.15 (7H, m, Ar-H), 6.86 (1H, s, Ind-H), 6.18 (1H, dd, J = 2.6 and 0.9 Hz, Ind-H), 6.13 (1H, dd, J = 2.6 and 0.9 Hz, Ind-H), 3 .71 (3H, s, —OCH ₃ ), 2.33 (3H, s, Ind—CH ₃ ), 1.41 (18H, s, —C(CH ₃ ) ₃ ), 1.15 (3H, s , Si—CH ₃ ), 1.02 (3H, s, Si—CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 680

[Synthesis Example 4-1]
A 300 mL reactor was charged with 9.74 g (40.4 mmol) of 4-bromo-7-methoxy-1-indanone, 35 mL of tetrahydrofuran, and 15 mL of methanol, and stirred. The solution was cooled to 0° C., 3.17 g (38.2 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 4 hours. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 2.98 g (about 12.3 mmol) of the residue obtained by distilling off the filtrate was taken in a 300 mL reactor, and 150 mL of toluene and p-toluenesulfonic acid monohydrate were added. 0.02 g (0.09 mmol) was added and heated in an 80° C. oil bath for 6 hours. After cooling the reaction solution to room temperature, saturated aqueous sodium hydrogencarbonate solution was added, soluble matter was extracted with n-hexane and ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. . After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-4a) (hereinafter referred to as compound (A-4a)). was obtained 1.77 g (yield 64%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.25 (1H, d, J=8.7 Hz, Ar—H), 7.04 (1H, dt, J=5.6 and 1.9 Hz, C=CH—C ), 6.68 (1H, d, J = 8.6 Hz, Ar-H), 6.49 (1H, dt, J = 5.6 and 1.9 Hz, C = CH-C), 3.86 (3H, s, —OCH3), 3.38 (2H, t, J=1.6 Hz, Ar—CH ₂ —C) ppm

[Synthesis Example 4-2]
0.46 g (18.8 mmol) of magnesium pieces were charged into a 300 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, J. Am. Chem. Soc. 2006, 128, 16486. 1-Bromo-3,5-di-tert-butyl-4-methoxybenzene 5.17g (17.3mmol) diluted by 1-bromo-3,5-di-tert-butyl-4-methoxybenzene by the described method was added dropwise to 30mL diluted solution of tetrahydrofuran (after adding 1.0mL, iodine was added with a dryer. After the reaction was started, the mixture was heated under reflux until the color disappeared, and the remaining drops were dropped after the reaction was started. After cooling this reaction solution to −78° C., 2.20 mL (19.8 mmol) of trimethoxyborane was slowly added, and stirring was continued for 19 hours while the temperature was slowly returned to room temperature. A 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with di-iso-propyl ether, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was added with 3.38 g (15.0 mmol) of the compound (A-4a) obtained in Synthesis Example 4-1 and tripotassium phosphate 7. 34 g (34.6 mmol), 0.03 g (0.15 mmol) of palladium acetate, 0.10 g (0.23 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), 35 mL of tetrahydrofuran, distilled 7 mL of water was charged and heated under reflux in an oil bath for 2 hours. After cooling the reaction solution to room temperature, saturated aqueous ammonium chloride solution was added, soluble matter was extracted with n-hexane and ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-4b) (hereinafter referred to as compound (A-4b)). was obtained 5.44 g (yield 99%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.40 (2H, s, Ar-H), 7.20 (1H, d, J = 8.3 Hz, Ar-H), 7.14-6.98 ( 1H, m, C = CH-C), 6.89 (1H, d, J = 8.3 Hz, Ar-H), 6.54-6.45 (1H, m, C = CH-C), 3 .93 (3H, s, -OCH3), 3.75 (3H, s, -OCH3), 3.51 (2H, s, Ar-CH2-C), 1.47 (18H, s, -C (CH3 ) 3) ppm

