JP2021046555A - Catalyst for olefin polymerization and method for producing ethylenic polymer using the same - Google Patents

Abstract

To provide a catalyst for olefin polymerization which makes it possible to stably produce an ethylenic polymer with excellent moldability, and a method for producing the ethylenic polymer.SOLUTION: The catalyst comprises a component (A) represented by general formula (I), a component (B) represented by general formula (II), and the like.SELECTED DRAWING: None

Description

The present invention relates to a catalyst for olefin polymerization and a method for producing an ethylene polymer using the same, and more specifically, olefin polymerization capable of stably producing an ethylene polymer having excellent molding processability. It relates to a catalyst for use and a method for producing an ethylene polymer using the catalyst.

It is well known that ethylene-based polymers obtained by Ziegler catalysts and metallocene catalysts generally have a small melt tension and tend to be inferior in moldability to high-pressure low-density polyethylene.
In order to solve this problem, a method of blending a high-pressure low-density polyethylene with an ethylene-based polymer obtained by using a Ziegler catalyst or a metallocene catalyst as in Patent Document 1, and a specific metallocene catalyst as in Patent Document 2 are used. A method for producing a long-chain branched ethylene-based polymer using it is disclosed.

Patent Documents 3 and 4 report that by using two specific crosslinked metallocene compounds, a large number of long-chain branches can be introduced and an ethylene-based polymer having excellent molding processability can be produced. Further, a production method capable of reducing the occurrence of fouling and the like during polymerization, including such an ethylene polymer, is also disclosed (Patent Documents 5 to 7).
Patent Documents 8 to 11 also report methods for producing long-chain branched ethylene-based polymers using two types of metallocene compounds.

Japanese Unexamined Patent Publication No. 7-26079 Japanese Unexamined Patent Publication No. 4-213309 Japanese Unexamined Patent Publication No. 2006-233208 Japanese Unexamined Patent Publication No. 2009-144148 Japanese Unexamined Patent Publication No. 2013-224408 Japanese Unexamined Patent Publication No. 2015-160858 Japanese Unexamined Patent Publication No. 2015-160859 Special Table 2007-520597 JP-A-2010-431152 Japanese Unexamined Patent Publication No. 2011-6674 Japanese Unexamined Patent Publication No. 2012-214780

The above-mentioned Patent Documents 1 to 4, 8 to 11 do not disclose problems such as the occurrence of fouling during the polymerization reaction.
As a result of examination by the present inventors, even with the techniques of Patent Documents 5 to 7, fouling and the like are suppressed particularly when the production speed is increased or under relatively harsh conditions such as large-scale production. Was found to be a problem that may not be sufficient.

As a result of further studies by the present inventors, it has been hypothesized that the cause may be that the polymerization activity may change significantly with the fluctuation of the polymerization temperature.
The present invention has been made in view of the above-mentioned new problems, and is a catalyst for olefin polymerization capable of stably producing an ethylene-based polymer having excellent molding processability, and the catalyst. It is an object of the present invention to provide a method for producing an ethylene-based polymer to be used.

As a result of diligent research in view of the above situation, the present inventors have obtained an ethylene-based polymer having a large number of long-chain branches by using two types of crosslinked metallocene compounds having a specific structure in combination in the same polymerization system. We have found that the variation in polymerization activity due to the polymerization temperature is smaller than that in the prior art while maintaining the property of giving, and have completed the present invention.

That is, the catalyst for olefin polymerization of the present invention is characterized by containing the component (A), the component (B), and the component (C).
Component (A); A crosslinked metallocene compound represented by the following general formula (I).

〔一般式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、互いに同一でも異なっていてもよいが、全てが同時に水素原子ではなく、隣接する基が互いに結合して脂肪族環を形成していてもよい。Ｑ¹は、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、Ｘは、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕
成分（Ｂ）；下記一般式（ＩＩ）で表される架橋型メタロセン化合物。

[In the general formula (I), R ¹ , R ² , R ³ and R ⁴ contain a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, and a phosphorus-containing group. It is selected from groups, silicon-containing groups, germanium-containing groups and tin-containing groups, which may be the same or different from each other, but they are not all hydrogen atoms at the same time, and adjacent groups are bonded to each other to form an aliphatic ring. You may. Q ¹ is selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and X is an independent hydrogen atom, halogen atom and hydrocarbon group, respectively. , A halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group, and M is a titanium atom, a zirconium atom or a hafnium atom. ]
Component (B); A crosslinked metallocene compound represented by the following general formula (II).

〔一般式（ＩＩ）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、また、隣接もしくは近傍にある複数の置換基は互いに結合して環を形成してもよい。Ｑ²は、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、Ｍは、チタン原子、ジルコニウム原子およびハフニウム原子から選ばれ、Ｘは、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕

[In general formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms and hydrocarbons. Groups selected from groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, which are the same or different from each other. Alternatively, a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring. Q ² is selected from hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, M is selected from titanium atoms, zirconium atoms and hafnium atoms, and X Is a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. It is a titanium atom, a zirconium atom or a hafnium atom. ]

Component (C); At least one component selected from the group consisting of the following (c-1), (c-2) and (c-3).
(C-1) Organometallic compound represented by the following formula (III), (IV) or (V) (c-2) Organoaluminium oxy compound (c-3) Reaction with component (A) and component (B) and compound to form an ion pair _{^{R a m Al (ОR b)}} n H p X q ··· (III)
[In formula (III), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦. 3, n is the number of 0 ≦ n <3, p is the number of 0 ≦ p <3, q is the number of 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ··· (IV}} )
Wherein (IV), M ^a represents a Li, Na or K, R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t・ ・ ・ (V)
[In formula (V), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b represents Mg, Zn or Cd, and X represents Mg, Zn or Cd. , R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
It is preferable that the component (B) is at least one crosslinked metallocene compound selected from the group represented by the following general formulas (II-α), (II-β) and (II-γ).

〔一般式（ＩＩ−α）、（ＩＩ−β）および（ＩＩ−γ）中、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、隣接する基は互いに結合して脂肪族環を形成していてもよい。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸およびＲ³⁹は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、また、隣接もしくは近傍にある複数の置換基は互いに結合して環を形成してもよい。Ｑ²は、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、Ｍは、チタン原子、ジルコニウム原子およびハフニウム原子から選ばれ、Ｘは、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕

[Formula (II-α), (II -β) and (II-gamma) ^{in, R 17, R 18, R} 19, R 20, R 21, R 22, R 23, R 24 and R ^25, A group selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and each other. It may be the same or different, and adjacent groups may be bonded to each other to form an aliphatic ring. R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are hydrogen atoms, hydrocarbon groups, A group selected from a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, which may be the same or different from each other. Also, a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring. Q ² is selected from hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, M is selected from titanium atoms, zirconium atoms and hafnium atoms, and X Is a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. It is a titanium atom, a zirconium atom or a hafnium atom. ]

In the general formulas (II-α), (II-β) and (II-γ), it is preferable that at least one of ^{R 17} , R ¹⁸ , R ¹⁹ and R ^{20 is a hydrocarbon group.}
It is also preferable that the component (B) is at least one crosslinked metallocene compound selected from the group represented by the following general formulas (II-δ), (II-ε) and (II-ζ).

〔一般式（ＩＩ−δ）、（ＩＩ−ε）および（ＩＩ−ζ）中、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、隣接する複数の基は互いに結合して脂肪族環を形成していてもよい。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸およびＲ³⁹は、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、また、隣接もしくは近傍にある複数の置換基は互いに結合して環を形成してもよい。Ｑ²は、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、Ｍは、チタン原子、ジルコニウム原子およびハフニウム原子から選ばれ、Ｘは、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕

[In the general formulas (II-δ), (II-ε) and (II-ζ), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen. A group selected from a containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, which may be the same or different from each other, and may be the same or different from each other. The groups may be attached to each other to form an aliphatic ring. R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are hydrogen atoms, hydrocarbon groups, A group selected from a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, which may be the same or different from each other. Also, a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring. Q ² is selected from hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, M is selected from titanium atoms, zirconium atoms and hafnium atoms, and X Is a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. It is a titanium atom, a zirconium atom or a hafnium atom. ]

In the general formula (I), it is preferable that at least one of ^{R 1} , R ² , R ³ and R ^{4 is a hydrocarbon group.}
It is preferable that the component (C) contains at least the above (c-2).
The catalyst for olefin polymerization of the present invention preferably contains a solid carrier (S).
The solid support (S) is preferably a porous oxide.
In the method for producing an ethylene-based polymer of the present invention, ethylene or ethylene and an olefin having 3 or more and 20 or less carbon atoms are polymerized in the presence of the catalyst for olefin polymerization.

The catalyst for olefin polymerization of the present invention has a feature that the activity fluctuates little depending on the polymerization temperature and a property that a macromonomer giving a long-chain branched structure is relatively easy to react. Therefore, an ethylene polymer having excellent properties such as moldability can be stably produced.

FIG. 1 shows the polymerization temperature (70 ° C., 80 ° C., 90 ° C.) and the polymerization activity ratio (activity ratio when the polymerization activity at 80 ° C. of each experimental example is 1) in Example 11, Example 12, and Comparative Example 3. ) And the relationship.

Hereinafter, the catalyst for olefin polymerization according to the present invention and the method for producing an ethylene polymer using the catalyst will be specifically described. In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymer but also copolymer. May be used in the same sense.
First, each component used in the catalyst for olefin polymerization of the present invention will be described.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization of the present invention comprises a component (A), a component (B), and a component (C).

(Ingredient (A))
The component (A) is a crosslinked metallocene compound represented by the following general formula (I). The catalyst for olefin polymerization of the present invention contains at least one crosslinked metallocene compound represented by the following general formula (I). That is, as the component (A), a plurality of types of crosslinked metallocene compounds represented by the general formula (I) may be used.

一般式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は一価の基であり、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基である。Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立であり、互いに同一でも異なっていてもよいが、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴の全てが同時に水素原子ではなく、隣接する基が互いに結合して脂肪族環を形成していてもよい。

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ are monovalent groups, which are a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and sulfur. It is a containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. R ¹ , R ² , R ³ and R ⁴ are independent of each other and may be the same or different from each other, but all of R ¹ , R ² , R ³ and R ⁴ are not hydrogen atoms at the same time but are adjacent to each other. The groups may be bonded to each other to form an aliphatic ring.

In the present specification, "may be the same or different from each other" means that the substituents listed in the metallocene compound or the substituents described by the same number are the same or different. Often, it also means that different metallocene compounds may have the same or different substituents with the same number.

The hydrocarbon group (monovalent hydrocarbon group) is preferably an alkyl group consisting of carbon and hydrogen having 1 to 20 carbon atoms, a cycloalkyl group consisting of carbon and hydrogen having 3 to 20 carbon atoms, and a carbon number of carbon atoms. An alkenyl group composed of 2 or more and 20 or less carbon and hydrogen, an aryl group composed of carbon and hydrogen having 6 or more and 20 or less carbon atoms, or an arylalkyl group composed of carbon and hydrogen having 7 or more and 20 or less carbon atoms are shown. Examples of the alkyl group composed of carbon having 1 or more and 20 or less carbon atoms and hydrogen include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neopentyl, and the like. Examples thereof include n-hexyl, n-octyl, nonyl, dodecyl, and icosyl (icosyl). Examples of the cycloalkyl group composed of carbon having 3 or more and 20 or less carbon atoms and hydrogen include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the alkenyl group composed of carbon having 2 or more and 20 or less carbon atoms and hydrogen include vinyl, propenyl, cyclohexenyl group and the like. Examples of the aryl group composed of carbon having 6 or more and 20 or less carbon atoms and hydrogen include phenyl, trill, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, and the like. Examples thereof include phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, acetylenylyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Examples of the arylalkyl group composed of carbon having 7 or more and 20 or less carbon atoms and hydrogen include benzyl, phenylethyl, and phenylpropyl.

