JP2020050615A - Transition metal compound, olefin polymerization catalyst, and olefin polymer production method - Google Patents

Abstract

To provide a transition metal compound and the like which allow a polymer with many long chain branches introduced therein to be produced with high catalytic activity even with an olefin polymerization catalyst comprising only one transition metal compound.SOLUTION: The transition metal compound is represented by the general formula [1] in the figure, where M is a group 4 transition metal; X is H, halogen, hydrocarbon, or an anionic or neutral ligand; Q is a group 14 atom; Rto Rare each independently H, C1-40 hydrocarbon, or the like; and Ris not H.SELECTED DRAWING: None

Description

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

  Olefin polymers are molded by various molding methods and used for various applications. For example, an extruded product of an ethylene-based polymer is used for a film or sheet used for packaging foodstuffs, liquids, daily necessities and the like. The characteristics required for the olefin polymer vary depending on the molding method or application. For example, when performing T-die molding, stable molding can be performed even at high speed (high-speed film forming processability), Is required to have a processing performance such as a small size.

  Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branched structure, has high melt tension, and therefore has good moldability such as small neck-in. Has been offered to. However, there still remain problems such as low mechanical strength such as tensile strength, tear strength or impact resistance of the molded product, and poor high-speed film forming workability in T-die molding.

  On the other hand, ethylene polymers produced using Ziegler catalysts or metallocene catalysts, in contrast to LDPE, have high tensile strength, tear strength or high impact strength due to their molecular structure, and therefore have a high mechanical strength. Although it is used for applications requiring strength, there is a problem that the melt tension is small and the moldability is poor.

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

  Further, as a method for producing an ethylene-based polymer having a long-chain branch in the presence of a solid catalyst component comprising one kind of transition metal compound and a solid support, a crosslinked bis (1-indenyl) type compound is used as a transition metal compound. (Patent Document 3 and the like) and a method using a crosslinked cyclopentadienyl (1-indenyl) type compound (Patent Documents 4 and 5 and the like).

  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 below.

JP 2006-233208 A JP 2009-144148 A JP 2007-119716 A WO 2015/152268 JP 2014-118550 A JP-A-11-315089 JP-A-11-292934 JP 2001-220404 A JP 2001-302687 A

Macromolecules, 2004, 37 (7), 2342

  When an ethylene-based polymer is produced using a solid catalyst component comprising two types of transition metal compounds and a solid support described in Patent Documents 1 and 2, etc., one type of transition metal compound and a solid support are used. The method for controlling the polymer composition is more complicated than 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 single transition metal compound, the ratio of the amount of polymer produced from each transition metal compound is also a variable factor of the obtained polymer composition. This is because The ratio of the amount of polymer generated from each transition metal compound can be controlled by the contact ratio of each transition metal compound to be brought into contact with the solid support, but also depending on the amount of catalyst poison such as moisture. Can fluctuate. In fact, when slurry polymerization or gas phase polymerization is carried out batchwise or continuously by introducing ethylene in the presence of a solid catalyst, the composition of the obtained polymer may fluctuate and the product may be out of specification. Therefore, from the viewpoint of simplification of the control method of the polymer composition, it is desired that only one transition metal compound is used for the solid catalyst component.

  On the other hand, in the method for producing an ethylene-based polymer having a long-chain branch in the presence of a solid catalyst component comprising one type of transition metal compound and a solid support described in Patent Documents 3 to 5, etc. There have been 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 is a transition metal compound that can be used as a component of an olefin polymerization catalyst, and a transition metal compound contained in the olefin polymerization catalyst. A transition metal compound capable of producing an ethylene-based polymer into which many long-chain branches have been introduced with high catalytic activity even if only one is used, and an olefin represented 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.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have solved the above-mentioned problems by using a bridged (2-indenyl) (1-indenyl) type compound having a specific substituent on a 1-indenyl ring. We have found what we can do and completed the present invention.

  Olefin polymerization using a transition metal compound having a 2-indenyl group is reported in Patent Documents 6 to 9 and Non-Patent Document 1, and for example, Patent Document 6 discloses production of an amorphous (co) polymer. For this reason, it is described that ethylene polymerization was carried out in the presence of (2-indenyl) (1-indenyl) dimethylsilylzirconium dichloride (Example 11 and the like). -Indenyl) (2-phenyl-1-indenyl) dimethylsilyl] in the presence of zirconium dichloride is described as copolymerization of ethylene and propylene and copolymerization of ethylene and 1-hexene. However, there is no description or suggestion about production of an ethylene polymer having a long chain branch.

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およびＲ¹⁴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、
Ｒ¹⁰およびＲ¹¹のうち、少なくとも１つは水素原子ではなく、
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〜Ｒ¹²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、
Ｒ¹³およびＲ¹⁴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 transition metal atom belonging to Group 4 of the periodic table,
n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, Group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group, and when n is 2 or more, a plurality of groups represented by X are the same as each other May be different from each other, and may combine with each other to form a ring,
Q is a Group 14 atom in the periodic table;
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 and R ¹⁴ 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,
At least one of R ¹⁰ and R ¹¹ is not a hydrogen atom,
Adjacent substituents among R ^{1 to} R ⁶ may be bonded to each other to form a ring which may have a substituent,
Adjacent substituents among R ^{7 to} R ¹² may be bonded to each other to form a ring which may have a substituent,
R ¹³ and R ¹⁴ may 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,
X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group,
Q is a carbon atom or a silicon atom,
R ^{1 to} R ¹⁴ 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, The transition metal compound [A] according to the above [1], which is a nitrogen-containing group or a sulfur-containing group having 1 to 20 carbon atoms.

[3]
In the general formula [1],
Q is a silicon atom,
R ^{1 to} R ¹⁴ 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 1 to 20 carbon atoms. The transition metal compound [A] of the above [2], which is a nitrogen-containing group.

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

[5]
In the general formula [1],
The transition metal compound [A] according to the above [4], wherein R ^{2 to} R ⁵ and R ⁸ are hydrogen atoms.

[6]
In the general formula [1],
The transition metal compound [A] of the above-mentioned [5], wherein at least one of R ¹⁰ and R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

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

[8]
Further, [B] [B-1] an organometallic compound,
[B-2] an organic aluminum oxy compound, and [B-3] at least one compound selected from the group consisting of compounds which react with the transition metal compound [A] to form an ion pair. Olefin polymerization catalyst.

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

[10]
The method for producing an olefin polymer according to [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.

  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 olefin polymerization catalyst contains only one kind of transition metal compound, ethylene having a long chain branch introduced therein A polymer can be produced with high catalytic activity.

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

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

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

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

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine or bromine.
As the hydrocarbon group, for example,
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), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3 -Methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamil group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, Linear or branched alkyl groups such as 3,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), and 4,4-dimethylpentyl group; Kill 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) , Buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbut-3-en-1-yl group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) A) a linear or branched alkenyl group or an unsaturated double bond-containing group;
A linear or branched alkynyl group or an unsaturated triple bond-containing group such as an ethynyl group, a prop-2-yn-1-yl group, a propargyl group (prop-1-yn-1-yl group);
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 linear groups such as -tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group) Or a branched alkyl group and an unsaturated double bond-containing group;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group and 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), and 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- and aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group.

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

  Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, and a 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 preferable.
Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, and a tris ( Trimethylsilyl) silyl group and trimethylsilylmethyl group.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
Examples of the oxygen-containing group include methoxy, ethoxy, n-propoxy, iso-propoxy, allyloxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, and benzyloxy. 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 preferable.
Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), Examples include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group).