[Synthesis Example 4-3]
0.97 g (40.1 mmol) of magnesium pieces were charged into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A solution of 1.95 g (10.0 mmol) of 2-bromoindene diluted in 15 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, heating under reflux with a dryer until the color of iodine disappeared, and after starting the reaction, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 6.00 mL (50.2 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 20 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.00 mL (10.6 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 3.65 g (10.0 mmol) of the compound (A-4b) obtained in Synthesis Example 4-2 and 25 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and replaced with argon, and 6.50 mL of an n-butyllithium solution was added. (Hexane solution, 1.55 M, 10.1 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 21 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-4L) (hereinafter referred to as compound (A-4L)). was obtained as an isomeric mixture of 4.32 g (80% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.48-7.28 (4H, m, Ar-H), 7.26-7.18 (2H, m, Ar-H), 7.18-7. 08 (1H, m, Ar-H), 7.08-6.96 (2H, m, Ar-H & C = CH-C), 6.73 (1H, d, J = 8.2 Hz, Ar-H) , 6.67 (1H, dd, J=5.3 and 1.8 Hz, C=CH—C), 3.73 (3H, s, —OCH ₃ ), 3.71 (3H, s, —OCH ₃ ), 3.56-2.90 (1H, m, Si—CH), 3.27 (2H, s, Ar—CH ₂ —C), 1.44 (18H, s, —C(CH ₃ ) ₃ ), 0.29 (3H, s, Si--CH ₃ ), 0.17 (3H, s, Si--CH ₃ ) ppm

[Example 4A]
1.07 g (2.00 mmol) of the compound (A-4L) obtained in Synthesis Example 4-3, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. This 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 20 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off through a glass filter, and the residue is dried under reduced pressure to give the following formula (A-4). Dimethylsilylene (2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl)zirconium dichloride (hereinafter referred to as compound ( A-4)) was obtained (1.01 g, yield 72%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.74-7.63 (1H, m, Ar-H), 7.40-7.17 (6H, m, Ar-H), 6.98 (1H, d, J = 3.3 Hz, Ind-H), 6.57 (1H, d, J = 7.8 Hz, Ar-H), 6.18-6.12 (2H, m, Ind-H), 5 .97 (1H, dd, J = 2.5 and 0.9 Hz, Ind-H), 4.10 (3H, s, -OCH ₃ ), 3.70 (3H, s, -OCH ₃ ), 1.40 ( 18H,s,-C( _CH3 ) ₃ ), 1.06(3H,s,Si- _CH3 ), 0.83(3H,s,Si- _CH3 ) ppm
FD-mass spectroscopy (M ⁺ ): 696

[Synthesis Example 5-1]
0.62 g (25.4 mmol) of magnesium pieces were introduced into a 300 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, J. Am. Chem. Soc. 2006, 128, 16486. Tetrahydrofuran 30 mL diluted solution of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene 6.89 g (23.0 mmol) synthesized by the described method was added dropwise (after adding 1.0 mL, iodine was added with a dryer. After the reaction was started, the mixture was heated under reflux until the color disappeared, and the remaining drops were dropped after the reaction was started. After cooling the reaction solution to −78° C., 2.90 mL (26.1 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while the temperature was slowly returned to room temperature. A 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with di-iso-propyl ether, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 4-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method described in JP-A-2012-121882 was added to the residue obtained by distilling off the filtrate. 4.72 g (20.1 mmol), tripotassium phosphate 9.80 g (46.1 mmol), palladium acetate 0.05 g (0.20 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S- Phos) 0.14 g (0.34 mmol), tetrahydrofuran 50 mL, and distilled water 10 mL were charged, and heated under reflux in an oil bath for 2 hours. After the reaction solution was cooled to room temperature, saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-5a) (hereinafter referred to as compound (A-5a)). was obtained 7.18 g (yield 96%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.31-7.24 (3H, m, Ar—H), 6.87 (1H, dt, J=5.6 and 1.8 Hz, C=CH—C), 6.49 (1H, dt, J=5.6 and 1.8 Hz, C=CH—C), 3.75 (3H, s, —OCH ₃ ), 3.32 (2H, s, Ar—CH ₂ —C ), 3.00 (2H, t, J=7.4 Hz, Ar--CH ₂ --CH ₂ ), 2.85 (2H, t, J=7.3 Hz, Ar--CH ₂ --CH ₂ ), 2. 07 (2H, q, J = 7.3 Hz, _CH2 - _CH2 - _CH2 ), 1.45 (18H, s, -C( _CH3 ) ₃ ) ppm