Examples of the halogen-containing group (monovalent halogen-containing group) include a halogen atom and a group in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, for example, a trifluoromethyl group. ..

Examples of the oxygen-containing group (monovalent oxygen-containing group) include methoxy and ethoxy groups.
Examples of the sulfur-containing group (monovalent sulfur-containing group) include thiols and sulfonic acid groups.

Examples of the nitrogen-containing group (monovalent nitrogen-containing group) include a dimethylamino group.
Examples of the phosphorus-containing group (monovalent phosphorus-containing group) include a phenylphosphine group.

Examples of the boron-containing group (monovalent boron-containing group) include bolangyl, bolantriyl, and diboranyl group.
Examples of the silicon-containing group (monovalent silicon-containing group) include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl and di. Examples thereof include naphthylsilyl, cyclodimethylenesilyl, cyclotrimethylenylsilyl, cyclotetramethylenesilyl, cyclopentamethylenesilyl, cyclohexamethylenesilyl, cycloheptamethylenesilyl group and the like.

Examples of the germanium-containing group (monovalent germanium-containing group) or the tin-containing group (monovalent tin-containing group) include a group obtained by converting silicon into germanium or tin in the silicon-containing group.

Examples of cases where adjacent groups bind to each other to form an aliphatic ring include tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4-trimethyltetrahydroindenyl, 4-phenyltetrahydroindenyl, 4 Examples thereof include -cyclohexyltetrahydroindenyl, 2-methyl-4-phenyltetrahydroindenyl, 2-methyl-4-cyclohexyltetrahydroindenyl and the like.

Preferred groups of R ¹ , R ² , R ³ and R ⁴ are groups selected from hydrogen atoms, hydrocarbon groups and halogen-containing groups, more preferably at least one is a hydrocarbon group and even more preferably. , At least one is a hydrocarbon group having 1 or more and 15 or less carbon atoms, the rest is a hydrocarbon group or a hydrogen atom, and even more preferably, at least one is a hydrocarbon group having 3 or more and 8 or less carbon atoms and the rest. Is a hydrocarbon group or a hydrogen atom. The most preferable groups of R ¹ , R ² , R ³ and R ⁴ have a hydrocarbon group having 3 to 8 carbon atoms at the 3-position of the cyclopentadienyl group, and the rest are hydrocarbon groups or hydrogen atoms. is there. As the hydrocarbon group, an alkyl group is preferable.

Q ¹ is a divalent group that binds two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, a cycloalkylene group, and an alkylidene group, and a halogen-containing group. It is a silicon-containing group, a germanium-containing group, or a tin-containing group.

Specific examples of the alkylene group, the substituted alkylene group, the cycloalkylene group and the alkylidene group, which are the hydrocarbon groups having 1 to 20 carbon atoms (divalent hydrocarbon groups having 1 to 20 carbon atoms), include methylene. Alkylene groups such as ethylene, propylene and butylene, isopropyrine, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, Substituent alkylene groups such as methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, cyclo Cycloalkylene groups such as propylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, Examples thereof include alkyridene groups such as ethylidene, propylidene and butylidene.

Examples of the silicon-containing group (divalent silicon-containing group) include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylcilylene, dicyclohexylsilylene, methylcyclohexylcilylene, and methylphenylcilylene. , Diphenyl silylene, ditril cilylene, methylnaphthyl silicate, dinaphthyl silicate, cyclodimethylene silicate, cyclotrimethylene silicate, cyclotetramethylene silicate, cyclopentamethylene silicate, cyclohexamethylene silicate, cycloheptamethylene silicate group and the like. , Preferably dimethylsilylene, dibutylsilylene, diphenylcilylene.

Examples of the germanium-containing group (divalent germanium-containing group) or the tin-containing group (tin-containing group) include a group obtained by converting silicon into germanium or tin in the silicon-containing group.

As the halogen-containing group (divalent halogen-containing group), one or more of the hydrogen atoms in the alkylene group, the substituted alkylene group, the cycloalkylene group, the alkylidene group and the silicon-containing group are substituted with an appropriate halogen atom. Examples include bis (trifluoromethyl) methylene, 4,4,4-trifluorobutylmethyl methylene, bis (trifluoromethyl) silylene, 4,4,5-tri. Fluorobutylmethylsilylene group and the like can be mentioned.

Preferred groups of Q ¹ include an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group, an alkylidene group, a halogen-containing alkylene group, a halogen-containing substituted alkylene group, a halogen-containing cycloalkylene group and a halogen-containing alkylidene group. , A silicon-containing group or a halogen-containing silicon-containing group, and a more preferable group is a silicon-containing group or a halogen-containing silicon-containing group.

X is a monovalent group and is independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. It is a group, preferably a halogen atom or a hydrocarbon group. Xs may be the same or different from each other, but are preferably the same.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus-containing group are R ^{1 above.} The same thing as the one that was done can be mentioned.
M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

In general, the reactivity of an olefin polymerization catalyst with an ethylene-based polymer increases as the molecular weight of the ethylene-based polymer decreases and as the number of terminal vinyl groups increases, producing many long-chain branches. Can be done. Since the component (A) has a relatively low molecular weight and can produce a polymer having a large number of terminal vinyl groups, the polymer obtained by the component (A) is efficiently taken up by the component (B) and is conventionally known. It is possible to produce an ethylene-based polymer having a large number of long-chain branches with respect to the polymer of. Further, due to the polymerization activity of the component (A), an ethylene-based (co) polymer having a long-chain branch can be produced with high productivity.

Since the crosslinked metallocene compound represented by the general formula (I) can produce an olefin polymer having a relatively low molecular weight and a large number of terminal vinyl groups with high catalytic activity, it is a polymer having a long chain branch. Preferred in production.

The crosslinked metallocene compound represented by the general formula (I) and the method for producing the same are not particularly limited as long as the effects of the present invention are exhibited, and specific examples thereof include, for example, JP-A-2009-143901 and JP-A-2009. Examples thereof include those exemplified in JP-A-144148.

In the present invention, the compound represented by the general formula (I) may be used alone, or two or more kinds of metallocene compounds having different chemical structures may be used among these compounds. Further, structural isomers having the same chemical structure may be used alone, or structural isomer mixtures having the same chemical structure (for example, meso-form mixture or racemic mixture) may be used.

(Component (B))
The component (B) is a crosslinked metallocene compound represented by the following general formula (II). The catalyst for olefin polymerization of the present invention contains at least one crosslinked metallocene compound represented by the following general formula (II). That is, as the component (B), a plurality of types of crosslinked metallocene compounds represented by the general formula (II) may be used.

一般式（ＩＩ）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶は、一価の基であり、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、また、隣接もしくは近傍にある複数の置換基は互いに結合して環を形成してもよい。

In general formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are monovalent groups. , Hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group. It may be the same or different from each other, and a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring.

The hydrocarbon group (monovalent hydrocarbon group) is preferably an alkyl group consisting of carbon and hydrogen having 1 to 20 carbon atoms, a cycloalkyl group consisting of carbon and hydrogen having 3 to 20 carbon atoms, and a carbon number of carbon atoms. An alkenyl group composed of 2 or more and 20 or less carbon and hydrogen, an aryl group composed of carbon and hydrogen having 6 or more and 20 or less carbon atoms, or an arylalkyl group composed of carbon and hydrogen having 7 or more and 20 or less carbon atoms are shown. Examples of the alkyl group composed of carbon having 1 or more and 20 or less carbon atoms and hydrogen include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neopentyl, and the like. Examples thereof include n-hexyl, n-octyl, nonyl, dodecyl, and icosyl (icosyl). Examples of the cycloalkyl group composed of carbon having 3 or more and 20 or less carbon atoms and hydrogen include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the alkenyl group composed of carbon having 2 or more and 20 or less carbon atoms and hydrogen include vinyl, propenyl, cyclohexenyl group and the like. Examples of the aryl group composed of carbon having 6 or more and 20 or less carbon atoms and hydrogen include phenyl, trill, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, and the like. Examples thereof include phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, acetylenylyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Examples of the arylalkyl group composed of carbon having 7 or more and 20 or less carbon atoms and hydrogen include benzyl, phenylethyl, and phenylpropyl.

Examples of the halogen-containing group (monovalent halogen-containing group) include a halogen atom and a group in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, for example, a trifluoromethyl group. ..

Examples of the oxygen-containing group (monovalent oxygen-containing group) include methoxy, ethoxy, benzyloxy, phenoxy, naphthoxy, allylphenoxy, frill, methylfuryl, tetrahydrofuryl, pyranyl, tetrahydropyranyl, flofuryl, benzofuryl and dibenzofuryl group. And so on.

Examples of the nitrogen-containing group (monovalent nitrogen-containing group) include cyano, dimethylamino, benzylamino, pyrrolidinyl, piperidinyl, moricholyl, azepinyl, formamide, acetamide, benzamide, naphthamide, iminomethyl, dimethylhydrazonomethyl, imide, nitro, and the like. Examples thereof include nitrophenyl, aminophenyl, pyridyl, quinolyl, tetrahydroquinolyl, indolyl, indolinyl, carbazolyl, imidazolyl, oxazolyl, oxazolidinyl group and the like.

Examples of the boron-containing group (monovalent boron-containing group) include bolangyl, bolantriyl, and diboranyl group.
Examples of the sulfur-containing group (monovalent sulfur-containing group) include methylthio, ethylthio, benzylthio, phenylthio, naphthylthio, phenylthioallyl, thienyl, methylthienyl, tetrahydrothienyl, thiazolyl, dibenzothienyl, benzothiazolyl, benzenesulfonyl, and methanesulfonate. Group etc. can be mentioned.

Examples of the phosphorus-containing group (monovalent phosphorus-containing group) include dimethylphosphino, di-t-butylphosphino, and diphenylphosphino group.
Examples of the silicon-containing group (monovalent silicon-containing group) include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl and di. Examples thereof include naphthylsilyl, cyclodimethylenesilyl, cyclotrimethylenylsilyl, cyclotetramethylenesilyl, cyclopentamethylenesilyl, cyclohexamethylenesilyl, cycloheptamethylenesilyl group and the like.

Examples of the germanium-containing group (monovalent germanium-containing group) or the tin-containing group (monovalent tin-containing group) include a group obtained by converting silicon into germanium or tin in the silicon-containing group.

A mode in which a plurality of adjacent or neighboring groups are bonded to each other to form a ring is, for example, a mode in which R ¹¹ and R ¹² of the formula (II) are bonded to each other, or in the vicinity such as R ¹¹ and R ¹⁶ . Also included is an embodiment in which the located substituents are bonded to each other to form a ring structure. When a plurality of adjacent or neighboring groups are bonded to each other to form a ring, the ring is preferably a 5- to 7-membered ring. That is, in the present invention, the term "neighborhood" means a distance at which a 5- to 7-membered ring can be formed when a plurality of groups are bonded to each other.

Examples of the case of forming a ring as described above include indenyl, tetrahydroindenyl, fluorenyl, benzofluorenyl, octahydrofluorenyl, dibenzofluorenyl, octamethyloctahydrodibenzofluorenyl, and the like. Be done.