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

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

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, and (benzyl) (tris (pentafluorophenyl) A) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is independently hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like; Shown)).
As the aluminum-containing group, for example,

（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).)
And a group represented by AlR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

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

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

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

"R ¹ ~R ^14"
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 ¹³ and R ¹⁴ are each independently A hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, and at least one of R ¹⁰ and R ¹¹ is hydrogen Substituents similar to those described above other than atoms.

Examples of the hydrocarbon group having 1 to 40 carbon atoms as R ^{1 to} R ¹⁴ include a hydrocarbon group having 1 to 20 carbon atoms, and more specific examples include those described above for X. Specific examples of the hydrocarbon group are given.

  The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (however, 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 includes a substituent having an aromatic structure such as an arylalkyl group.

As the hydrocarbon group having 1 to 40 carbon atoms, for example,
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group , 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group Tert-pentyl group (1,1-dimethylpropyl group), siamil 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-di Butyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3- Yl, heptane-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptane-4-yl, A linear group having 1 to 40 carbon atoms such as a 4-propylheptane-4-yl group, a 2,3,3-trimethylbutan-2-yl group, and a 2,4,4-trimethylpentan-2-yl group; Or a branched alkyl group;
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, buta-1,3 -Dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-ene- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1 , 4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-diene 1-yl group), penta-2,4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl Group, hexa-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-penta-4 -En-1-yl group, hexa-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2 , 3-Dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hexa-3,5-diene- 1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-di Tyl-buta-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentane A linear or branched alkenyl group having 2 to 40 carbon atoms or an unsaturated double bond-containing group such as dienyl) ethyl group;
An ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-1-yn-1-yl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, Penta-1-yn-1-yl group, penta-2-yn-1-yl group, penta-3-yn-1-yl group, penta-4-yn-1-yl group, 3-methyl-buta- 1-yn-1-yl group, penta-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, penta-4-yn-2-yl group, hexa-1- In-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 A linear or branched group having 2 to 40 carbon atoms, such as a -1-yl group, a hexa-4-yn-1-yl group, and a hexa-5-yn-1-yl group; Jo alkynyl group or unsaturated triple 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-triphenyl Lopan-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- Enylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl Group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1- (Indacenyl) propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-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, An aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms such as a (1-azulenyl) ethyl group and an unsaturated double bond-containing group;
Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, dimethylcyclopentadienyl, n-butylcyclopentadienyl, n-butyl-methylcyclopentadienyl, 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, cycloheptyl, cycloheptenyl, cycloheptatrienyl, 1-methylcycloheptyl, 1-allylcycloheptyl, 1-benzylcycloheptyl, cyclooctyl, cyclooctenyl, cyclooctyl Octadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group , 2-methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] 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, tetrahydroindase A cyclic saturated or unsaturated hydrocarbon group having 3 to 40 carbon atoms, such as a nyl group, a benzoindenyl group or an azulenyl group;
Phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, julyl 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, 4-adamantylphenyl, 3,5-di-adamantylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, ferrocenyl and the like An aromatic substituent having 6 to 40 carbon atoms is exemplified.

  Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl Group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl Group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane-4-yl group, 4-propylheptane-4-yl group, 2,4,4-trimethylpentane -2-yl group and the like are preferable, 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, A 4-dimethylpentan-2-yl group and a 2,4,4-trimethylpentan-2-yl group are more preferred.

  Among the linear or branched alkenyl or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl, allyl, but-3-en-1-yl, crotyl, methallyl Group, penta-4-en-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-en-2-yl Preferred are an yl group, a 2- (cyclopentadienyl) propan-2-yl group, a 2- (cyclopentadienyl) ethyl group and the like, and a vinyl group, an allyl group, a but-3-en-1-yl group, a penta group A -4-en-1-yl group, a prenyl group and a hexa-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, prop-2-yn-1-yl, propargyl, but-2-yn -1-yl group, but-3-yn-1-yl group, penta-3-yn-1-yl group, penta-4-yn-1-yl group, 3-methyl-but-1-yn-1 -Yl group, 3,3-dimethyl-but-1-yn-1-yl group, hexa-4-yn-1-yl group, hexa-5-yn-1-yl group and the like are preferable. In-1-yl, propargyl, but-2-yn-1-yl and but-3-yn-1-yl are more preferred.

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

  Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, 1-methylcyclopentyl, 1-allylcyclopentyl Group, 1-benzylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, 1-allylcyclohexyl, 1-benzylcyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, 1-methylcyclo Heptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [2.2 1] heptane-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group and the like are preferable, and cyclopentyl group, cyclo Pentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, and 1-adamantyl are more preferred.

  Among the aromatic substituents having 6 to 40 carbon atoms, phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-di-iso-propylphenyl, 2,4,6-triphenyl -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 , A binaphthyl group, a phenanthryl group, an anthracenyl group, a ferrocenyl group and the like are preferable, and a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-triene -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl , Allyl phenyl group, 4-adamantyl phenyl group, a naphthyl group, a biphenyl group, phenanthryl group, anthracenyl group are more preferable.

  Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, and a 3,3,3-trifluoro 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, trifluoromethylthio Phenyl, bistrifluoromethylthiophenyl, fluorobiphenyl, difluorobiphenyl, trifluorobiphenyl, tetrafluorobiphenyl, pentafluorobiphenyl, di-tert-butyl-fluorobiphenyl, trifluoromethylbiphenyl, bistrifluoro Methylbiphenyl 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, trif Oro-methoxyphenoxy group, bistrifluoroacetic methoxyphenoxy group, difluoromethylene dioxy phenyl group, bis-trifluoromethylphenyl imino methyl group, trifluoromethylthio group, and the like.

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

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

  Among the silicon-containing groups, trimethylsilyl, triethylsilyl, tri-iso-propylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, An indenyldimethylsilyl group, an indenyldiphenylsilyl group, a fluorenyldimethylsilyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, 3,5-bis (trimethylsilyl) phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-trimethylsilyl group Chill silyl phenyl group, 4-tri -iso- propyl silyl phenyl group, 3,5-bis (trimethylsilyl) phenyl group is more preferable.

  Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, and a methallyloxy group. , Prenyloxy, benzyloxy, methoxymethoxy, methoxyethoxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, iso-propoxy Phenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxy Ethyl 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, methylenedioxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furyl, methylfuryl, tetrahydro Lil group, pyranyl group, tetrahydropyranyl group, Furofuriru group, benzofuryl group, a dibenzofuryl group.

  Among the oxygen-containing groups, an alkoxy group having 1 to 20 (preferably 1 to 10) carbon atoms is preferable. Specifically, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a tert group -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, dimethyldiol Sanyl 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 preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group , Dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4 -Methoxyphenyl group, free Group, methyl furyl group, benzofuryl group, dibenzofuryl group is more preferable.

  Examples of the nitrogen-containing group include, for example, amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, azepinyl group, Dimethylaminomethyl, dibenzylaminomethyl, pyrrolidinylmethyl, dimethylaminoethyl, benzylaminomethyl, benzylaminoethyl, pyrrolidinylethyl, dimethylaminovinyl, benzylaminovinyl, pyrrolidini Vinyl, dimethylaminopropyl, benzylaminopropyl, pyrrolidinylpropyl, dimethylaminoallyl, benzylaminoallyl, pyrrolidinylallyl, aminophenyl, dimethylaminophenyl, 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 , A benzimidazolyl group, Kisazoriru group, oxazolidinyl group, such as benzoxazolyl group.

  Among the nitrogen-containing groups, an amino group having 1 to 20 (preferably 1 to 10) carbon atoms is preferable, and specifically, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, a dibenzylamino Group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethyl Aminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl Group, tetramethyljulolidinyl group, pyrrolidinyl Phenyl, pyrrolylphenyl, carbazolylphenyl, di-tert-butylcarbazolylphenyl, pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, iso-quinolyl, tetrahydro-iso-quinolyl , An indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzooxazolyl group are preferable. Amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group , Tetramethyljuro Jiniru group, pyrrolidinylmethyl phenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, an imidazolyl group is more preferable.