[Synthesis Example 5-2]
1.45 g (59.8 mmol) of magnesium pieces were charged into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A diluted solution of 2.93 g (15.0 mmol) of 2-bromoindene in 15 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, heating under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 19 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. A 100 mL reactor sufficiently dried and replaced with argon was charged with 5.62 g (15.0 mmol) of the compound (A-5a) obtained in Synthesis Example 5-1 and 15 mL of tetrahydrofuran, and 9.70 mL of an n-butyllithium solution. (Hexane solution, 1.55 M, 15.0 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 45 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-5L) (hereinafter referred to as compound (A-5L)). was obtained as an isomeric mixture of 7.67 g (94% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.54-7.04 (8H, m, Ar-H&C=CH-C), 6.87 (1H, dd, J=5.4 and 1.9 Hz, C=CH -C), 6.55 (1H, dd, J = 5.4 and 1.9 Hz, C = CH-C), 3.73 (3H, s, -OCH ₃ ), 3.69 (1H, s, Si- CH), 3.52-3.18 (2H, s, Ar--CH ₂ --C), 3.14-2.78 (4H, m, Ar--CH ₂ --CH ₂ ), 2.06 (2H, q, J=7.3 Hz, CH ₂ —CH ₂ —CH ₂ ), 1.43 (18H, s, —C(CH ₃ ) ₃ ), 0.27 (3H, s, Si—CH ₃ ), 0 .16 (3H,s,Si—CH ₃ ) ppm

[Example 5A]
1.10 g (2.01 mmol) of the compound (A-5L) obtained in Synthesis Example 5-2, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. This solution was cooled to 0° C., 0.47 g (2.01 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 resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to give the following formula (A-5) Yellow powdery compound dimethylsilylene (2-indenyl) (4-(3,5-di-tert-butyl-4-methoxyphenyl)-1,5,6,7-tetrahydro-s-1-indacenyl ) 0.51 g of zirconium dichloride (hereinafter referred to as compound (A-5)) was obtained (36% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.66-7.57 (1H, m, Ar-H), 7.48-7.37 (1H, m, Ar-H), 7.37-7. 28 (3H, m, Ar-H), 7.27-7.17 (2H, m, Ar-H), 6.86 (1H, d, J = 3.3 Hz, Ind-H), 6.12 (1H, dd, J=2.6 and 0.8 Hz, Ind-H), 6.10-6.04 (2H, m, Ind-H), 3.70 (3H, s, -OCH ₃ ), 3. 05-2.90 (4H, m, Ar—CH ₂ —CH ₂ ), 2.03 (2H, q, J=7.0 Hz, CH ₂ —CH ₂ —CH ₂ ), 1.39 (18H, s , —C(CH ₃ ) ₃ ), 1.11 (3H, s, Si—CH ₃ ), 0.87 (3H, s, Si—CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 706