Further, when the cyclopentadienyl ring portion forms a ring together with ^{R 5 to} R ^{8 , the structure formed from the cyclopentadienyl ring portion and R 5 to} R ⁸ is an indenyl ring and an indenyl ring. Substituents that bind to may be formed. In this case, the ^{structure formed from the cyclopentadienyl ring moiety and R 5 to} R ⁸ may be the same as the structure formed from the indene ring moiety and R ^{9 to} R ¹⁶ , and the indene ring moiety may be used. And may have a structure formed from an indene ring and a substituent different from the structure formed from ^{R 9 to} R ^16.

Q ² is a divalent group that binds two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. These groups include the same substituents as those listed above Q ^1. Preferably, it is an alkylene group, a substituted alkylene group, an alkylidene group, or a silicon-containing group. More preferably, alkylene groups such as methylene, ethylene, propylene and butylene, isopropyridene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, Dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, etc. It is a substituted alkylene group of.

Q ² may ^{form a 3- to 8-membered ring containing Q 2} , preferably a 5- to 6-membered ring, and examples of the structure in this case include cyclopentane, cyclohexane, sirolan, and silinan ring.

X is a monovalent group and is independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. It is a group, preferably a halogen atom or a hydrocarbon group. Xs may be the same or different from each other, but are preferably the same.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus-containing group are R ^{5 above.} The same thing as the one that was done can be mentioned.
M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

The crosslinked metallocene compound represented by the general formula (II) has a double bond at the position of the 4-position of the indenyl group which is a ligand, that is, a structure having a specific group which is a structure of a conjugated system. .. Probably due to the electronic effect and steric effect of this conjugated structure, the polymer having a terminal vinyl group produced by the component (A) can be efficiently taken in, and the ethylene-based (co) weight having a high molecular weight is high. It is speculated that coalescence can be manufactured.

Further, it is presumed that the crosslinked metallocene compound represented by the general formula (II) has a small variation in catalytic activity depending on the polymerization reaction temperature. This is because the above-mentioned metallocene compound has a relatively large conformational change when the polymerization temperature rises, for example, as compared with the metallocene compound used in the comparative example described later, and this change suppresses the rise in the polymerization activity. I think it might be.

If the variation in the polymerization activity due to the polymerization temperature is small, the change in the heat of reaction is small even if the polymerization temperature rises a little, and it is considered that the resulting polymer is unlikely to be melted. Therefore, it is expected that the polymer particles are less likely to adhere to the wall surface of the polymerizer, that is, fouling is less likely to occur, the heat removal efficiency is less likely to decrease, and it is advantageous for stable operation.

The component (B) preferably contains a crosslinked metallocene compound represented by the following general formulas (II-α), (II-β), and (II-γ). Further, as another preferable example, an embodiment containing at least one crosslinked metallocene compound represented by (II-δ), (II-ε) and (II-ζ) can be mentioned.

一般式（ＩＩ−α）、（ＩＩ−β）、（ＩＩ−γ）、（ＩＩ−δ）、（ＩＩ−ε）および（ＩＩ−ζ）中、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、一価の基であり、それぞれ独立に、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、隣接する基は互いに結合して脂肪族環を形成していてもよい。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸およびＲ³⁹は、一価の基であり、それぞれ独立に、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、互いに同一でも異なっていてもよく、また、隣接もしくは近傍にある複数の置換基は互いに結合して環を形成してもよい。
これらの基としては、前記Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶で挙げたものと同様の基が挙げられる。

In the general formulas (II-α), (II-β), (II-γ), (II-δ), (II-ε) and (II-ζ), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are monovalent groups, which are independently hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups and boron-containing groups, respectively. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group, which may be the same or different from each other, and adjacent groups are bonded to each other to form an aliphatic ring. May be. R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are monovalent groups. Independently selected from hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group. It may be the same or different from each other, and a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring.
These groups are the same as those listed in ^{R 5} , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^16. Can be mentioned.

The general formulas (II-α), (II-β), (II-γ), (II-δ), (II-ε) and (II-ζ) are ethylene systems having more long-chain branches. This is a preferred embodiment in which a polymer (homogeneous polymer, copolymer) can be produced and the variation in catalytic activity due to the polymerization reaction temperature tends to be small. In particular, the general formulas (II-α), (II-β) and (II-γ) have higher polymerization reaction temperatures than the general formulas (II-δ), (II-ε) and (II-ζ). Since the fluctuation of the catalytic activity due to the above tends to be smaller, it is expected that the formation of polymer lumps in the polymer can be effectively prevented.

When R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are all hydrogen atoms, the molecular weight is relatively low as used as a catalyst for macromonomer production in Japanese Patent Application Laid-Open No. 2008-50278, so that the molecular weight is high. In the production of ethylene-based polymers, it is preferable that not all of them are hydrogen atoms at the same time. Of R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ , at least one group is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 or more carbon atoms and 2 or less carbon atoms, and even more preferably R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are all hydrocarbon groups having 1 or more and 2 or less carbon atoms.

The method for producing the metallocene compound represented by the general formula (II) is not particularly limited as long as the metallocene compound exhibiting the effect of the present invention can be obtained, and can be produced by a known method. An example of a typical synthetic route is shown below, but the aspect of the present invention is not limited thereto.

First, the substituted cyclopentadiene 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, "Organometallics 1988,7,1828.", WO1998 / 015510, "Organometallics 1996,15,4857.", "Organometallics 1997,16,2503.", "J.Orm. 1999, 577, 211. ”, WO2000 / 049029, JP2000-136195,“ Org. Let. 2008, 10, 2545. ”,“ Chem. Rev. 1992, 92, 965. ”,“ Science. 2012, 338, 504. ”and the like.

Further, the substituted indene compound as a starting material can also be produced by a known method, and the production method is not particularly limited. Known manufacturing methods include, for example, WO1998 / 040331, WO1998 / 046547, "J. Organomet. Chem. 1998, 571, 171.", "Tetrahedron Letter. 1999, 40, 7445.", JP-A-2004. 2259, "Organometrics 2006, 25, 1217.", US Pat. No. 7910783, JP 2011-500800, "Organometrics 2011, 30, 5744.", "Chem. Eur. J. 2012, 18, 4174." , "Organometrics 2012, 31, 4962.", Japanese Patent Application Laid-Open No. 2014-201519, Japanese Patent Application Laid-Open No. 7-286005 by the Applicant, and the like.

Further, the precursor compound (ligand) of the metallocene compound represented by the general formula (II) can be produced by a known method using the substituted cyclopentadiene compound or the substituted indene compound as a raw material, and in particular, The manufacturing method is not limited. As known production methods, for example, in addition to those mentioned as the production method of the substituted indene compound, "New J. Chem. 1990, 14, 499", "Angew. Chem. Int. Ed. 1995, 34, 2273." , "Organometallics 2003, 22, 2790.", "J. Organomet. Chem. 1997, 530, 75.", "J. Organomet. Chem. 2001, 619, 280." Examples thereof include Japanese Patent Application Laid-Open No. 2003-201259, Japanese Patent Application Laid-Open No. 2011-144157, and Japanese Patent Application Laid-Open No. 2014-193846.

Further, the target metallocene compound represented by the general formula (II) can be produced by a known method using the precursor compound (ligand), and the production method is not particularly limited. .. As a known production method, for example, in addition to the method for producing the precursor compound (ligand), US Pat. No. 5,972822, JP-A-10-109996, "J. Organomet. Chem. 1997, 527". , 297. ”, Japanese Patent Application Laid-Open No. 2002-88092,“ Оrganometrics 2012, 31, 4340. ”, And the like.

Specific examples of the metallocene compound represented by the general formula (II) according to the present invention are shown below, but the scope of the present invention is not particularly limited by this. In the present invention, the compound represented by the general formula (II) may be used alone, or two or more kinds of metallocene compounds having different chemical structures may be used among these compounds. Further, structural isomers having the same chemical structure may be used alone, or structural isomer mixtures having the same chemical structure (for example, meso-form mixture or racemic mixture) may be used.

Of the metallocene compounds represented by the general formula (II), for convenience, _{the ligand structure of the metallocene compound excluding MX 2} (metal moiety) is replaced with the cyclopentadienyl ring moiety, the indene ring moiety, and the indene ring moiety at the 2-position. The structure is divided into seven: a group (V), a substituent (W) at the 3-position of the indene ring portion, a substituent (Y) at the 4-position of the indene ring portion, an oxygen atom bond substituent (Z) at the indene ring portion, and a bridged portion. .. The abbreviation of the cyclopentadienyl ring moiety is (1), the abbreviation of the inden ring moiety is (2), the abbreviation of the substituent (V) at the 2-position of the inden ring moiety is (3), and the abbreviation of the substituent at the 3-position of the inden ring moiety (3). The abbreviation of W) is (4), the abbreviation of the substituent (Y) at the 4-position of the inden ring portion is (5), the abbreviation of the inden ring partial oxygen atom bond substituent (Z) is (6), and the structure of the crosslinked portion is constructed. The abbreviation is (7), and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

Specific examples of the metal portion MX _{n is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2 , Ti (η ⁴ -1,3- butadienyl), Ti (η ⁴ -1,3- pentadienyl), Ti (η ⁴ -2,4- hexadienyl), Ti (η ⁴ -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 (η 4 -1 , 3-butadienyl), Zr (eta ⁴ -1,3-pentadienyl), Zr (η ⁴ -2,4- hexadienyl), Zr (η ⁴ -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 (η 4 -1,3- butadienyl), Hf (eta ⁴ -1,3-pentadienyl), Hf (η ⁴ -2,4- hexadienyl), Hf (η ⁴ -1,4- _{diphenyl-1,3-pentadienyl), Hf (CH 2 -Si (} Me) ₃ ) ₂ , Hf (ОMe) ₂ , Hf (ОiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf (ОTf) _{2 and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and ОMs is a methanesulfonate. The group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

According to the above notation, the cyclopentadienyl ring moiety is (1) -4 in [Table 1], the indene ring moiety is (2) -9 in [Table 2], and the substituent at the 2-position of the indene ring moiety. (V) is (3) -1 in [Table 3], substituent (W) at the 3-position of the indene ring portion is (4) -1 in [Table 4], and substituent (Y) at the 4-position of the indene ring portion. ) Is (5) -11 in [Table 5], the indene ring partial oxygen atom bond substituent (Z) is (6) -1 in [Table 6], and the crosslinked portion is (7) in [Table 7]. When it is composed of a combination of -4 and the MX _{n of} the metal portion is Zr (NMe ₂ ) ₂ , the following compound [1] is exemplified.

The cyclopentadienyl ring moiety is (1) -20 in [Table 1], the indene ring moiety is (2) -4 in [Table 2], and the substituent (V) at the 2-position of the indene ring moiety is [ (3) -8 in [Table 3], the substituent (W) at the 3-position of the indene ring portion is (4) -1 in [Table 4], and the substituent (Y) at the 4-position of the indene ring portion is [Table 5]. ], The crosslinked portion is composed of the combination of (7) -26 in [Table 7], and when the MX _{n of} the metal portion is ZrCl ₂ , the following compound [2] is exemplified. There is.

Further, the indene ring moiety is (2) -2 in [Table 2], the substituent (V) at the 2-position of the indene ring moiety is (3) -13 in [Table 3], and the substituent at the 3-position of the indene ring moiety. (W) is (4) -1 in [Table 4], the substituent (Y) at the 4-position of the indene ring portion is (5) -33 in [Table 5], and the crosslinked portion is (Table 7]. 7) When it is composed of a combination of −32 and the MX _{n of} the metal portion is HfMe ₂ , the following compound [3] is exemplified. In the following compound [3], in the metallocene compound represented by the general formula (II), the cyclopentadienyl ring moiety forms a substituent that binds to the indenyl ring and the indenyl ring together with ^{R 5 to} R ^8. This is the mode.