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

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

Adjacent substituents of R ^{1 to} R ⁶ (eg, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ ) It may combine to form a ring which may have a substituent. The ring formed in this case is a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may be substituted and which is condensed with the indenyl ring portion. A 5- to 8-membered ring is preferred. When a plurality of rings are present, they may be the same or different. Although not particularly limited as long as the effects of the present invention can be obtained, the ring is more preferably a 5- or 6-membered ring. Examples thereof include a benzyl ring, a substituted tetrahydroindacene ring and a substituted cyclopentatetrahydronaphthalene, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

Adjacent substituents of R ^{7 to} R ¹² (eg, R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ and R ¹² ) It may combine to form a ring which may have a substituent. The ring formed in this case is a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may be substituted and which is condensed with the indenyl ring portion. A 5- to 8-membered ring is preferred. When a plurality of rings are present, they may be the same or different. Although not particularly limited, as long as the effects of the present invention can be obtained, the ring is more preferably a 5- or 6-membered ring. In this case, the combined structure of the ring and the indenyl ring portion of the mother nucleus includes, for example, Examples include a benzyl ring, a substituted tetrahydroindacene ring, a substituted cyclopentatetrahydronaphthalene, a substituted tetrahydrofluorene ring, and a substituted fluorene ring, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferable.

R ¹³ and R ¹⁴ may combine with each other to form a ring containing Q. The ring formed in this case is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is preferably a 4- to 6-membered ring. In this case, as a structure obtained by combining R ¹³ and R ¹⁴ with Q, for example, a substituted cyclobutane ring, a substituted cyclo Pentane ring, substituted fluorene ring, substituted silacyclobutane (silethane) ring, substituted silacyclopentane (silorane) ring, substituted silacyclohexane (silinane), substituted silafluorene ring; substituted cyclopentane ring, substituted silacyclobutane ring, substituted Silacyclopentane rings are preferred.

R ^{1 to} R ⁶ and R ⁸ 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, 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, particularly preferably a hydrogen atom It is.

R ⁷ , R ⁹ and R ^{12 to} R ¹⁴ 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 preferred are 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, and a nitrogen-containing group having 1 to 20 carbon atoms.

R ¹⁰ and R ¹¹ 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, 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, particularly preferably at least one is It is a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
In addition, in at least one of R ⁷ , R ⁹ and R ¹² , particularly R ⁷ , the oxygen-containing group, the nitrogen-containing group or the sulfur-containing group may be a heterocyclic aromatic group described later.

<< Preferred embodiment of transition metal compound [A] >>
Preferred embodiments of the transition metal compound [A] include:
In the general formula [1],
M is a zirconium atom or a hafnium atom,
X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group,
Q is a carbon atom or a silicon atom,
R ^{1 to} R ¹⁴ 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, A nitrogen-containing group or a sulfur-containing group having 1 to 20 carbon atoms,
Transition metal compound [A-1] in which at least one of R ¹⁰ and R ¹¹ is not a hydrogen atom
And more preferred embodiments include
In the general formula [1],
Q is a silicon atom,
R ^{1 to} R ¹⁴ 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 1 to 20 carbon atoms. A nitrogen-containing group,
Transition metal compound in which at least one of R ¹⁰ and R ¹¹ is not a hydrogen atom [A-2]
Is mentioned.

As a more preferred embodiment of the transition metal compound [A-2], R ^{1 to} R ⁶ and R ⁸ in the general formula [1] are hydrogen atoms,
A transition metal compound [A-3] in which at least one of R ¹⁰ and R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

In the above transition metal compound [A-1], a 5-membered ring containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur, which is one of the options of R ⁷ , R ⁹ and R ^12. Examples of the heterocyclic aromatic group which may have a substituent (hereinafter, also referred to as “hetero five-membered ring”) include, for example, groups represented by the following general formulas [4a] to [4h] Is mentioned.

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, and R ^d is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. Is also good.

In addition, the wavy lines in the general formulas [4a] to [4h] indicate binding 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 those described above as examples of the hydrocarbon group having 1 to 40 carbon atoms as R ^{1 to} R ^14. And methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, iso-propyl, 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 , Benzhydryl, cumyl, 1,1-diphenylethyl, trityl, 2-phenylethyl, 3-phenylpropyl, cinnamyl, phenyl, tolyl, xylyl, mesityl, cumenyl, 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, Kurohekishiru group, 1-adamantyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, mesityl group, naphthyl group, biphenyl group, and ter phenyl group.

R ^d each independently bonded to one another with adjacent R ^d together are condensed to heterocyclic 5-membered ring moiety, which may have a substituent, 5-8 membered with heterocyclic 5-membered ring moiety of atoms 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 effects of the present invention are exerted, but is preferably a 5- or 6-membered ring. In this case, as a structure combining this ring and a 5-membered heterocyclic ring portion of the mother nucleus. Examples thereof include a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

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

<< Example of transition metal compound [A] >>
Hereinafter, specific examples of the transition metal compound [A] will be shown, but the scope of the present invention is not particularly limited by these examples.

For convenience, the ligand structure of the transition metal compound [A] excluding the portion represented by MXn (metal portion) is replaced with a 2-indenyl ring portion, a 1-indenyl ring portion, an indenyl ring portion R ¹ , R ⁶ and R ^8. Substituents, indenyl ring moieties R ² , R ⁵ , R ⁹ , and R ¹² substituents, indenyl ring moieties R ³ , R ⁴ , R ¹⁰ , and R ¹¹ substituents, 1-indenyl ring moiety R ⁷ substituents, cross-linking It is divided into seven parts. The abbreviation of the 2-indenyl ring portion is α, the abbreviation of the 1-indenyl ring portion is β, the abbreviation of the indenyl ring portions R ¹ , R ⁶ and R ⁸ is γ, the indenyl ring portions R ² , R ⁵ , R ⁹ , and abbreviations R ¹² substituents [delta], indenyl ring moiety ^{R 3, R 4, R 10} , and the abbreviation R ¹¹ substituents epsilon, 1-indenyl ring portion abbreviations R ⁷ substituents zeta, the structure of the bridging moiety Is represented by η, and the abbreviations of the respective substituents are shown in [Table 1] to [Table 7].

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。

In addition, the wavy line in the above [Table 1] and [Table 2] indicates a binding site with a crosslinked portion.

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 from each other in the combination.

前記［表４］中のＲ²、Ｒ⁵、Ｒ⁹およびＲ¹²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 , R ⁹ and R ¹² substituents in Table 4 above may be the same or different from each other in the combination.

前記［表５］中のＲ³、Ｒ⁴、Ｒ¹⁰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。ただし、Ｒ¹⁰およびＲ¹¹置換基のうち、少なくとも一つはε−１とはならない。

The R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituents in the above [Table 5] may be the same or different from each other in the combination. However, at least one of the R ¹⁰ and R ¹¹ substituents is not ε-1.

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

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

Further, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the indenyl ring portions R ¹ , R ⁶ and R ⁸ are all substituents. All of the γ-1,2-indenyl ring moieties R ² and R ^{5 in} Table 3 are the same as those of the δ-2,2-indenyl ring moieties R ³ and R ^{4 in} Table 4. [Table 5] epsilon-1,1-indenyl ring moiety R ⁷ substituent of the zeta-2,1-indenyl ring moiety R ⁹ substituent in Table 6 in Table 4 in [delta]-43, The 1-indenyl ring moiety R ¹⁰ substituent is ε-3 in [Table 5], and the 1-indenyl ring moiety R ¹¹ substituent is ε- ^{12 and} 1-indenyl ring moiety R ^{12 in} [Table 5] substituent. [Table 4] [delta]-1 in the crosslinked portion formed by a combination of the eta-20 in Table 7], MXn metal parts in the case of ZrBN _2, represented by the following formula [6] The compounds are exemplified.