[Synthesis Example 6-1]
0.61 g (25.0 mmol) of magnesium pieces were charged into a 300 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. Org. Chem. 2006, 2727. and 6.55 g (23.0 mmol) of 4-bromo-2,6-di-iso-propyl-N,N-dimethylaniline synthesized by the method described in WO2007/034975 was added dropwise to 20 mL of tetrahydrofuran (1. After adding 0 mL, the solution was heated under reflux with a drier until the color of iodine disappeared, and after the reaction was started, the remaining droplets were dropped), and after the completion of dropping, the solution was heated under reflux in an oil bath at 80° C. for 1 hour. After cooling the reaction solution to −78° C., 2.90 mL (26.1 mmol) of trimethoxyborane was slowly added, and stirring was continued for 17 hours while the temperature was slowly returned to room temperature. An aqueous ammonium chloride solution was added, the soluble matter was extracted with di-iso-propyl ether, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 4-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method described in JP-A-2012-121882 was added to the residue obtained by distilling off the filtrate. 4.72 g (20.1 mmol), tripotassium phosphate 9.80 g (46.1 mmol), palladium acetate 0.05 g (0.20 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S- Phos) 0.14 g (0.34 mmol), tetrahydrofuran 50 mL, and distilled water 10 mL were charged, and heated under reflux in an oil bath for 2 hours. After the reaction solution was cooled to room temperature, saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-6a) (hereinafter referred to as compound (A-6a)). was obtained 5.57 g (yield 77%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.26 (1H, s, Ar-H), 7.10 (2H, s, Ar-H), 6.87 (1H, dt, J = 5.6 and 1. 8Hz, C = CH-C), 6.48 (1H, dt, J = 5.6 and 1.8Hz, C = CH-C), 3.38 (2H, sep, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 3.33 (2H, s, Ar--CH ₂ --C), 2.99 (2H, t, J=7.3 Hz, Ar--CH ₂ --CH ₂ ), 2.89 (6H, s, —NC(CH ₃ ) ₂ ), 2.86 (2H, t, J=7.3 Hz, Ar—CH ₂ —CH ₂ ), 2.06 (2H, q, J=7.27 Hz, CH ₂ —CH ₂ —CH ₂ ), 1.23 (12H, d, J=6.9 Hz, —CH(CH ₃ ) ₂ ) ppm

[Synthesis Example 6-2]
1.45 g (59.8 mmol) of magnesium pieces were charged into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 10 mL of tetrahydrofuran were charged and stirred. A diluted solution of 2.94 g (15.1 mmol) of 2-bromoindene in 15 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, heating under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 19 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 5.40 g (15.0 mmol) of the compound (A-6a) obtained in Synthesis Example 6-1 and 15 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and replaced with argon, and 9.70 mL of an n-butyllithium solution was added. (Hexane solution, 1.55 M, 15.0 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 21 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-6L) (hereinafter referred to as compound (A-6L)). was obtained as an isomeric mixture of 6.95 g (87% yield).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.56-7.35 (2H, m, Ar-H), 7.35-7.00 (6H, m, Ar-H&C=CH-C), 7. 00-6.78 (1H, m, C=CH-C), 6.70-6.40 (1H, m, C=CH-C), 3.80-3.58 (1H, m, Si- CH), 3.52-3.24 (4H, m, —CH(CH ₃ ) ₂ &, Ar—CH ₂ —C), 3.16-2.70 (4H, m, Ar—CH ₂ —CH ₂ ), 2.88 (6H, s, --NC(CH ₃ ) ₂ ), 2.07 (2H, q, J=7.27 Hz, CH ₂ --CH ₂ --CH ₂ ), 1.35-1. 15 (12H, m, -CH( _CH3 ) ₂ ), 0.27 (3H, s, Si- _CH3 ), 0.16 (3H, s, Si- _CH3 ) ppm

[Example 6A]
1.07 g (2.00 mmol) of the compound (A-6L) obtained in Synthesis Example 6-2, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. This solution was cooled to 0° C., 0.47 g (2.01 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 20 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to give the following formula (A-6) Dimethylsilylene (2-indenyl) (4-(3,5-di-iso-propyl-4-(N,N-dimethylamino)phenyl)-1,5,6,7- 0.30 g of tetrahydro-s-1-indacenyl)zirconium dichloride (hereinafter referred to as compound (A-6)) was obtained (yield 22%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.67-7.56 (1H, m, Ar-H), 7.48-7.40 (1H, m, Ar-H), 7.33 (1H, br-s, Ar-H), 7.30-7.20 (3H, m, Ar-H), 7.15 (1H, br-s, Ar-H), 6.90 (1H, br-s , Ind-H), 6.15-6.07 (2H, m, Ind-H), 6.06 (1H, d, J = 2.6 Hz, Ind-H), 3.31 (2H, br- s, —NC(CH ₃ ) ₂ ), 3.08-2.92 (4H, m, Ar—CH ₂ —CH ₂ ), 2.85 (6H, br-s, —CH(CH ₃ ) ₂ ) , 2.13-1.90 (2H, m, CH ₂ —CH ₂ —CH ₂ ), 1.27-1.08 (12H, m, —CH(CH ₃ ) ₂ ), 1.11 (3H, s, Si--CH ₃ ), 0.88 (3H, s, Si--CH ₃ ) ppm
FD-Mass Spec (M ⁺ ): 691