Further, when the _{two indene ring portions bonded to the metal portion MX n} are not the same but different, one indene ring portion is located at (2) -11 in [Table 2] and the indene ring portion at the second position. The substituent (V) is (3) -2 in [Table 3], the substituent (W) at the 3-position of the indene ring portion is (4) -1 in [Table 4], and the other indene ring portion. Is (2) -1 in [Table 2], the substituent (V) at the 2-position of the indene ring portion is (3) -11 in [Table 3], and the substituent (W) at the 3-position of the indene ring portion is [ (4) -1 in [Table 4], the substituent (Y) at the 4-position of the indene ring portion is (5) -26 in [Table 5], and the crosslinked portion is (7) -1 in [Table 7]. formed by a combination, MX _n of the metal parts in the case of Ti (eta ^{4-1,3-pentadienyl),} illustrates the following compounds [4]. In the following compound [4], in the metallocene compound represented by the general formula (II), the cyclopentadienyl ring moiety forms a substituent that binds to the indenyl ring and the indenyl ring together with ^{R 5 to} R ^8. This is the mode.

(Component (C))
The component (C) is at least one component selected from the group consisting of the following (c-1), (c-2) and (c-3).
(C-1) Organometallic compound represented by the following formula (III), (IV) or (V) (c-2) Organoaluminium oxy compound (c-3) Reaction with component (A) and component (B) Compounds that form an ion pair These compounds may be used alone or in combination of two or more.

R ^a _m Al (ОR ^b ) _n H _p X _q・ ・ ・ (III)
In formula (III), R ^a and R ^b each independently represent a hydrocarbon group having 1 or more and 15 or less carbon atoms, which may be the same or different from each other, where X represents a halogen atom and m is. 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3.

_{^{M a AlR a 4 ··· (IV}} )
In formula (IV), Ma represents ^a lithium atom, a sodium atom or a potassium atom, and ^Ra represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

R ^a _r M ^b R ^b _s X _t・ ・ ・ (V)
In formula (V), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other, and M ^b is a magnesium atom, a zinc atom or a zinc atom. A cadmium atom and X represent a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2.

Among the organic metal compounds (c-1) represented by the formulas (III), (IV) or (V), the organic metal compound represented by the general formula (III) is preferable, and the organic metal compound represented by the general formula (III) is represented. Specific examples of the organic metal compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri2-ethylhexylaluminum, dimethylaluminum chloride, and diethyl. Dialkylaluminum halides such as aluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, alkylaluminum sesquibride such as ethylaluminum sesquibramide. , Methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalide such as ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutyl Alkyl aluminum hydrides such as aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum hydride, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum Examples thereof include dialkylaluminum alcokiside such as methoxide and diisobutylaluminum ethoxide.

Examples of the formula (IV) include lithium aluminum hydride and the like.
Further, examples of the above formula (V) include dialkylzinc compounds described in JP-A-2003-171412 and the like, and they can also be used in combination with phenol compounds and the like.

As the organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable.
Such organoaluminum oxy compounds are used alone or in combination of two or more.

Examples of the compound (c-3) that reacts with the component (A) and the component (B) to form an ion pair include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179005. , Lewis acid, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US5321106 and the like, as well as heteropoly compounds and Isopoly compounds and the like can be used.

In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, it not only exhibits extremely high polymerization activity with respect to the olefin compound, but also with active hydrogen in the solid support. The component (C) preferably contains at least an organoaluminum oxy compound (c-2) because the solid carrier component containing the co-catalyst component can be easily prepared by reacting.

[Method for preparing catalyst for olefin polymerization]
Next, the method for preparing the catalyst for olefin polymerization in the present invention will be described.
The catalyst for olefin polymerization according to the present invention can be prepared by adding the component (A), the component (B) and the component (C) in an activated carbon or in a polymerization system using an activated carbon.

The order of addition of each component is arbitrary, but a preferred order is, for example,
(I) Method of adding component (C), component (A), and component (B) to the polymerization system in this order (ii) In the polymerization system in the order of component (C), component (B), and component (A) Method of adding to (iii) Component (A) and component (C) mixed and contacted to add to the polymerization system, and then to add component (B) to the polymerization system (iv) Component (B) ) And the component (C) in mixed contact are added to the polymerization system, and then the component (A) is added to the polymerization system. (V) The component (C) is added to the polymerization system, and then the component (C) is added to the polymerization system. Method of adding a contact material in which the component (A) and the component (B) are mixed and contacted into the polymerization system (vi) Add the component (C), the component (A), and the component (B) to the polymerization system in this order. , The method of adding the component (C) to the polymerization system again (vi) The component (C), the component (B), and the component (A) are added to the polymerization system in this order, and the component (C) is added to the polymerization system again. Method of adding to (viii) A contact product obtained by mixing and contacting the component (A) and the component (C) is added to the polymerization system, then the component (B) is added to the polymerization system, and then the component (C) is again added. (Ix) A contact product obtained by mixing and contacting the component (B) and the component (C) is added to the polymerization system, then the component (A) is added to the polymerization system, and then again. Method of adding component (C) to the polymerization system (x) The component (C) is added to the polymerization system, and then a contact material obtained by mixing and contacting the component (A) and the component (B) is added to the polymerization system. After that, a method of adding the component (C) to the polymerization system again can be mentioned. Among these, particularly preferable contact sequences include the above-mentioned (i), (ii) and (v).

Further, the catalyst for olefin polymerization according to the present invention is one in which a solid catalyst component (X) containing the component (A), the component (B) and the component (C) is preferable. The solid catalyst component (X) is a method for contacting the component (C) with the following solid carrier (S), JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, It can be prepared by insolubilizing the component (C) by the method described in WO2010 / 55652A1 pamphlet or the like.

Examples of the solid catalyst component (X) containing the solid carrier (S) include the solid catalyst component (XA) formed from the solid carrier (S), the component (C) and the component (A). , A catalyst for olefin polymerization composed of a solid catalyst component (XB) formed from a solid carrier (S), a component (C) and a component (B), and a solid carrier (S), a component (A), a component. An example is an olefin polymerization catalyst composed of the solid catalyst component (XC) formed from the component (B) and the component (C). Among these, a catalyst for olefin polymerization composed of the solid catalyst component (XC) is more preferable.

The contact order of each component is arbitrary, but a preferred method is, for example,
(Xi) The component (C) and the solid carrier (S) are brought into contact with each other, and then the solid catalyst component (XA) prepared by contacting the component (A) is brought into contact with the component (C) and the component (S). Then, a method using the solid catalyst component (X-B) prepared by contacting the component (B) (xi) The component (A) and the component (C) are mixed and contacted, and then contacted with the solid carrier (S). A method using the solid catalyst component (XB) prepared by mixing and contacting the solid catalyst component (XA), the component (B), and the component (C), and then contacting the component (S) (xiii). ) Solid catalyst component (XA), component (C) and solid prepared by contacting the component (C) with the solid carrier (S) and then contacting the contact material between the component (A) and the component (C). Method using solid catalyst component (X-B) prepared by contacting the state carrier (S) and then contacting the contact material of the component (B) and the component (C) (xiv) The component (C) and the solid carrier The solid catalyst component (XA), the component (C), and the solid carrier (S), which are prepared by contacting (S), then contacting the component (A), and then contacting the component (C) again, are contacted. A method using a solid catalyst component (X-B) prepared by contacting the component (B) and then contacting the component (C) again (xv) The component (C) is mixed with the solid carrier (S). A method using a solid catalyst component (XC) prepared by contacting the components (A) and then contacting the components (B) (xvi) The component (C) is added to the solid carrier (S). Method using solid catalyst component (XC) prepared by contacting component (A) after mixed contact and then contacting component (B) (xvii) Component (C) on solid carrier (S) A method using a solid catalyst component (XC) prepared by contacting and then contacting a contact mixture of the component (A) and the component (B).
(Xviii) A method using a solid catalyst component (XC) prepared by mixing and contacting the component (A) and the component (B), then contacting the component (C), and subsequently contacting the solid carrier (S). ,
(Xix) A solid catalyst component prepared by contacting the component (C) with the solid carrier (S), further contacting the component (C), and then contacting the component (A) and then the component (B) in this order. Method using (XC) (xx) The component (C) is brought into contact with the solid carrier (S), and the component (C) is further contacted, and then the component (B) and the component (A) are contacted in this order. Method using solid catalyst component (XC) prepared by contacting (xxi) After contacting the component (C) with the solid carrier (S), further contacting the component (C), and then the component (A). Method using a solid catalyst component (XC) prepared by contacting a contact mixture of the component (B) with the component (B) (xxii) The component (C) is mixed and contacted with the solid carrier (S), and then the component (A) is combined with the component (A). Method using solid catalyst component (XC) prepared by contacting a contact mixture of component (B) and component (C) (xxiii) Mixing contact of component (C) with a solid carrier (S), then component Method using solid catalyst component (XC) prepared by contacting a contact mixture of (A) and component (C) and further contacting component (B) (xxiv) Component (C) on solid carrier (S) ) Is mixed and contacted, then the contact mixture of the component (B) and the component (C) is brought into contact with each other, and then the component (A) is brought into contact with each other to prepare a solid catalyst component (XXv). After contacting the component (C) with the carrier (S) and further contacting the component (C), a contact mixture of the component (A) and the component (C), and a contact mixture of the component (B) and the component (C) are then contacted. Method using solid catalyst component (X-C) prepared by contacting in the order of (xxvi) The component (C) is brought into contact with the solid carrier (S), and the component (C) is further brought into contact with the component (C), and then the component (C) is contacted. Method using solid catalyst component (XX) prepared by contacting the contact mixture of (B) and component (C) and the contact mixture of component (A) and component (C) in this order (xxvii) Solid carrier ( The solid catalyst component (S) is prepared by contacting the component (C) with the component (C), further contacting the component (C), and then contacting the contact mixture of the component (A), the component (B), and the component (C). Method using XX) (xxviii) A mixture of a component (A) and a component (C) and a mixture of a component (B) and a component (C) are mixed in advance, and this is mixed with a solid carrier (S) and a component (C). ) Method using a solid catalyst component (XC) prepared by contacting the contact material (xxix) A mixture of the component (A) and the component (C) and a mixture of the component (B) and the component (C) are mixed in advance. Then, this is used as a solid carrier (S) and a component (C). ), Further, a method using a solid catalyst component (X-C) prepared by contacting the contact with the component (C) with the contact material and the like can be mentioned.

When a plurality of components (C) are used, the components (C) may be the same or different from each other. Of these, particularly preferable contact sequences include (xxi), (xiii), (xv), (xvi), (xvii), (xxiii), (xxiii) and (xxiv).

The contact between the component (C) and the solid support (S) causes the reaction site in the component (C) to react with the reaction site in the solid carrier (S) to cause the component (C) and the solid carrier (S) to react. It is chemically bonded to form a contact between the component (C) and the solid support (S). The contact time between the component (C) and the solid support (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually −50 to 200 ° C., preferably -20 to 120 ° C. Is. When the initial contact between the component (C) and the solid carrier (S) is abruptly performed, the solid carrier (S) collapses due to the reaction heat generation and reaction energy, and the morphology of the obtained solid catalyst component (X) deteriorates. However, when this is used for polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between the component (C) and the solid carrier (S), the reaction is brought into contact at a low temperature of -20 to 30 ° C. or the reaction heat generation is controlled to control the initial contact temperature for the purpose of suppressing the reaction heat generation. It is preferable to react at a sustainable rate. The same applies to the case where the component (C) and the solid carrier (S) are brought into contact with each other and the component (C) is further brought into contact with each other. The molar ratio of contact between the component (C) and the solid carrier (S) (component (C) / solid carrier (S)) can be arbitrarily selected, but the higher the molar ratio, the more the component (A), The contact amount of the component (B) can be increased, and the activity of the solid catalyst component (X) can be improved.