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

Further, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-8 in [Table 2], the 2-indenyl ring portions R ¹ and R ⁶ are all [ Table 3] gamma-1,2-indenyl ring moiety R ² substituents in Table 4 in [delta]-7, both indenyl ring moiety R ³ and R ⁴ substituents in the Table 5] .epsilon. The 1,2-indenyl ring moiety R ⁵ substituent is [delta] -2,1-indenyl ring moiety R ^{7 in} [Table 4] The substituent is [Sigma] -1,1-indenyl ring moiety R ^{8 in} [Table 6]. The group is γ- ^{9 in} [Table 3], the 1-indenyl ring moiety R ⁹ and R ¹² are all δ-1 in [Table 4], and the cross-linking moiety is η-4 in [Table 7]. When the metal portion MXn is composed of Ti (1,3-pentadienyl) in combination, the compound represented by the following formula [8] is exemplified.

  Further, the transition metal compound [A] has two directions of an indenyl ring portion bonded to the central metal with the crosslinked portion interposed therebetween (front surface and rear surface). Therefore, when there is no symmetry plane in the 2-indenyl ring portion, two types of structural isomers represented by the following general formula [9a] or [9b] exist as examples.

同様に、架橋部分の置換基Ｒ¹³とＲ¹⁴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, when the substituents R ¹³ and R ¹⁴ in the cross-linking portion are not the same, there are two types of structural isomers represented by the following general formula [10a] or [10b] as an example.

  Purification, fractionation, or selective production of the structural isomers can be performed by a known method, and the production method is not particularly limited. As well-known production methods, in addition to those mentioned as the method for producing the transition metal compound [A], JP-A-10-109996, “Оrganometallics 1999, 18, 5347.”, “Оrganometallics 2012, 31, 4340. And the manufacturing method disclosed in Japanese Patent Application Publication No. 2011-502192.

  In addition, within the range of the transition metal compound [A], one transition metal compound may be used alone, two or more transition metal compounds may be used in combination, or a mixture of 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 a transition metal compound constituting a catalyst for olefin polymerization. However, as long as this effect is not impaired, one or more transition metal compounds different from the transition metal compound [A] may be used in combination as the transition metal compound. At this time, the transition metal compound [A] may be any of the above-described embodiments.

<< Method for producing transition metal compound [A] >>
The transition metal compound [A] can be produced using a conventionally known method, and examples of typical synthetic routes are shown below, but the production method is not particularly limited. In the following [Formula 1] to [Formula 5], R ^{1 to} R ¹⁴ , Q, M, X and n have the same meanings as those described in the general formula [1].

  The substituted indene compound as a starting material can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, "@rganomemetallics 1994, 13,954.", "@Rganometallics 2006, 25, 1217.", JP-T-2006-509059, "Bioorg. Med. Chem. 2008, 16, 7399." W @ 2009/080216, "@rganometallics 2011, 30, 5744.", JP-T-2011-500800, "@rganometallics 2012, 31,4962.", "Chem. Eur. J. 2012, 18, 4174." Japanese Patent Application Laid-Open No. 2012-012307, Japanese Patent Application Laid-Open No. 2012-121882, Japanese Patent Application Laid-Open No. 2014-196319, Japanese Patent Application Laid-Open No. 2014-513735, Japanese Patent Application Laid-Open No. 2015-063495. JP 2016-501952 Patent manufacturing method disclosed in such publications can be mentioned.

  Of the substituted indene compounds, the 2-position unsubstituted one can be brominated at the 2-position by a known method as described below, 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. The indene compound has a 5-membered ring partial double bond positional isomer, and a mixture of these isomers may be used. Known production methods include, for example, the production methods disclosed in JP-A-2014-111568 in addition to JP-A-2012-121882 and JP-A-2015-063495 described above.

  The 2-position brominated substituted indene compound and the 4-position brominated substituted indene compound can produce a corresponding coupling product by a known method such as the following palladium-catalyzed Suzuki-Miyaura coupling reaction, The production 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。

Similar to the above, there are positional isomers of the 5-membered ring double bond of the indene compound, and a mixture of these isomers may be used.

  In addition, other boron compounds such as various boronic esters and boroxines may be used instead of boronic acid, and a halogenated compound and a metal reagent, and then a reaction mixture of the boron compound may be used without isolation and purification, A nickel catalyst or an iron catalyst may be used instead of the palladium catalyst. Known production methods include, for example, Japanese Patent Application Laid-Open No. 2014-196274, in addition to those described above.

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

  In the production of the coupling product, a known method such as a direct coupling reaction using a palladium catalyst using the 2-position unsubstituted indene compound and an aromatic halide may be used.

前記［式３］中、Ａｒは芳香族置換基を示し、インデン化合物５員環部分二重結合位置異性体の混合物を用いてもよい。公知の製造方法として例えば、特表２０００−５１２６６１号公報、特開２０１４−２０１５１９号公報などが挙げられる。

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

  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 method or the like. When Q is a silicon atom, a germanium atom or a tin atom, it can be produced by the following method, and the production method is not particularly limited.

  In the above [Formula 4], in the synthesis of the precursor compound (ligand), the organomagnesium reagent adjusted from the 2-brominated substituted indene compound and the organolithium reagent adjusted from the substituted 1-indene compound are stepwise. Preferably reacts 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 in an inert atmosphere, and the reaction product is used after being isolated by distillation, crystallization or washing. Is also good. At the time of the reaction with the organometallic reagent in the second step, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N, N'-dimethylpropylene urea) or HMPA (hexamethylphosphoric triamide) is used. It is preferable to add 0.1 to 5.0 equivalents to the organometallic reagent, more preferably DMI, and 1.0 equivalent. In addition, the substituted indene compound and the precursor compound (ligand) include a 5-membered ring partial double bond position isomer 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, for example, those disclosed in JP-A-11-315089, JP-A-2001-302687, and JP-A-2001 in addition to those described above. -220404, "Polymer Paper Collection 2002, 59,243.", JP-T-2003-522194, "Macromolecules 2004, 37, 2342.", JP-A-2007-320935, JP-A-2011-126913. Gazettes and the like.

  When Q is a carbon atom, it can be produced by the following method, 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, an organic metal compound such as sodium hydride, n-butyllithium, or Grignard reagent, sodium hydroxide, or potassium hydroxide. And an organic base such as diethylamine and pyrrolidine, but is not limited thereto. In the presence of a basic substance, a fulvene compound can be synthesized by a known method from a substituted 1-indene compound and a carbonyl compound, and the precursor compound (C) can be synthesized by reaction with an organomagnesium reagent prepared from a 2-brominated substituted indene compound. Is manufactured. In addition, the substituted indene compound and the precursor compound (ligand) include a 5-membered ring partial double bond position isomer 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, for example, "Macromolecules 2003, 36, 9325." and "Organometrics 2004, 23, 5332." , "Eur. J. Inorg. Chem. 2005, 1003.", "Eur. J. Inorg. Chem. 2009, 1759.", and the like.

[Olefin polymerization catalyst]
The olefin polymerization catalyst of the present invention contains the transition metal compound [A] of the present invention.
The catalyst for olefin polymerization of the present invention typically includes a catalyst for ethylene polymerization.