[Comparative Example 1A]
Dimethylsilylene(cyclopentadienyl)(1-indenyl)zirconium dichloride represented by the following formula (A-7) (hereinafter referred to as compound (A-7)) was prepared according to Macromolecules 1995, 28, 3771. Synthesized by the method described.

[Comparative Example 2A]
Dimethylsilylene(cyclopentadienyl)(4-(4-trimethylsilylphenyl)-1-indenyl)zirconium dichloride (hereinafter referred to as compound (A-8)) represented by the following formula (A-8) is prepared according to WO2012/133717. It was synthesized by the method described in the publication.

[Comparative Example 3A]
Dimethylsilylenebis(1-indenyl)zirconium dichloride represented by the following formula (A-9) (hereinafter referred to as compound (A-9)) was purchased from Wako Pure Chemical Industries.

[Comparative Example 4A]
Ethylenebis(1-indenyl)zirconium dichloride represented by the following formula (A-10) (hereinafter referred to as compound (A-10)) was purchased from Wako Pure Chemical Industries.

[Reference Example 1A]
Dimethylsilylene (2-indenyl) (1-indenyl) zirconium dichloride represented by the following formula (A-11) (hereinafter referred to as compound (A-11)) was synthesized by the method described in JP-A-11-292934. .

[Example 1]
<Preparation of solid catalyst component (X-1)>
Using a reactor with a stirrer with an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Co., Ltd., cumulative 50% particle size of volume distribution by laser light diffraction scattering method: 70 μm, ratio 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]) was suspended in 77 L of toluene, and Cooled to ~5°C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise over 30 minutes as component (B). At this time, the temperature in the system was kept at 0 to 5°C. Then, after contacting them at 0 to 5°C for 30 minutes, the temperature in the system was raised to 95°C over 1.5 hours, and then contacted at 95°C for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry having a total volume of 115 liters. A portion of the resulting slurry was sampled and analyzed to find that the solid concentration was 122.6 g/L and the Al concentration was 0.612 mol/L.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-1) in a slurry state as a solid content were charged, and then added with ethylene at 80° C. The temperature was raised to 8 MPaG, the pressure was increased, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 112.7 g of an ethylene-based polymer. The catalytic activity was 3,760 g-PE/g-solid catalyst component.

To the obtained ethylene-based polymer, 0.1% by mass of IrganoX1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1% by mass of Irgafos168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) are added as heat stabilizers. , Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and melt-kneaded for 5 minutes at a resin temperature of 180° C. and a rotation speed of 50 rpm. Further, this molten polymer was cooled using a press molding machine (manufactured by Shindo Kinzoku Kogyo Co., Ltd.) under conditions of a cooling temperature of 20° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg/cm ² . Using the obtained sample as a measurement sample, physical properties were measured. Table 9 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 20.0 mg of the solid catalyst component (X-2) in a slurry state as a solid content were charged, and then 25 mL of hydrogen was added to ethylene. The temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 74.5 g of an ethylene-based polymer. The catalytic activity was 3,720 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 24.0 mg of the solid catalyst component (X-3) in a slurry state as a solid content were charged, and then a hydrogen concentration of 0.10 vol% was added. Using an ethylene/hydrogen mixed gas, the temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 85.6 g of an ethylene-based polymer. The catalytic activity was 3,570 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 12 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 20.0 mg of the solid catalyst component (X-4) in a slurry state as a solid content were charged, and then added with ethylene at 80° C. The temperature was raised to 8 MPaG, the pressure was increased, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 73.6 g of an ethylene-based polymer. The catalytic activity was 3,680 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 24.0 mg of the solid catalyst component (X-5) in a slurry state as a solid content were charged, and then a hydrogen concentration of 0.10 vol% was added. Using an ethylene/hydrogen mixed gas, the temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 76.9 g of an ethylene-based polymer. The catalytic activity was 3,200 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