As a preferable range, the molar ratio of the component (C) to the solid carrier (S) [= molar amount of the component (C) / molar amount of the solid carrier (S)] is usually 0.2 to 2.0, particularly 0.2 to 2.0. Preferably, it is 0.4 to 2.0.

Regarding the contact between the contact material of the component (C) and the solid carrier (S) and the component (A) and the component (B), the contact time is usually 0 to 5 hours, preferably 0 to 2 hours, and the contact time. The temperature is usually in the range of −50 to 200 ° C., preferably −50 to 100 ° C. The amount of contact of the component (A) and the component (B) with respect to the component (C) largely depends on the type and amount of the component (C), and in the case of the component (c-1), the component (c-1) and the component. The molar ratio [(c-1) / M] with all the transition metal atoms (M) in (A) and the component (B) is usually 0.01 to 100,000, preferably 0.05 to 50,000. Used in quantity, in the case of component (c-2), the molar ratio of aluminum atoms in component (c-2) to all transition metal atoms (M) in component (A) and component (B) [( c-2) / M] is usually used in an amount such that it is usually 10 to 500,000, preferably 20 to 100,000. In the case of the component (c-3), the molar ratio [(c-3) / M] of the component (c-3) to all the transition metal atoms (M) in the component (A) and the component (B) is , Usually used in an amount such that 1 to 10, preferably 1 to 5. The molar ratio of the component (C) to the total transition metal atoms (M) in the component (A) and the component (B) can be determined by inductively coupled plasma emission spectrometry (ICP analysis method).

Examples of the solvent used for preparing the solid catalyst component (X) include an inert hydrocarbon solvent, and specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Examples include alicyclic hydrocarbons such as hydrogen, cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Be done.

In each method showing the contact sequence form, a step including contact between the solid carrier (S) and the component (C), a step including contact between the solid carrier (S) and the component (A), and the solid carrier (S). ) And the component (B), and the solid carrier (S) and the component (A) and the component (B). , (G-2) higher aliphatic amides, (g-3) polyalkylene oxides, (g-4) polyalkylene oxide alkyl ethers, (g-5) alkyl diethanolamines, and (g-6) polyoxyalkylene alkyl amines. At least one compound selected from the above may coexist. By coexisting the component (G), fouling during the polymerization reaction can be suppressed, and the particle properties of the produced polymer are improved. Among the components (G), (g-1), (g-2), (g-3), and (g-4) are preferable.

Next, the solid carrier (S) will be described in detail.
The solid support (S) that can be used as needed in the present invention is an inorganic or organic compound, which is a solid in the form of granules or fine particles.

Among these, examples of the inorganic compound include porous oxides, inorganic halides, clays, clay minerals, ion-exchange layered compounds and the like. Among these inorganic compounds, porous oxides are preferable.

Examples of the porous oxide include a porous oxide having a composition such as _{SiО 2} , Al ₂ О ₃ , Mg _{О, Zr О, Ti О 2} , B ₂ О ₃ , Ca _{О, Zn О, Ba О and Th О 2 or a composition thereof.} Examples thereof include composite oxides containing, or mixtures of these porous oxides, and specific examples thereof include natural or synthetic zeolites, SiО _2- MgО, SiО _2- Al ₂ О ₃ , SiО _2- TiО ₂ , and SiО ₂ −. V ₂ o _5, include a porous oxide having a composition such as SiО ₂ -Cr _{2 О 3} and SiО ₂ -TiО ₂ -MgО. Of these, _{a porous oxide containing SiО 2} as a main component is preferable.

The porous oxides include 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 О, K ₂ О, Li ₂ О and other carbonates, sulfates, nitrates and oxide components may be contained.

Although the properties of such a porous oxide differ depending on the type and production method, the carrier preferably used in the present invention has a particle size of 0.2 to 300 μm, preferably 1 to 200 μm, and a specific surface area of 50. ~1200m ² / g, preferably in the range of 100~1000m ² / g, it is desirable that the pore volume is in the range of 0.3~30cm ³ / g. Such a carrier is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . 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 product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.

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

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

Such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, alophen, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dicite. , halloysite, and examples of the ion-exchange layered _{compounds, α-Zr (HAsО 4)} 2 · H 2 О, α-Zr (HPО 4) 2, α-Zr (KPО 4) 2 · 3H 2 О, α-Ti (HPО ₄ ) ₂ , α-Ti (HAsО ₄ ) ₂ · H ₂ О, α-Sn (HPО ₄ ) ₂ · H ₂ О, γ-Zr (HPО ₄ ) ₂ , γ-Ti (HPО ₄₎ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ , H ₂ O, and other crystalline acidic salts of polyvalent metals can be mentioned.

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, preferably 0.3 to 5 cc / g. Especially preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ^{4 Å by a mercury intrusion method using a mercury porosimeter.}

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

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

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include, for example, a polymer produced mainly of an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene. , Polymers and reactants produced with divinylbenzene as the main component, and granular or fine particle solids composed of variants thereof.

As the solid carrier (S), a porous oxide is preferable from the viewpoint of preventing foreign substances during molding.
The usage ratio of the component (A) to the component (B) can be appropriately determined according to the molecular weight and the molecular weight distribution of the polymer to be produced.

The solid catalyst component (X) as described above can be used as it is for the polymerization of the olefin, but it is used after prepolymerizing the olefin with the solid catalyst component (X) to form the prepolymerization catalyst component (XP). You can also do it.

The prepolymerization catalyst component (XP) can be prepared by introducing an olefin in the presence of the solid catalyst component (X), usually in an inert hydrocarbon solvent. As the reaction method, any of a batch method, a semi-continuous method and a continuous method can be used. The reaction can be carried out under reduced pressure, normal pressure or pressure. By this prepolymerization, a polymer of usually 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g is produced per 1 g of the solid catalyst component.

The prepolymerization catalyst component (XP) prepared in the inert hydrocarbon solvent is separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin is introduced into the obtained suspension. Alternatively, the olefin may be introduced after drying.

The prepolymerization temperature is usually -20 to 80 ° C, preferably 0 to 60 ° C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component (X) used for the prepolymerization, those already described can be used without limitation. Further, the component (C) is used as needed, and in particular, the organoaluminum compound represented by the above formula (III) in (c-1) is preferably used. When the organoaluminum compound of the formula (III) is used as the component (C), the molar ratio (component) of the aluminum atom (Al) in the component (C) to the transition metal compound which is the component (A) and (B). (C) / Transition metal compound), usually in an amount of 0.1 to 10000, preferably 0.5 to 5000.

The concentration of the solid catalyst component (X) in the prepolymerization system is usually 1 to 1000 g / liter, preferably 10 to 500 g / liter in a ratio of the solid catalyst component (X) / polymerization volume of 1 liter. At the time of prepolymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

Further, for the purpose of improving the fluidity of the prepolymerization catalyst component (XP), heat spot seating during polymerization, and suppressing the generation of polymer lumps, the component (G) is added to the prepolymerization catalyst component (XP) once generated by prepolymerization. You may make contact. At this time, the above-mentioned (g-1), (g-2), (g-3), and (g-4) are preferable as the component (G) to be used.

The temperature at which the component (G) is mixed and contacted is usually −50 to 50 ° C., preferably -20 to 50 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.
When the solid catalyst component (X) and the component (G) are mixed and contacted, the component (G) is usually 0.1 to 20 parts by weight, preferably 0. It is used in an amount of 3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

The mixed contact between the solid catalyst component (X) and the component (G) can be carried out in an inert hydrocarbon solvent, and the inert hydrocarbon solvent is the same as the solvent used for preparing the solid catalyst component (X). Can be mentioned.

The olefin polymerization catalyst according to the present invention can be used as a dry prepolymerization catalyst by drying the prepolymerization catalyst component (XP). The prepolymerization catalyst component (XP) is usually dried after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerization catalyst by filtration or the like.

The prepolymerization catalyst component (XP) is dried by keeping the prepolymerization catalyst component (XP) at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of an inert gas. The amount of the volatile component of the obtained dry prepolymerization catalyst is preferably 2.0% by weight or less, preferably 1.0% by weight or less. The smaller the amount of the volatile component of the dry prepolymerization catalyst, the better, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 3 to 8 hours, although it depends on the drying temperature. If the amount of the volatile component of the dry prepolymerization catalyst exceeds 2.0% by weight, the fluidity of the dry prepolymerization catalyst may decrease, and stable supply to the polymerization reactor may not be possible.

Here, the amount of the volatile component of the dry prepolymerization catalyst is measured by, for example, a weight loss method, a method using gas chromatography, or the like.
In the weight loss method, the weight loss when the dry prepolymerization catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is obtained and expressed as a percentage of the dry prepolymerization catalyst before heating.

In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dry prepolymerization catalyst, a calibration curve is prepared according to the internal standard method, and the amount is calculated as% by weight from the GC area.

As a method for measuring the amount of volatile components of the dry prepolymerization catalyst, a weight loss method is adopted when the amount of volatile components of the dry prepolymerization catalyst is about 1% by weight or more, and the amount of volatile components of the dry prepolymerization catalyst is about 1. When it is less than% by weight, a method using gas chromatography is adopted.

Examples of the inert gas used for drying the prepolymerization catalyst component (XP) include nitrogen gas, argon gas, neon gas and the like. Such an inert gas has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (volume basis), and a water content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (weight basis). ) Is desirable. If the oxygen concentration and water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be significantly reduced.

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

[Method for producing olefin polymer]
Next, the method for producing the olefin polymer according to the present invention will be described. An olefin polymer is obtained by polymerizing (homopolymerizing or copolymerizing) an olefin in the presence of the above-mentioned olefin polymerization catalyst. In the present invention, by using the catalyst for olefin polymerization, it is possible to efficiently produce an ethylene-based copolymer having high polymerization activity, excellent molding processability and mechanical strength, and having many long-chain branches. It is preferable to contain ethylene as the olefin. The ethylene-based polymer in the present invention refers to a polymer containing 10 mol% or more of ethylene.

In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method, but in the suspension polymerization method and the gas phase polymerization method, the solid catalyst component (X) is used. It is preferable to use it.

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 methyl. Aliphatic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane and mixtures thereof. Further, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

When polymerizing an olefin using the above catalyst for olefin polymerization, the components (A) and (B) are usually 10 ^-12 to 10 ^-1 mol, preferably 10 ^-8 to 10 mol, per liter of the reaction volume. It is used in an amount that makes it ^{-2 mol.} Further, the component (C) is used, and in particular, the organoaluminum compound represented by the general formula (III) in (c-1) is preferably used.

The polymerization temperature of the olefin using the above-mentioned solid catalyst component is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C., and particularly preferably 60 to 170 ° C. The polymerization pressure is usually under the conditions of normal pressure to 100 kg / cm ² , preferably normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Can be done. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

Further, the olefin supplied to the polymerization reaction in the present invention is not particularly limited as long as the effect of the present invention is exhibited, but is preferably one or more monomers selected from olefins having 2 or more and 20 or less carbon atoms. Specific examples of the olefin having 2 or more and 20 or less carbon atoms include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Α-olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4 Cyclic olefins such as 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; and the like. Specific examples of the above olefins include, for example, styrene, vinylcyclohexane, diene, acrylate, methacrylic acid, fumaric acid, maleic anhydride, etc .; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid and the like. Such as polar monomers and the like can also be mentioned.