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

As the organometallic compound [B-1], the compounds disclosed in JP-A-11-315109 or EP0874005A by the present applicant can be used without limitation.
As the organometallic compound [B-1], those represented by the general formula (B-1a) are preferable, and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, Trialkylaluminums such as octylaluminum and tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, dialkylaluminum halides such as diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquichloride Alkyl aluminum sesquihalides such as kibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di- Alkyl aluminums such as n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminum hydride Examples thereof include hydride, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and dialkylaluminum alkoxide such as diisobutylaluminum ethoxide.

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

  Examples of the compound [B-3] which forms an ion pair by reacting with the transition metal compound (A) include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, Lewis acids, ionic compounds, borane compounds and carborane compounds described in Kaihei 3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat. Can use heteropoly compounds and isopoly compounds without limitation.

  In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound [B-2] such as methylaluminoxane is used in combination as a cocatalyst component, the catalyst 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), since the solid support component containing the co-catalyst component can be easily prepared by reacting with active hydrogen in the carrier.

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

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2, and the} like, or a composite or mixture containing these. can be used, further, 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 or the like can be used. Among them, the porous oxide preferably contains SiO ₂ and / or Al ₂ O ₃ as a main component.

The porous oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, and other carbonate, sulfate, nitrate, and oxide components.

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

  Examples of the solid aluminoxane compound include 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 ( Aluminoxane selected from at least one kind of aluminoxane 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. 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, hydrocarbon groups such as ethylphenyl group can be exemplified, methyl group, ethyl group, isobutyl group is preferable, especially methyl group preferable. A part of R ^e is chlorine, substituted with a halogen atom such as bromine, and halogen content may be not more than 40 wt%, based on the R ^e. In (Sc) and (Sd), one straight line 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 to 500, preferably 6 to 300, particularly preferably 10 to 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 can maintain a substantially solid state under the reaction environment used.

  The solid aluminoxane compound, unlike conventionally known olefin polymerization catalyst carriers, does not contain an inorganic solid component such as silica or alumina or an organic polymer component such as polyethylene and polystyrene, and has been solidified as an alkyl aluminum compound as a main component. Things. "Solid state" means that the aluminoxane component maintains a substantially solid state under the used reaction environment. More specifically, when the transition metal compound [A] is brought into contact with an aluminoxane component to prepare an olefin polymerization catalyst (eg, an ethylene polymerization catalyst) as described below, and when the prepared olefin polymerization catalyst is used. When the polymerization (for example, suspension polymerization) of an olefin (for example, ethylene) is carried out by using the above, the aluminoxane component substantially maintains a solid state.

  Whether or not the aluminoxane component is in a solid state is the simplest method of visual confirmation, but it is often difficult to visually confirm, for example, during polymerization. In that case, for example, it can be determined from the properties of the polymer powder obtained after the polymerization, the state of adhesion to the reactor, and the like. Conversely, as long as the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the aluminoxane component elutes in the polymerization environment, the gist of the present invention is not deviated. Indices for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the presence of an amorphous polymer. The polymer bulk density is preferred from the viewpoint of quantitativeness. The bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

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

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

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

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

Next, the weight average particle diameter of the solid aluminoxane compound is determined by the following equation using the particle diameter 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.
MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used as the inorganic halide. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a solution obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating the fine particles with a precipitant.

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

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

Further, as clays and clay minerals, kaolin, bentonite, Kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, Halloy sites and the like,
As the ion-exchange layered compound, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples include crystalline acidic salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of a radius of 20 ° or more measured by a mercury intrusion method of 0.1 cc / g or more, and more preferably 0.3 to 5 cc / g. Is particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of a pore radius of 20 to 30,000 °.

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

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by utilizing ion-exchangeability and exchanging exchangeable ions between layers with another large bulky ion. Such a bulky ion plays a role of a support for supporting the layered structure, and is usually called a pillar. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ And the like. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides (R represents a hydrocarbon group or the like) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO ₂ or the like can also be allowed to coexist. In addition, examples of the pillar include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating.

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

Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound that can be used as the carrier [S] include a granular or particulate solid having a particle size in the range of 1 to 300 μm. Specifically, a polymer mainly composed of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene or vinylcyclohexane or styrene is mainly used. And modified products thereof can be exemplified.

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

As a method of contacting each component, focusing on the order of contact, for example,
(I) Method of contacting component (B) with component (A) (ii) Method of contacting component (A) with component (S) (iii) Contact of component (B) with component (S) and then component (A) Method of Contacting (A) Component (A) is Contacted with Component (B), and then Component (S) is Contacted (v) Component (S) is Contacted with Component (B), and then Component (S) A method of contacting a mixture of (A) and component (B),
(Vi) A method of contacting the component (B) with the component (S), further contacting the component (B), and then contacting a mixture of the component (A) and the component (B). When a plurality 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 above-mentioned contact sequence, in the step including the contact between the component (S) and the component (B) and the step including the contact between the component (S) and the component (A), the component (G) is used. The coexistence of the compound suppresses fouling during the polymerization reaction and improves the particle properties of the produced polymer. As the component (G), a compound having a polar functional group can be used, and a nonionic (nonionic) surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, and a polyalkylene oxide alkyl ether are used. , Alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, and N-acylamino acid are more preferable. These may be used alone or in combination of two or more.

  Examples of the solvent used for preparing the catalyst for olefin polymerization according to the present invention include inert hydrocarbon solvents, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other fats. Alicyclic hydrocarbons such as aromatic 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 be used as a solvent.

  In the contact between the component (B) and the component (S), the reaction site in the component (B) and the reaction site in the component (S) are chemically bonded to each other, whereby the component (B) and the component (S) are chemically bonded. ) 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 200C, preferably -20 to 120C. Done in When the initial contact between the component (B) and the component (S) is rapidly performed, the component (S) collapses due to the reaction heat or reaction energy, and the morphology of the obtained solid catalyst component is deteriorated. If so, continuous operation often becomes difficult due to poor polymer morphology. Therefore, in the initial stage of contact between the component (B) and the component (S), contact is made at a lower temperature or reaction is controlled at a speed capable of maintaining the initial contact temperature in order to suppress reaction heat generation. Is preferred. The same applies to the case where the component (B) is brought into contact with the component (S) and then the component (B) is brought into contact. The contact weight ratio of component (B) to component (S) (weight of component (B) / weight of component (S)) can be arbitrarily selected, but the higher the contact weight ratio, the more components (A) ) Can be brought into contact, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of the component (B) to the component (S) [= the weight of the component (B) / the weight of the component (S)] is preferably from 0.05 to 3.0, particularly preferably from 0.1 to 2 0.0.
When the contact product of the component (B) and the component (S) is brought into contact with the component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours. Is usually in the range of -50 to 200C, preferably -50 to 100C.

  Component (B-1) has a molar ratio [(B-1) / M] between component (B-1) and all transition metal atoms (M) in component (A) of usually 0.01 to 100, 000, preferably 0.05 to 50,000.

  Component (B-2) has a molar ratio [(B-2) / M] of component (B-2) (in terms of aluminum atoms) of all transition metal atoms (M) in component (A) of usually 10%. ５００500,000, preferably 20-100,000.

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

  In the olefin polymerization, the olefin polymerization catalyst according to the present invention can be used as it is. Alternatively, the olefin polymerization catalyst may be preliminarily polymerized with an olefin to form a prepolymerized solid catalyst component and then used.

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

  After the pre-polymerized solid catalyst component formed in the inert hydrocarbon solvent is separated from the suspension, it is suspended again in the inert hydrocarbon, and an olefin (eg, ethylene) is introduced into the obtained suspension. After drying, an olefin (eg, ethylene) may be introduced.

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

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

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

  Also, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot sheeting during polymerization, and suppressing the generation of polymer lumps, the component (G) is brought into contact with the prepolymerized solid catalyst component once formed by prepolymerization. Is also good.