[Example 6]
<Preparation of solid catalyst component (X-6)>
A slurry of the solid catalyst component (X-6) was prepared in the same manner as in Example 1 except that the compound (A-6) obtained in Example 6A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 12 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 24.0 mg of the solid catalyst component (X-6) in a slurry state as a solid content were charged, and then 50 mL of hydrogen was added to ethylene. The temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 88.8 g of an ethylene-based polymer. The catalytic activity was 3,690 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

[Comparative Example 1]
<Preparation of solid catalyst component (X-7)>
A slurry of the solid catalyst component (X-7) was prepared in the same manner as in Example 1 except that the compound (A-7) obtained in Comparative Example 1A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 250 mg of the solid catalyst component (X-7) in a slurry state as a solid content were charged, and then ethylene was added at 80° C. and 0.8 MPaG. , and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 110.0 g of an ethylene-based polymer. The catalytic activity was 440 g-PE/g-solid catalyst component. Table 9 shows the results.

[Comparative Example 2]
<Preparation of solid catalyst component (X-8)>
A slurry of the solid catalyst component (X-8) was prepared in the same manner as in Example 1, except that the compound (A-8) obtained in Comparative Example 2A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 120 mg of the solid catalyst component (X-8) in a slurry state as a solid content were charged, and then ethylene was added at 80° C. and 0.8 MPaG. , and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 79.1 g of an ethylene-based polymer. The catalytic activity was 660 g-PE/g-solid catalyst component. Table 9 shows the results.

[Comparative Example 3]
<Preparation of solid catalyst component (X-9)>
A slurry of the solid catalyst component (X-9) was prepared in the same manner as in Example 1, except that the compound (A-9) obtained in Comparative Example 3A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 50.0 mg of the solid catalyst component (X-9) in a slurry state as a solid content were charged, and then a hydrogen concentration of 0.45 vol% was added. Using an ethylene/hydrogen mixed gas, the temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 55.1 g of an ethylene-based polymer. The catalytic activity was 1,100 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

[Comparative Example 4]
<Preparation of solid catalyst component (X-10)>
A slurry of the solid catalyst component (X-10) was prepared in the same manner as in Example 1 except that the compound (A-10) obtained in Comparative Example 4A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-10) in a slurry state as a solid content were charged. Using an ethylene/hydrogen mixed gas, the temperature and pressure were increased to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 125.5 g of an ethylene-based polymer. The catalytic activity was 4,180 g-PE/g-solid catalyst component. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 9 shows the results.

[Reference example 1]
<Preparation of solid catalyst component (X-11)>
A slurry of the solid catalyst component (X-11) was prepared in the same manner as in Example 1, except that the compound (A-11) obtained in Reference Example 1A was used instead of the compound (A-1). .

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a SUS autoclave having an internal volume of 1 liter which was sufficiently purged with nitrogen, ethylene was circulated to saturate the interior of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 60.0 mg of the solid catalyst component (X-11) in a slurry state as a solid content were charged, and then added with ethylene at 80° C. The temperature was raised to 8 MPaG, the pressure was increased, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 90.0 g of an ethylene-based polymer. The catalytic activity was 1,500 g-PE/g-solid catalyst component. Table 9 shows the results.

Examples using the transition metal compound [A] (bridged (2-indenyl)(1-indenyl) type compound) of the present invention are Comparative Example 1 using a bridged cyclopentadienyl (1-indenyl) type compound, 2 showed higher catalytic activity. Furthermore, it exhibited a higher catalytic activity than Reference Example 1 using a bridged (2-indenyl)(1-indenyl) type compound having no specific substituent on the 1-indenyl ring. Also, the value of [η]/Mw ^0.776 is smaller than in Comparative Examples 3 and 4 using bridged bis(1-indenyl) type compounds, which means that the amount of long-chain branching introduced is large.