Among the methods for producing an olefin polymer, a method for producing an ethylene-based polymer in which ethylene or ethylene and an olefin having 3 or more and 20 or less carbon atoms are polymerized in the presence of the olefin polymerization catalyst is preferable.

[Ethylene polymer]
The ethylene-based polymer according to the present invention polymerizes ethylene or ethylene with an olefin having 3 or more and 20 or less carbon atoms in the presence of the catalyst for olefin polymerization, and is preferably selected from ethylene and an olefin having 3 or more and 20 or less carbon atoms. It is obtained by including a step of copolymerizing with one or more kinds of monomers. The ethylene-based polymer is not particularly limited, but preferably has the properties shown in the following requirements (1) to (4). The measurement method of these requirements is as described in the examples.

(1) a density of at 875kg / m ³ or more 970 kg / m ³ or less, the lower limit is preferably 885kg / m ^3, more preferably at 905 kg / m ^3, the upper limit is preferably 964kg / m ^3, more preferably 960kg / M ³ .

When the density is equal to or higher than the lower limit, the surface stickiness of the film formed from the ethylene polymer is small and the blocking resistance is excellent. When the density is equal to or lower than the upper limit, the impact of the film formed from the ethylene polymer is high. The strength is good, and the mechanical strength such as heat seal strength and bag breaking strength is good.

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

(2) According to the standard method of ASTM D1238-89, the melt flow rate [MFR (g / 10 minutes)] at 190 ° C. under a 2.16 kg load is 0.01 to 100 g / 10 minutes, which is the lower limit. Is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes, and the upper limit is preferably 50 g / 10 minutes, more preferably 30 g / 10 minutes.

When the MFR is 0.01 g / 10 minutes or more, the shear viscosity of the ethylene polymer is not too high and the moldability is excellent. For example, the appearance of a film is good. When the MFR is 100 g / 10 minutes or less, the tensile strength and heat seal strength of the ethylene polymer are good.

(3) The ratio [MT / η * (g / P)] of the melt tension [MT (g)] at 190 ° C. to the shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec is 1. It is .2 × 10 ^{-4 to} 10.0 × 10 ^-4 , the lower limit is preferably 1.4 × 10 ^-4 , and the upper limit is preferably 8.0 × 10 ^-4 .

MT / η * indicates the melt tension per unit shear viscosity, and when this value is large, the melt tension becomes large for the shear viscosity. That is, when MT / η * is at least the lower limit value, the balance between extrusion characteristics and bubble stability or neck-in is good in the ethylene polymer. Further, when MT / η * is not more than the upper limit value, the high-speed moldability is good in the ethylene-based polymer.

It is considered that MT / η * depends on the long-chain branching content and the high molecular weight component amount of the ethylene polymer. The larger the long-chain branching content and the high molecular weight component amount, the larger the MT / η * and the long-chain branching content. MT / η * tends to be smaller as the amount of high molecular weight components is smaller.

(4) Extreme viscosity [[η] (dl / g)] measured in 135 ° C. decalin and weight average molecular weight measured by gel permeation chromatography (GPC) -viscosity detector method (GPC-VISCO) ( Mw) satisfies the following relational expression (Eq-1).
0.90 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 −−−−− (Eq-1)

The lower limit is preferably 0.95 × 10 ^-4 × Mw ^0.776 , more preferably 1.00 × 10 ^-4 × Mw ^0.776 , and the upper limit is preferably 1.58 × 10 ^-4 × Mw ^0.776 , more preferably 1.50. × 10 ^-4 × Mw ^0.776 .

It is known that when a long-chain branch is introduced into an ethylene-based polymer, the ultimate viscosity [η] (dl / g) becomes smaller for the molecular weight than a linear ethylene-based polymer without a long-chain branch. (For example, Walther Chain, ADVANCES IN Polymer)
SCIENCE, 143, Branched Composer II, p. 137 (1999)). Therefore, even in this ethylene-based polymer, when the ultimate viscosity [η] (dl / g) is 1.65 × 10 ^-4 × Mw ^0.776 or less, it has a large number of long-chain branches, so that the moldability is improved. Excellent fluidity.

The ethylene-based polymer particles obtained by the polymerization reaction and other components added as desired can be melted, kneaded, and granulated by any method for the purpose of suppressing variations in physical property values.

The ethylene polymer obtained in the present invention may be pelletized by the following method.
(I) A method in which an ethylene polymer and other components added if desired are mechanically blended using an extruder, a kneader, or the like and cut into a predetermined size.

(Ii) The ethylene-based polymer and other components added as desired are dissolved in a suitable good solvent (eg, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is added. A method of removing and then mechanically blending using an extruder, kneader, etc. and cutting to a predetermined size.

The ethylene-based polymer obtained in the present invention contains weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, antifogging agents, lubricants, pigments, as long as the object of the present invention is not impaired. Additives such as dyes, nucleating agents, plasticizers, antistatic agents, hydrochloric acid absorbers, and antioxidants may be blended as needed.

The ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive are processed by general film molding, blow molding, injection molding and extrusion molding. In film molding, it is obtained by extrusion laminating molding, T-die film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing) and the like. The film obtained by using the ethylene-based polymer can be used as a single layer, but can be further imparted with various functions by forming a multilayer. In that case, the coextrusion method in each of the molding methods can be mentioned. On the other hand, by a laminating laminating molding method such as extrusion laminating molding or dry laminating method, laminating with paper or barrier film (aluminum foil, thin film, coating film, etc.) that is difficult to coextrude can be mentioned. It is possible to produce high-performance products by multi-layering by the coextrusion method in blow molding, injection molding, and extrusion molding in the same manner as in film molding.

Examples of the molded product obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive include a film, a blow infusion bag, a blow bottle, and a gasoline tank. Examples include extrusion-molded tubes, pipes, tear-off caps, injection-molded products such as daily miscellaneous goods, fibers, and large-sized molded products by rotary molding.

Further, the ethylene-based polymer obtained in the present invention and, if necessary, a film obtained by processing a resin composition containing a thermoplastic resin or an additive can be used as a water packaging bag, a liquid soup packaging bag, or a liquid paper container. , Lami raw fabric, specially shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, various packaging films for food packaging, protective films, infusion bags, agriculture Suitable for materials and the like. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the description of the following examples.
<(1) Synthesis of component (A)>
[Synthesis Example 1]
Dimethylsilylene-1- (3-n-propylcyclopentadienyl) -1- (cyclopentadienyl) zirconium dichloride (hereinafter referred to as component (A-1)) is synthesized by the method described in Japanese Patent No. 5455354. did.

<(2) Synthesis of component (B)>
[Synthesis Example 2-1]
In a 100 mL reactor that was thoroughly dried and substituted with argon, ORGANOMETALLICS 2006, 25, 1217. 1.04 g (5.02 mmol) of 2-methyl-4-phenylindene synthesized by the method described and 15 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., 3.20 mL of n-butyllithium solution (hexane solution, 1.60 M, 5.12 mmol) was added to the solution, and the mixture was stirred at room temperature for 3 hours. This solution was added to a diluted solution of 1.20 mL (5.43 mmol) of chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-1-yl) silane purchased from Aldrich in Tetrahydrofuran (8 mL). The mixture was added slowly under cooling at −78 ° C. and stirred at room temperature for 16 hours. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product represented by the following formula (B-1a) (hereinafter referred to as compound (B-1a)). It was obtained as a 0.65 g (34% yield) isomer mixture.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.57-7.11 (8H, m, Ar-H), 6.79-6.67 (1H, m, Ar-CH = C), 3.78- 3.17 (2H, m, CH-Si-CH), 2.26-2.18 (3H, m, C-CH ₃ ), 2.02 (3H, s, C-CH ₃ ), 1.99 (3H, s, C-CH ₃ ), 1.89 (6H, s, C-CH ₃ ), -0.25 (3H, s, Si-CH ₃ ), -0.29 (3H, s, Si) −CH ₃ ) ppm

[Synthesis Example 2-2]
0.19 g (0.50 mmol) of the ligand (B-1a) obtained in [Synthesis Example 2-1], 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon. Stirred. The solution was cooled to 0 ° C., 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.01 mmol) was added, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After distilling off the solvent of the reaction solution, 10 mL of dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. After the obtained solution was concentrated under reduced pressure, the suspension was prepared by adding 5 mL of n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (B-1). ) Was obtained in the form of a yellow powder (hereinafter referred to as component (B-1)) in an amount of 0.17 g (yield 63%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.72-7.63 (2H, m, Ar-H), 7.56 (1H, d, J = 8.7 Hz, Ar-H), 7.51- 7.27 (4H, m, Ar-H), 7.10-7.00 (2H, m, Ar-H), 2.29 (3H, s, Ar-CH ₃ ), 2.09 (3H, 3H, s, Ar-CH ₃ ), 2.00 (3H, s, Ar-CH ₃ ), 1.93 (3H, s, Ar-CH ₃ ), 1.90 (3H, s, Ar-CH ₃ ), 1.22 (3H, s, Si-CH ₃ ), 1.11 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 544

[Synthesis Example 3-1]
0.42 g (17.2 mmol) of magnesium pieces were charged into a 200 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. To this solution, J. Am. Chem. Soc. 2006, 128, 16486. Slowly add a diluted solution of 1.67 g (15.6 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized by the method described in tetrahydrofuran (25 mL) and heat reflux in an oil bath for 1 hour. did. After cooling the reaction solution to −78 ° C., 2.00 mL (18.0 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while slowly returning to room temperature. A 1.0 M aqueous hydrochloric acid solution was added, soluble components were extracted with diethyl ether, and the obtained fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off, and the residue obtained was obtained by adding Organometallics 2006, 25, 1217. 2.70 g (12.0 mmol) of 4-bromo-2-methyl-1-indanone synthesized by the method described, 6.69 g (31.5 mmol) of tripotassium phosphate, 0.03 g (0.13 mmol) of palladium acetate, 0.08 g (0.18 mmol) of 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl (S-Phos), 30 mL of tetrahydrofuran and 6 mL of distilled water were charged, and the mixture was heated under reflux in an oil bath for 2 hours. After cooling the reaction solution to room temperature, saturated aqueous ammonium chloride solution was added, soluble components were extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product represented by the following formula (B-2a) (hereinafter referred to as compound (B-2a)). 4.09 g (yield 93%) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1 H, dd, J = 7.5 and 1.2 Hz, Ar-H), 7.61 (1 H, dd, J = 7.5 and 1.2 Hz, Ar-H) ), 7.45 (1H, t, J = 7.5Hz, Ar-H), 7.33 (2H, s, Ar-H), 3.76 (3H, s, -ОCH ₃ ), 3.56 -3.39 (1H, m, CH-CH ₃ ), 2.85-2.65 (2H, m, Ar-CH _2- C), 1.48 (18H, s, -C (CH ₃ ) ₃ ), 1.33 (3H, d, J = 7.3Hz, CH-CH ₃ ) ppm