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

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

  Drying of the pre-polymerized solid catalyst component is performed by maintaining the pre-polymerized solid catalyst component at a temperature of 70 ° C. or lower, preferably 20 to 50 ° C. under a flow of an inert gas. It is desirable that the amount of volatile components in the obtained dried prepolymerization catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The amount of the volatile component of the dry prepolymerization catalyst is preferably as small as possible, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

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

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

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

  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 (total of monomer units is 100 mol%). is there.

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

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

When polymerizing an olefin (eg, ethylene), the lower limit of the polymerization temperature is 0 ° C., preferably 40 ° C., and particularly preferably 60 ° C. Higher temperatures are advantageous in terms of heat removal in production on an industrial scale. The upper limit is usually 200 ° C., preferably 170 ° C., the polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2.

The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.
The molecular weight of the olefin polymer obtained by the method for producing an olefin polymer according to the present invention can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the above 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 the olefin 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 And cyclic olefins such as -dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

  Furthermore, a small amount of styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc. in a range not impairing the effects of the present invention; 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 polymer having many long-chain branches can be produced with high catalytic activity by using one kind of transition metal compound. In the method for producing the olefin polymer of the present invention, as a mechanism for introducing long-chain branching into the ethylene-based polymer, the present inventors have proposed that the transition metal compound (A) be a macromonomer that is a polymer having a terminal vinyl. It is presumed that it has both a role of forming and a role of copolymerizing the macromonomer competitively with the polymerization of ethylene and α-olefin. Further, by using the transition metal compound [A] in contact with a carrier [S] which is an optional component, the concentration of the macromonomer near the reaction point of the transition metal compound (A) can be increased. It is considered that an ethylene-based polymer into which long-chain branching has been introduced can be produced.

[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 an appropriate length, and preferably satisfies the following requirements (1) to (4).
(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is from 0.1 g / 10 min to 50 g / 10 min, preferably from 0.5 g / 10 min to 30 g / 10 min;
(2) density of 875kg / m ³ or more 965 kg / m ³ or less, preferably at 885kg / m ³ or more 945 kg / m ³ or less;
(3) The ratio of the zero shear viscosity at 200 ° C. [η ₀ (P)] to the weight-average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) to the 6.8 power (Mw ^6.8 ), 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) The 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 0.776 power (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 higher the molecular weight, and the higher 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 composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system (for example, "Catalytic Olefin Polymerization", edited by Kazuo Soga et al., Kodansha Scientific, 1990, p.376). For this reason, it is possible to increase or decrease the melt flow rate (MFR) of the ethylene polymer (α) by increasing or decreasing hydrogen / ethylene.

  The value of the density depends on the α-olefin content of the ethylene polymer. The density is higher as the α-olefin content is lower, and the density is lower as the α-olefin content is higher. It is known that the α-olefin content in an ethylene-based polymer is determined by the composition ratio of α-olefin and ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)). Therefore, by increasing or decreasing α-olefin / ethylene, an ethylene polymer having a density in the above range can be produced.

  The requirements (3) and (4) are both publicly known indices relating to long-chain branching. Their significance is described in, for example, JP-A-2006-233207, WO2006 / 080578, and WO2006 / 080578. 2013/099927 and the like can be referred to.

The olefin polymer (eg, ethylene polymer) produced according to the present invention may be pelletized.
The olefin polymer (eg, ethylene polymer) produced according to the present invention may include a weathering stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as long as the object of the present invention is not impaired. If necessary, additives such as antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, and antioxidants may be added.

The olefin polymer (eg, ethylene-based polymer) produced by the present invention can be processed by general film forming, blow molding, injection molding and extrusion molding.
Examples of the molded product obtained by processing the olefin polymer (eg, ethylene polymer) produced by the present invention include a film, a blow infusion bag, a blow bottle, a gasoline tank, a tube, a pipe, and a tear by extrusion. Injection molded articles such as caps, daily necessities and the like, fibers, large molded articles by rotational molding, and the like can be given.

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

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
[Measurement of various physical properties]
The method for measuring the physical properties of the ethylene polymer is shown below.
<Melt flow rate (MFR)>
It was measured at 190 ° C. under a load of 2.16 kg (kgf).

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

<Melting tension (MT)>
The melt tension (MT) at 190 ° C. (unit: g) was determined by measuring the stress when stretched at a constant speed. For the measurement, a capillary rheometer manufactured by Toyo Seiki Seisaku-sho, Ltd .: Capillograph 1D was used. 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, decrease the winding speed by 5 m / min. The nozzle diameter was 2.095 mmφ and the nozzle length was 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.
Shear viscosity (eta ^*) were the angular velocity [omega (rad / sec)] variance of a shear viscosity at a measurement temperature of 200 ° C. (eta ^*) measured in the range of 0.01 ≦ ω ≦ 100. A viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used for the measurement, a parallel plate of 25 mmφ was used as a sample holder, and the sample thickness was set to about 2.0 mm. The measurement points were 5 points per ω digit. The amount of distortion was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and the torque was not exceeded.

The sample used for the shear viscosity measurement was a press molding machine manufactured by Shinto Metal Industry Co., Ltd., with a preheating temperature of 190 ° C., a preheating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kgf / cm ² , and a cooling temperature of 20. The sample was prepared by press-molding the measurement sample to a thickness of 2 mm under the conditions of 0 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm ² .

<Zero shear viscosity (η ₀ )>
The zero shear viscosity (η ₀ ) (P) at 200 ° C. was determined by the following method.
At a measurement temperature of 200 ° C., the angular velocity ω (rad / sec) dispersion of the shear viscosity (η ^* ) was measured in the range of 0.01 ≦ ω ≦ 100. A viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used for the measurement, a parallel plate of 25 mmφ was used as a sample holder, and the sample thickness was set to about 2.0 mm. The measurement points were 5 points per ω digit. The amount of distortion was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and the torque was not exceeded.

The sample used for the shear viscosity measurement was a press molding machine manufactured by Shinto Metal Industry Co., Ltd., with a preheating temperature of 190 ° C., a preheating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kgf / cm ² , and a cooling temperature of 20. The sample was prepared by press-molding the measurement sample to a thickness of 2 mm under the conditions of 0 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm ² .

The zero shear viscosity (η ₀ ) was calculated by fitting a Carreau model of the following equation to an actually measured rheological curve [dispersion of angular velocity (ω) of shear viscosity (η ^* )] by the nonlinear least squares method.
η ^* = η ₀ [1+ (λω) ^a ] ^{(n-1) / a}
[Λ is a parameter having a time dimension, and n represents a power law index of a material. The 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 actually 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. After 5 ml of a decalin solvent was added to this decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) as shown in the following formula.
[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)>
The measurement was performed as follows using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent.

  Two Agilent PLgel Olexis were used for the analytical column, a differential refractometer and a three capillary viscometer were used for the detector, 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. Standard polystyrene manufactured by Tosoh Corporation was used. In the molecular weight calculation, an actually measured viscosity is calculated from a viscometer and a refractometer, and the number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), and the molecular weight distribution (Mw / Mn, Mz) are obtained from the measured universal calibration. / Mw).