Claims (10)

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

(In the general formula [1], M is a Group 4 transition metal atom of the periodic table,
n is 2;
X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing group, which may be the same or different, and the nitrogen-containing group is a dimethylamino group or a diethylamino group;
Q is a carbon atom or a silicon atom,
R1 ^{, R2 ,} R3, ^{R4 , R5} , R6, ^R7 , ^R8 , ^R9 , ^R10 , R11, ^{R12 , R13} , ^R14 , ^R15 , ^R16 , ^R17 and R ¹⁸ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms. is the basis,
R ⁹ and R ¹⁰ are bonded to each other to condense the indenyl ring moiety, optionally having a substituent, a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon; may form a 5- to 8-membered ring consisting of
Adjacent substituents among R ¹² to R ¹⁶ are bonded to each other to condense the benzene ring portion, optionally having a substituent, to form a saturated hydrocarbon (the hydrocarbon of the benzene ring portion is ) or may form a 5- to 8-membered ring composed of unsaturated hydrocarbons,
R ¹⁷ and R ¹⁸ may combine with each other to form a ring containing Q, which ring may have a substituent, is a 3- to 8-membered and saturated ring. ) In the general formula [1],
M is a zirconium atom or a hafnium atom,
R ¹ to R ⁶ , R ⁸ , R ¹² and R ¹⁶ are hydrogen atoms,
R ⁷ is hydrogen atom, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, cyclopropyl group, sec-butyl group, neopentyl group, methoxy group, ethoxy group, iso-propoxy group , a furyl group or a methylfuryl group,
R ⁹ and R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ¹¹ is hydrogen atom, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, phenyl group, tolyl group, xylyl group, mesityl group, 4-tert-butylphenyl group, 3, 5-di-tert-butylphenyl group, 4-trimethylsilylphenyl group, methoxy group, ethoxy group, iso-propoxy group, furyl group, methylfuryl group or 3,5-di-tert-butyl-4-methoxyphenyl group; can be,
R ¹³ and R ¹⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, an iso-propyl group, a sec-butyl group or a tert-butyl group;
R ¹⁴ is a hydrogen atom, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, tert-butyl group, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert- butyldimethylsilyl group, triphenylsilyl group, methoxy group, ethoxy group, iso-propoxy group, amino group, dimethylamino group, diethylamino group or pyrrolidinyl group;
R ¹⁷ and R ¹⁸ are methyl groups,
R ⁹ and R ¹⁰ are a 5-membered ring consisting of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion), optionally having a substituent, which is bonded to each other and condensed to the indenyl ring portion; may form
The transition metal compound [A] according to claim 1. In the general formula [1],
Q is a silicon atom,
R ⁷ is a hydrogen atom or a methyl group,
3. The transition metal compound [A] according to claim 2, wherein ^R11 is a hydrogen atom, a methyl group or a methoxy group. In the general formula [1],
4. The transition metal compound [A] according to claim 2 or 3, wherein ^R9 and ^R10 are hydrogen atoms. In the general formula [1] ,
Claim 2 or 3, wherein R ⁹ and R ¹⁰ are combined to form a 5-membered ring consisting of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) condensed to the indenyl ring portion. The described transition metal compounds [A]. In the general formula [1],
The transition metal compound [A] according to any one of claims 3 to 5, wherein X is a halogen atom, methyl group, benzyl group or dimethylamino group. An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 6. Furthermore, [B] [B-1] organometallic compound,
[B-2] organoaluminum oxy compound, and [B-3] transition metal compound [A] and at least one compound selected from the group consisting of a compound that forms an ion pair by reacting with [A]. of olefin polymerization catalysts. A method for producing an olefin polymer, comprising the step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7 or 8. 10. The method for producing an olefin polymer according to claim 9, 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 to 20 carbon atoms.