[Synthesis Example 3-2]
4.07 g (11.2 mmol) of the compound (B-2a) obtained in [Synthesis Example 3-1], 15 mL of tetrahydrofuran, and 5 mL of methanol were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and stirred. The solution was cooled to 0 ° C., 0.85 g (22.6 mmol) of sodium hydroborate was slowly added in small portions, and the mixture was stirred at room temperature for 2 hours. The solution was cooled to 0 ° C., a 1.0 M aqueous hydrochloric acid solution was slowly added, solubles were extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 0.05 g (0.24 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling off the filtrate, and the mixture was heated in an oil bath for 1 hour. Refluxed. After cooling the reaction solution to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, soluble components were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product (hereinafter referred to as compound (B-2b)) represented by the following formula (B-2b). 3.51 g (yield 90%) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.41 (2H, s, Ar-H), 7.35-7.17 (2H, m, Ar-H), 7.12 (1H, dd, J = 7.4and 1.3Hz, Ar-H), 6.53 (1H, dd, J = 2.9and1.4Hz, Ar-CH = C), 3.75 (3H, s, -ОCH ₃ ), 3.38 (2H, s, Ar-CH _2- C), 2.15 (3H, s, CH-CH ₃ ), 1.47 (18H, s, -C (CH ₃ ) ₃ ) ppm

[Synthesis Example 3-3]
1.05 g (3.00 mmol) of the compound (B-2b) obtained in [Synthesis Example 3-2] and 15 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. The solution was cooled to −78 ° C., 2.00 mL of n-butyllithium solution (hexane solution, 1.55 M, 3.10 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. After adding 0.30 mL (3.19 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, the mixture was cooled to −78 ° C. and chlorodimethyl (2,3,4,5-tetra) purchased from Aldrich. Methyl-2,4-cyclopentadiene-1-yl) silane 0.67 mL (3.03 mmol) was added, and stirring was continued for 18 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off, the obtained residue was purified by silica gel column chromatography, and the obtained residue was washed with methanol. The target product represented by the following formula (B-2c) (B-2c). Compound (B-2c) below) was obtained as an isomer mixture of 0.91 g (yield 58%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.41 (2H, s, Ar-H), 7.36 (1H, d, J = 7.5 Hz, Ar-H), 7.23 (1H, d, Ar-H) J = 7.5Hz, Ar-H), 7.13 (1H, t, J = 7.5Hz, Ar-H), 6.77 (1H, s, Ar-CH = C), 3.75 (3H) , S, -ОCH ₃ ), 3.70 (1H, s, CH-Si-CH), 3.26 (1H, s, CH-Si-CH), 2.24 (3H, s, C-CH ₃₎ ), 2.02 (3H, s, C-CH ₃ ), 1.99 (3H, s, C-CH ₃ ), 1.84 (6H, s, C-CH ₃ ), 1.48 (18H, s, -C (CH ₃ ) ₃ ), -0.25 (3H, s, Si-CH ₃ ), -0.28 (3H, s, Si-CH ₃ ) ppm

[Synthesis Example 3-4]
0.26 g (0.50 mmol) of the ligand (B-2c) obtained in [Synthesis Example 3-3], 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon. Stirred. To this solution, 0.65 mL of an n-butyllithium solution (hexane solution, 1.63 M, 1.06 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After the obtained solution was concentrated under reduced pressure, the suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (B-2). 0.17 g (yield 64%) of the yellow powder compound represented by (hereinafter referred to as component (B-2)) was obtained.

_{^{1 H NMR (270MHz, CDCl 3}} ) δ 7.56 (2H, s, Ar-H), 7.54 (1H, d, J = 8.7Hz, Ar-H), 7.29 (1H, dd, J = 7.0and 0.8Hz, Ar-H), 7.04 (1H, dd, J = 8.7and 7.0Hz, Ar-H), 7.01 (1H, s, Ar-H), 3.74 (3H, s, -ОCH ₃ ), 2.29 (3H, s, Ar-CH ₃ ), 2.09 (3H, s, Ar-CH ₃ ), 2.01 (3H, s, Ar-CH ₃₎ ), 1.93 (3H, s, Ar-CH ₃ ), 1.91 (3H, s, Ar-CH ₃ ), 1.48 (18H, s, -C (CH ₃ ) ₃ ), 1.22 (3H, s, Si-CH ₃ ), 1.10 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 686

[Synthesis Example 4-1]
0.53 g (22.0 mmol) of magnesium pieces was charged into a 200 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Euro. J. Org. Chem. 2006, 2727. And 30 mL of tetrahydrofuran diluted solution of 5.69 g (20.0 mmol) of 4-bromo-2,6-di-iso-propyl-N, N-dimethylaniline synthesized by the method described in WO2007 / 034975 was slowly added. The mixture was heated under reflux in an oil bath at 80 ° C. for 1 hour. After cooling the reaction solution to −78 ° C., 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while slowly returning to room temperature. In this reaction solution, Organometallics 2006, 25, 1217. 3.71 g (17.7 mmol) of 7-bromo-2-methylindene synthesized by the method described, 8.42 g (39.7 mmol) of tripotassium phosphate, 0.08 g (0.36 mmol) of palladium acetate, 2-dicyclohexyl 0.22 g (0.53 mmol) of phosphino-2', 6'-dimethoxybiphenyl (S-Phos) and 10 mL of distilled water were charged, and the mixture was heated under reflux in an oil bath for 2 hours. After cooling the reaction solution to room temperature, a 1.0 M aqueous hydrochloric acid solution was added, soluble components were extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, methanol was added to the residue obtained by distilling off the filtrate to prepare a suspension, the insoluble matter was filtered off, and the residue was dried under reduced pressure to obtain the following formula (B). 4.52 g (yield 76%) of the target product (hereinafter referred to as compound (B-3a)) shown in -3a) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.35-7.19 (4H, m, Ar-H), 7.14 (1H, dd, J = 7.4 and 1.3 Hz, Ar-H), 6. 58-6.50 (1H, m, Ar-CH = C), 3.49-3.31 (4H, m, Ar-CH ₂ -Cand-CH (CH ₃ ) ₂ ), 2.89 (6H) , S, -NC (CH ₃ ) ₂ ), 2.15 (3H, s, CH-CH ₃ ), 1.25 (12H, d, J = 6.9Hz, -CH (CH ₃ ) ₂ ) ppm

[Synthesis Example 4-2]
1.01 g (3.02 mmol) of the compound (B-3a) obtained in Synthesis Example 4-1 and 15 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution under ice cooling, 1.85 mL of n-butyllithium solution (hexane solution, 1.63M, 3.02 mmol) was added to this solution, and the mixture was stirred at room temperature for 2 hours. After adding 0.30 mL (3.19 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, the mixture was cooled to −30 ° C. and chlorodimethyl (2,3,4,5-tetra) purchased from Aldrich. Methyl-2,4-cyclopentadiene-1-yl) silane 0.67 mL (3.03 mmol) was added, and stirring was continued for 17 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product (hereinafter referred to as compound (B-3b)) represented by the following formula (B-3b). It was obtained as an isomer mixture of 0.91 g (yield 59%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.43-7.10 (5H, m, Ar-H), 6.78 (1H, s, Ar-CH = C), 3.69 (1H, s, CH-Si-CH), 3.40 (2H, sep, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 3.26 (1H, s, CH-Si-CH), 2.90 (6H) , S, -NC (CH ₃ ) ₂ ), 2.24 (3H, s, C-CH ₃ ), 2.02 (3H, s, C-CH ₃ ), 1.99 (3H, s, C- CH ₃ ), 1.85 (6H, s, C-CH ₃ ), 1.26 (12H, dd, J = 6.9 and 4.2Hz, -CH (CH ₃ ) ₂ ), -0.25 (3H, s, Si-CH ₃ ), -0.28 (3H, s, Si-CH ₃ ) ppm

[Synthesis Example 4-3]
0.26 g (0.50 mmol) of the ligand (B-3b) obtained in Synthesis Example 2b, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 0.65 mL of an n-butyllithium solution (hexane solution, 1.63 M, 1.06 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 15 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (B-3). 0.13 g (yield 38%) of the yellow powder compound represented by (hereinafter referred to as metallocene compound (B-3)) was obtained. _{^{1 H NMR (270MHz, CDCl 3}} ) δ 7.53 (1H, d, J = 8.6Hz, Ar-H), 7.42 (2H, s, Ar-H), 7.32 (1H, d, J = 6.9Hz, Ar-H), 7.04 (2H, m, Ar-H), 3.38 (2H, sep, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 2.89 (6H, s, -NC (CH ₃ ) ₂ ), 2.29 (3H, s, Ar-CH ₃ ), 2.09 (3H, s, Ar-CH ₃ ), 2.02 (3H, s, Ar-CH ₃ ), 1.93 (3H, s, Ar-CH ₃ ), 1.92 (3H, s, Ar-CH ₃ ), 1.32 (6H, d, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 1.22 (6H, d, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 1.21 (3H, s, Si-CH ₃ ), 1.10 (3H, s, Si-CH ₃ ) ppmFD-mass analysis (M ⁺ ): 671

[Synthesis Example 5]
Dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride (hereinafter referred to as component (B-4)) was synthesized by the method described in Japanese Patent No. 3737134 (racemic purity 100%).

[Synthesis Example 6]
Dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -2-methyl-1-indenyl) zirconium dichloride (hereinafter referred to as component (B-5)) is described in JP-A-2004-502690. (Racemic purity 50%).

[Synthesis Example 7-1]
In a 100 mL reactor that was thoroughly dried and substituted with argon, ORGANOMETALLICS 2006, 25, 1217. 4-Bromo-2-methyl-1-indanone 3.60 g (16.0 mmol), 2- (1-cyclohexenyl) -4,4,5,5-tetramethyl-1,3, synthesized by the method described. 2-Dioxaborolane 5.00 g (24.0 mmol), tripotassium phosphate 6.79 g (32.0 mmol), palladium acetate 0.37 g (0.16 mmol), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl 0.13 g (0.32 mmol) of (S-Phos), 30 mL of tetrahydrofuran, and 7.5 mL of distilled water were charged, and the mixture was heated under reflux in an oil bath for 11 hours. After cooling the reaction solution to room temperature, the insoluble components were filtered through Celite and washed thoroughly with dichloromethane. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off and the obtained residue is purified by silica gel column chromatography to obtain the target product (hereinafter referred to as compound (B-6a)) represented by the following formula (B-6a). Obtained quantitatively.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.64 (1 H, dd, J = 7.5 and 1.3 Hz, Ar-H), 7.42 (1 H, dd, J = 7.5 and 1.3 Hz, Ar-H) ), 7.33 (1H, t, J = 7.5Hz, Ar-H), 5.83-5.80 (1H, m, Ar-C = CH), 3.46-3.36 (1H, m, CH-CH ₃ ), 2.75-2.64 (2H, m, Ar-CH _2- C), 2.34-1.58 (8H, m, (CH ₂ ) ₂ ), 1.31 (3H, d, J = 7.3Hz, CH-CH ₃ ) ppm

[Synthesis Example 7-2]
2.27 g (10.0 mmol) of the compound (B-6a) obtained in [Synthesis Example 7-1], 10 mL of tetrahydrofuran, and 5 mL of methanol were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. The solution was cooled to 0 ° C., 0.40 g (11 mmol) of sodium hydroborate was slowly added in small portions, and the mixture was stirred at room temperature for 3 hours. The solution was cooled to 0 ° C., a 1.0 M aqueous hydrochloric acid solution was slowly added, solubles were extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 40 mg (0.20 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling off the filtrate, and the mixture was heated under reflux in an oil bath for 1 hour. .. After cooling the reaction solution to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, soluble components were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product (hereinafter referred to as compound (B-6b)) represented by the following formula (B-6b). 1.40 g (yield 66%) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.21-7.10 (2H, m, Ar-H), 6.98-6.94 (1H, m, Ar-H), 6.48-6. 46 (1H, m, Ar-CH = C), 5.89-5.86 (1H, m, Ar-C = CH), 3.32 (2H, s, Ar-CH _2- C), 2. 37-2.19 (4H, m, CH ₂ -C = C-CH ₂ ), 2.14 (3H, s, CH ₃ ), 1.82-1.65 (4H, m, (CH ₂ ) ₂₎ ) Ppm