<Synthesis of transition metal compound (A)>
[Synthesis Example 1-1]
0.62 g (25.4 mmol) of magnesium pieces was charged into a 300 mL reactor that had been sufficiently dried and purged with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, Am. Chem. Soc. 2006, 128, 16486. A solution of 6.89 g (23.0 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized by the method described in 30 mL of tetrahydrofuran was added dropwise (1.0 mL was added, and then iodine was added by a dryer. Was heated and refluxed until the color disappeared, and the remaining droplets were dropped after the start of the reaction. After the reaction solution was cooled to −78 ° C., 2.90 mL (26.1 mmol) of trimethoxyborane was slowly added thereto, and stirring was continued for 21 hours while slowly returning to room temperature. A 1.0 M aqueous hydrochloric acid solution was added, and the soluble matter was extracted with di-iso-propyl ether. The obtained fraction was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated, and the residue obtained was subjected to 4-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method described in JP-A-2012-121882. 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, a saturated aqueous solution of ammonium chloride was added, and the soluble matter was extracted with ethyl acetate. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated, and the residue obtained was purified by silica gel column chromatography to obtain the target compound represented by the following formula (A-1a) (hereinafter, referred to as compound (A-1a)) 7.18 g (96% yield) were obtained.
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 = 5.6and1.8Hz, C = CH-C), 3.75 (3H, s, -OCH 3), 3.32 (2H, s, Ar-CH 2 -C ), 3.00 (2H, t, J = 7.4Hz, Ar-CH 2 -CH 2), 2.85 (2H, t, J = 7.3Hz, Ar-CH 2 -CH 2), 2. 07 (2H, q, J = 7.3Hz, CH 2 -CH 2 -CH 2), 1.45 (18H, s, -C (CH 3) 3) ppm

[Synthesis Example 1-2]
1.45 g (59.8 mmol) of magnesium pieces was charged into a 200 mL reactor that had been sufficiently dried and purged 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 2.93 g (15.0 mmol) of 2-bromoindene in 15 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, the mixture was heated under reflux until the iodine color disappeared with a drier, and the remaining liquid drops after the start of the reaction). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78 ° C, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent and unreacted dimethylsilyl dichloride of the reaction solution, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 5.62 g (15.0 mmol) of the compound (A-1a) obtained in Synthesis Example 1-1 and 15 mL of tetrahydrofuran were charged into a 100 mL reactor which was sufficiently dried and purged with argon, and 9.70 mL of an 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 reaction residue solution cooled to −78 ° C., and stirring was continued for 45 hours while slowly returning to room temperature. A saturated aqueous ammonium chloride solution was added, and the soluble matter was extracted with ethyl acetate. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the target compound represented by the following formula (A-1L) (hereinafter, referred to as compound (A-1L)) Was obtained as a mixture of isomers (7.67 g, yield 94%).
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 = 5.4and1.9Hz, 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 = 7.3Hz, 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 1A]
1.10 g (2.01 mmol) of the compound (A-1L) obtained in Synthesis Example 1-2, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged and stirred in a 100 mL reactor which was sufficiently dried and purged with argon. After adding 2.60 mL of an n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) to this solution at room temperature, stirring was continued for 3 hours in a 40 ° C. oil bath. The 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 evaporating the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and insolubles were removed with celite on a glass filter. After the obtained solution was concentrated under reduced pressure, the suspension was adjusted by adding n-hexane, insolubles were filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (A-1) Compound dimethylsilylene (2-indenyl) (4- (3,5-di-tert-butyl-4-methoxyphenyl) -1,5,6,7-tetrahydro-s-1-indacenyl represented by the following formula: ) 0.51 g (yield 36%) of zirconium dichloride (hereinafter, referred to as compound (A-1)) was obtained.
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 = 2.6and0.8Hz , 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 = 7.0Hz, 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 spectrometry (M ⁺ ): 706

[Synthesis Example 2-1]
0.61 g (25.0 mmol) of magnesium pieces was charged into a 300 mL reactor that had been sufficiently dried and purged with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. Org. Chem. 2006, 2727. And a diluted solution of 6.55 g (23.0 mmol) of 4-bromo-2,6-di-iso-propyl-N, N-dimethylaniline in 30 mL of tetrahydrofuran synthesized by the method described in WO2007 / 034975 (1. After the addition of 0 mL, the mixture was heated and refluxed until the iodine color disappeared with a drier, and the remaining droplets were dropped after the reaction was started. After the completion of the dropwise addition, the mixture was heated and refluxed in an oil bath at 80 ° C. for 1 hour. After the reaction solution was cooled to −78 ° C., 2.90 mL (26.1 mmol) of trimethoxyborane was slowly added, and stirring was continued for 17 hours while slowly returning to room temperature. An aqueous solution of ammonium chloride was added, and the soluble matter was extracted with di-iso-propyl ether. The obtained fraction was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated, and the residue obtained was subjected to 4-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method described in JP-A-2012-121882. 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, a saturated aqueous solution of ammonium chloride was added, and the soluble matter was extracted with ethyl acetate. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the target compound represented by the following formula (A-2a) (hereinafter, referred to as compound (A-2a)) 5.57 g (yield 77%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.26 (1 H, s, Ar-H), 7.10 (2 H, s, Ar-H), 6.87 (1 H, dt, J = 5.6 and 1. 8 Hz, C = CH-C, 6.48 (1H, dt, J = 5.6 and 1.8 Hz, C = CH-C), 3.38 (2H, sep, J = 6.9 Hz, -CH (CH _{3) 2), 3.33 (2H} , s, Ar-CH 2 -C), 2.99 (2H, t, J = 7.3Hz, Ar-CH 2 -CH 2), 2.89 (6H, _{s, -NC (CH 3) 2} ), 2.86 (2H, t, J = 7.3Hz, Ar-CH 2 -CH 2), 2.06 (2H, q, J = 7.27Hz, CH 2 _{-CH 2 -CH 2), 1.23 (} 12H, d, J = 6.9Hz, -CH (CH 3) 2) ppm

[Synthesis Example 2-2]
1.45 g (59.8 mmol) of magnesium pieces was charged into a 200 mL reactor that had been sufficiently dried and purged 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 2.94 g (15.1 mmol) of 2-bromoindene in 15 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, the mixture was heated under reflux until the iodine color disappeared with a drier, and the remaining liquid drops after the start of the reaction). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78 ° C, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent and unreacted dimethylsilyl dichloride of the reaction solution, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. In a 100 mL reactor that is sufficiently dried and purged with argon, 5.40 g (15.0 mmol) of the compound (A-2a) obtained in Synthesis Example 2-1 and 15 mL of tetrahydrofuran are charged, and 9.70 mL of an n-butyllithium solution is charged. (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 reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 21 hours while slowly returning to room temperature. A saturated aqueous ammonium chloride solution was added, and the soluble matter was extracted with ethyl acetate. The obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the target compound represented by the following formula (A-2L) (hereinafter, referred to as compound (A-2L)) Was obtained as an isomer mixture in 6.95 g (87% yield).
_{^{1 H NMR (270MHz, 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 = 7.27Hz, CH 2 -CH 2 -CH 2), 1.35-1. 15 (12H, m, -CH ( CH 3) 2), 0.27 (3H, s, Si-CH 3), 0.16 (3H, s, Si-CH 3) ppm

[Example 2A]
1.07 g (2.00 mmol) of the compound (A-2L) obtained in Synthesis Example 2-2, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a 100 mL reactor which was sufficiently dried and purged with argon, and stirred. After adding 2.60 mL of an n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) to this solution at room temperature, stirring was continued for 3 hours in a 40 ° C. oil bath. The 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 evaporating the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and insolubles were removed with celite on a glass filter. After the obtained solution was concentrated under reduced pressure, the suspension was adjusted by adding n-hexane, insolubles were filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (A-2) Dimethylsilylene (2-indenyl) (4- (3,5-di-iso-propyl-4- (N, N-dimethylamino) phenyl) -1,5,6,7- 0.30 g (yield: 22%) of tetrahydro-s-1-indacenyl) zirconium dichloride (hereinafter, referred to as compound (A-2)) was obtained.
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 (hereinafter, referred to as compound (A-3)) represented by the following formula (A-3) is described in Macromolecules 1995, 28, 3771. It was synthesized by the method described.

[Comparative Example 2A]
Dimethylsilylene (cyclopentadienyl) (4- (4-trimethylsilylphenyl) -1-indenyl) zirconium dichloride (hereinafter, referred to as compound (A-4)) represented by the following formula (A-4) is described in WO2012 / 133717. The synthesis was carried out according to the method described in Japanese Patent Publication No.

[Comparative Example 3A]
Dimethylsilylenebis (1-indenyl) zirconium dichloride (hereinafter, referred to as compound (A-5)) represented by the following formula (A-5) was purchased from Wako Pure Chemical Industries.

[Comparative Example 4A]
Ethylene bis (1-indenyl) zirconium dichloride (hereinafter, referred to as compound (A-6)) represented by the following formula (A-6) was purchased from Wako Pure Chemical Industries.

[Reference Example 1A]
Dimethylsilylene (2-indenyl) (1-indenyl) zirconium dichloride (hereinafter, referred to as compound (A-7)) represented by the following formula (A-7) was synthesized by the method described in JP-A-11-292934. .

[Example 1]
<Preparation of solid catalyst component (X-1)>
Silica gel (manufactured by Fuji Silysia Chemical Ltd., 50% cumulative particle size of laser light diffraction / scattering method: 70 μm, ratio: 70 μm) was used as a solid support [S] in a nitrogen atmosphere in a reactor with a stirrer having an inner volume of 270 L Surface area: 340 m ² / g, pore volume: 1.3 cm ³ / g, dried at 250 ° C. for 10 hours, 10 kg of solid carrier [S-1]) was suspended in 77 L of toluene, and then suspended. Cool to ５5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) as a component (B) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5C. Next, these were contacted at 0 to 5 ° C. for 30 minutes, then 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 amount of 115 liters. When a part of the obtained slurry was collected and analyzed, the solid concentration was 122.6 g / L and the Al concentration was 0.612 mol / L.

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

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside 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-1) in a slurry state were charged as a solid, and then a hydrogen concentration of 0.10 vol% was obtained. Using an ethylene / hydrogen mixed gas, the temperature was raised to 80 MPa and 0.8 MPaG, the pressure was increased, and the polymerization reaction was performed 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 catalyst activity was 3,200 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. Using a Labo Plast Mill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the mixture was melt-kneaded at a resin temperature of 180 ° C. and a rotation speed of 50 rpm for 5 minutes. Further, this molten polymer was cooled using a press molding machine (manufactured by Shinto Metal Industry Co., Ltd.) under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Physical properties were measured using the obtained sample as a measurement sample. Table 8 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>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside of the reactor with ethylene. Next, 12 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 24 mg of the solid catalyst component (X-2) in a slurry state were charged as solids, 50 mL of hydrogen was added, and 80 mL of ethylene was added. The temperature was raised to 0.8 MPaG and the temperature was raised to 0.8 MPaG, and the polymerization reaction was performed 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 catalyst activity was 3,690 g-PE / g-solid catalyst component. The obtained ethylene 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 8 shows the results.

[Comparative Example 1]
<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 Comparative Example 1A was used instead of the compound (A-1). .

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside 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-3) in the form of a slurry were charged as a solid, and the mixture was then charged with ethylene 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 catalyst activity was 440 g-PE / g-solid catalyst component. Table 8 shows the results.

[Comparative Example 2]
<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 Comparative Example 2A was used instead of the compound (A-1). .

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside 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-4) in the form of a slurry were charged as solids, and then 80 ° C. and 0.8 MPaG with ethylene. , And the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it vacuum-dried at 80 degreeC for 10 hours, and 79.1 g of ethylene polymers were obtained. The catalyst activity was 660 g-PE / g-solid catalyst component. Table 8 shows the results.

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

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside 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-5) in a slurry state as a solid content were charged, and then a hydrogen concentration of 0.45 vol% Using an ethylene / hydrogen mixed gas, the temperature was raised to 80 MPa and 0.8 MPaG, the pressure was increased, and the polymerization reaction was performed 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 polymer. The catalyst activity was 1,100 g-PE / g-solid catalyst component. The obtained ethylene 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 8 shows the results.

[Comparative Example 4]
<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 Comparative Example 4A was used instead of the compound (A-1). .

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-6) in a slurry state were charged as a solid, and then a hydrogen concentration of 0.20 vol% Using an ethylene / hydrogen mixed gas, the temperature was raised to 80 MPa and 0.8 MPaG, the pressure was increased, and the polymerization reaction was performed 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 catalyst activity was 4,180 g-PE / g-solid catalyst component. The obtained ethylene 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 8 shows the results.

[Reference 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 Reference Example 1A was used instead of the compound (A-1). .

<Production of ethylene polymer>
In a nitrogen atmosphere, 500 ml of heptane was added to a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and then ethylene was passed through the reactor to saturate the inside 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-7) in the form of a slurry were charged as a solid, and then charged at 80 ° C. The temperature was raised to 8.8 MPaG, the pressure was increased, and the polymerization reaction was performed 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 catalyst activity was 1,500 g-PE / g-solid catalyst component. Table 8 shows the results.

In Examples 1 and 2 using the transition metal compound [A] (bridged (2-indenyl) (1-indenyl) type compound) of the present invention, comparison using a bridged cyclopentadienyl (1-indenyl) type compound was performed. As compared with Examples 1 and 2, higher catalytic activity was exhibited. Furthermore, the catalyst activity was higher than that of Reference Example 1 using a bridged (2-indenyl) (1-indenyl) type compound having no specific substituent on the 1-indenyl ring. ^Further , the value of [η] / Mw ^0.776 was smaller than that of Comparative Examples 3 and 4 using a crosslinked bis (1-indenyl) type compound, which means that the amount of long-chain branching introduced was large.

Claims (10)

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

(In the general formula [1], M is a transition metal atom belonging to Group 4 of the periodic table,
n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, Group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group, and when n is 2 or more, a plurality of groups represented by X are the same as each other May be different from each other, and may combine with each other to form a ring,
Q is a Group 14 atom in the periodic table;
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 and R ¹⁴ 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,
At least one of R ¹⁰ and R ¹¹ is not a hydrogen atom,
Adjacent substituents among R ^{1 to} R ⁶ may be bonded to each other to form a ring which may have a substituent,
Adjacent substituents among R ^{7 to} R ¹² may be bonded to each other to form a ring which may have a substituent,
R ¹³ and R ¹⁴ may combine with each other to form a ring containing Q, and this ring may have a substituent. ) In the general formula [1],
M is a zirconium atom or a hafnium atom,
X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group,
Q is a carbon atom or a silicon atom,
R ^{1 to} R ¹⁴ 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, The transition metal compound [A] according to claim 1, which is a nitrogen-containing group or a sulfur-containing group having 1 to 20 carbon atoms. In the general formula [1],
Q is a silicon atom,
R ^{1 to} R ¹⁴ 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 1 to 20 carbon atoms. The transition metal compound [A] according to claim 2, which is a nitrogen-containing group. In the general formula [1],
The transition metal compound [A] according to claim 3, wherein R ¹ and R ⁶ are a hydrogen atom. In the general formula [1],
The transition metal compound [A] according to claim 4, wherein R ^{2 to} R ⁵ and R ⁸ are hydrogen atoms. In the general formula [1],
The transition metal compound [A] according to claim 5, wherein at least one of R ¹⁰ and R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.   An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 6. Further, [B] [B-1] an organometallic compound,
8. The composition according to claim 7, comprising at least one compound selected from the group consisting of [B-2] an organic aluminum oxy compound, and [B-3] a compound which forms an ion pair by reacting with the transition metal compound [A]. Olefin polymerization catalyst.   A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7.   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.