[Synthesis Example 7-3]
0.95 g (4.51 mmol) of the compound (B-6b) obtained in [Synthesis Example 7-2] and 10 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. The solution was cooled to −78 ° C., 2.77 mL of n-butyllithium solution (hexane solution, 1.63M, 4.51 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. After adding 0.330 mL (4.51 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, cool to −78 ° C., add 0.272 mL (2.26 mmol) of dichlorodimethylsilane, and slowly bring it to room temperature. Stirring was continued for 20 hours while returning to. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain the target product (hereinafter referred to as compound (B-6c)) represented by the following formula (B-6c). It was obtained as a 0.80 g (74% yield) isomer mixture.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.19-7.39 (2H, m, Ar-H), 6.95-7.09 (4H, m, Ar-H), 6.70-6. 76 (2H, m, Ar-CH = C), 5.82-5.90 (2H, m, Ar-C = CH), 3.71 (2H, s, CH-Si-CH), 1.71 -2.51 (22H, m, C-CH ₃ , CH ₂ ), -0.29 (6H, m, Si-CH ₃ ) ppm

[Synthesis Example 7-4]
0.24 g (0.50 mmol) of the ligand (B-6c) obtained in [Synthesis Example 7-3], 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon. Stirred. To this solution, 0.67 mL of an n-butyllithium solution (hexane solution, 1.63 M, 1.09 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 10 mL of n-hexane and 0.5 mL of diethyl ether were added to the obtained solid. The suspension was cooled to 0 ° C., 0.128 g (0.549 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 15 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After the obtained solution was concentrated under reduced pressure, the suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (B-6). 53 mg (yield 17%) of the yellow powder compound (hereinafter referred to as component (B-6)) shown in (3) was obtained (racemic purity 37%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.50 (4H, d, J = 8.6 Hz, Ar-H), 7.18 (2H, d, J = 6.9 Hz, Ar-H), 6. 71-7.01 (10H, m, Ar-H), 5.98-6.03 (4H, m, Ar-C = CH), 2.18-2.45 (28H, m, C-CH ₃₎ , CH ₂ ), 1.65-1.76 (16H, m, CH ₂ ), 1.41 (3H, s, Si-CH ₃ ) 1.28 (6H, s, Si-CH ₃ ), 1. 22 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 636

[Synthesis Example 8-1]
680 mg (2.54 mmol) of tetrakis (dimethylamino) zirconium and 5 mL of toluene were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. This suspension was cooled to −78 ° C., and 1.06 g (2.50 mmol) of 2,2-bis (7-phenyl-3-indenyl) propane synthesized by the method described in Japanese Patent No. 5710035 was suspended in 10 mL of toluene. After adding the turbid liquid, stirring was continued for 2 hours in an oil bath at 120 ° C. After distilling off the solvent of the reaction solution, hexane was added to the residue to prepare a suspension, and the insoluble material was filtered off with a glass filter. A suspension is prepared by concentrating the obtained solution under reduced pressure, and the obtained solid is filtered off and dried to obtain an orange powdery compound represented by the following formula (B-7a) (hereinafter referred to as a metallocene compound). (B-7a)) was obtained in an amount of 0.80 g (yield 53%, racemic purity 83%).

^{1 1} H NMR (270 MHz, C ₆ D ₆ ) δ 8.25 (meso-, d, J = 8.9 Hz, Ar-H), 7.77-7.65 (6 H, m, Ar-H), 7 .28-7.22 (4H, m, Ar-H), 7.16-6.93 (6H, m, Ar-H), 6.83 (2H, d, J = 3.5Hz, Cp-H) ), 6.63 (meso-, d, J = 3.3Hz, Cp-H), 6.37 (2H, d, J = 3.5Hz, Cp-H), 5.83 (meso-, d, J = 3.4Hz, Cp-H), 2.49 (12H, s, -N (CH ₃ ) ₂ ), 2.08 (6H, s, C-CH ₃ ) ppm

[Synthesis Example 8-2]
0.30 g (0.50 mmol) of the metallocene compound (B-7a) obtained in [Synthesis Example 8-1] and 2.5 mL of toluene were charged into a 30 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. After adding 0.13 mL (1.0 mmol) of chlorotrimethylsilane to this suspension at room temperature, stirring was continued for 3 hours in an oil bath at 70 ° C. After distilling off the solvent of the reaction solution, dichloromethane is added to the obtained solid to prepare a suspension, the insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to be represented by the following formula (2). 0.17 g (yield 56%) of the dark pink powdery compound isopropylidenebis (4-phenyl-1-indenyl) dichloromethane dichloride (hereinafter referred to as the component (B-7)) was obtained (100% racemic purity). ..

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.74 (2H, d, J = 8.9 Hz, Ar-H), 7.58 (4H, d, J = 8.9 Hz, Ar-H), 7. 45-7.27 (8H, m, Ar-H), 7.15-7.10 (2H, m, Ar-H), 6.80 (2H, d, J = 3.6Hz, Cp-H) , 6.23 (2H, d, J = 3.6Hz, Cp-H), 2.41 (6H, s, C-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 584

[Synthesis Example 9]
Dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride (hereinafter referred to as component (B-8)) was synthesized by the method described in Japanese Patent Application Laid-Open No. 2001-011089 (racemic purity 100%). ).

[Synthesis Example 10]
Dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride (hereinafter referred to as component (B-9)) was synthesized by the method described in Japanese Patent No. 3919837 (racemic purity 100%).

[Synthesis Example 11]
Dimethylsilylene (tetramethylcyclopentadienyl) (1-indenyl) zirconium dichloride (hereinafter referred to as component (B-10)) is an organometrics.
2003, 22, 2790. It was synthesized by the method described.

[Synthesis Example 12]
As the dimethylsilylene bisindenyl zirconium dichloride (hereinafter referred to as component (B-11)), a commercially available product from Wako Pure Chemical Industries, Ltd. was purchased and used as it was.

[Synthesis Example 13]
Isopropyridene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (hereinafter referred to as component (B-12)) is based on the method described in JP-A-4-69394. Was synthesized.

<(3) Preparation of solid catalyst component (X)>
[Preparation Example 1]
Using a reactor with an internal volume of 270 L, silica gel (manufactured by Fuji Silysia Chemical Ltd .: cumulative 50% particle size 70 μm, specific surface area 340 m ² / g, pore volume) (1.3 cm ³ / g, dried at 250 ° C. for 10 hours) 10 kg was suspended in 77 L of toluene and then cooled to 0-5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) as a component (C) was added dropwise over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C.

Then, after contacting at 0 to 5 ° C. for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, followed by contact at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the residue was washed twice with toluene to prepare a total amount of 115 liters of toluene slurry. When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 122.6 g / L.

Toluene 30 mL and the slurry 8.2 mL (solid content weight 1.0 g) were charged into a reactor with a stirrer having an internal volume of 200 mL sufficiently nitrogen-substituted. Next, 5 mL of a 2 mmol / L toluene solution of the component (A-1) as the component (A) and 7.5 mL of the 2 mmol / L toluene solution of the component (B-1) as the component (B) were added, and the system temperature was 20 to 25. After contacting at ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was washed twice with hexane to prepare a solid catalyst component (X-1) slurry having a total volume of 50 mL.

[Preparation Examples 2 to 11]
Solid catalyst component (X-2) to (X-11) slurries were prepared in the same manner as in Preparation Example 1 except that component (A) and component (B) were changed to the components shown in Table 8.

<(4) Preparation of prepolymerization catalyst component (XP)>
[Preparation Example 12]
Same as Preparation Example 1 except that 5 mL of a 2 mmol / L toluene solution of the component (A-1) was added as the component (A) and 7.5 mL of the 2 mmol / L toluene solution of the component (B-2) was added as the component (B). A solid catalyst component slurry was prepared by the method of. After cooling the obtained solid catalyst component slurry to 10 ° C., 2.5 mmol of diisobutylaluminum hydride (DiBAl-H) was added. Further, ethylene was continuously supplied into the system for several minutes under normal pressure. During this period, the temperature in the system was maintained at 10 to 15 ° C., and then 0.36 mL of 1-hexene was added. After the addition of 1-hexene, the temperature inside the system was raised to 35 ° C., and 3 equal amounts of ethylene were polymerized with respect to the solid catalyst component in terms of weight. Then, the supernatant was removed by decantation, washed 4 times with hexane, and then hexane was added to make the total volume 50 mL. Next, after raising the temperature in the system to 35 ° C., 40 mg of a hexane solution of Chemistat 2500 (manufactured by Sanyo Chemical Industries, Ltd.) was added as a component (G), and the mixture was contacted for 2 hours. Then, the supernatant was removed by decantation and washed 4 times with hexane. Next, the hexane slurry obtained above was transferred to a glass filter, and hexane was distilled off by filtration and drying under reduced pressure to obtain 4.0 g of a prepolymerization catalyst component (XP-12).

[Preparation Example 13]
Same as Preparation Example 12 except that 5 mL of a 2 mmol / L toluene solution of the component (A-1) was added as the component (A) and 7.5 mL of the 2 mmol / L toluene solution of the component (B-4) was added as the component (B). In the above method, 4.0 g of the prepolymerization catalyst component (XP-13) was obtained.

[Preparation Example 14]
Preparation Example 12 except that 6.3 mL of a 2 mmol / L toluene solution of the component (A-1) was added as the component (A) and 6.3 mL of the 2 mmol / L toluene solution of the component (B-11) was added as the component (B). In the same manner as above, 4.0 g of the prepolymerization catalyst component (XP-14) was obtained.

<(5) Production of ethylene polymer>
The method for measuring the physical characteristics of the ethylene polymer is shown below.
(1) Melt flow rate (MFR, g / 10 minutes)
Melt flow rate (MFR) was measured according to ASTM D1238-89 under the conditions of 190 ° C. and 2.16 kg load (kgf).

(2) Density (D, kg / m ³ )
The density was measured by the density gradient tube method after heat-treating the strand obtained at the time of MFR measurement at 100 ° C. for 1 hour and further leaving it at room temperature for 1 hour in accordance with JIS K7112.

(3) Extreme viscosity (η, dL / g)
For the ultimate viscosity, about 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity ηsp was measured in the same manner. This dilution operation is repeated twice more, and the value of ηsp / C when the concentration (C) is extrapolated to 0 as shown in the following formula (Eq-2) is the limit viscosity [η] (unit: dl / g). Asked as.
[Η] = lim (ηsp / C) (C → 0) -------- (Eq-2)

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

(5) Shear viscosity (η *, P) at 200 ° C. and an angular velocity of 1.0 rad / sec.
For the shear viscosity (η *), the angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η *) at a measurement temperature of 200 ° C. was measured in the range of 0.01 ≦ ω ≦ 100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Pearl Co., Ltd. was used, a parallel plate of 25 mmφ was used as a sample holder, and the sample thickness was about 2.0 mm. The measurement points were 5 points per ω digit. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and the torque was not exceeded. The sample used for 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 / cm2, and a cooling temperature of 20 ° C. The measurement sample was press-molded to a thickness of 2 mm under the conditions of a cooling time of 5 minutes and a cooling pressure of 100 kgf / cm2.

(6) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), the number average molecular weight (Mn), and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) by the GPC-VISCO method were determined by using GPC / V2000 manufactured by Waters Co., Ltd. as follows. It was measured. The guard column uses Shodex AT-G, the analysis column uses two AT-806, the column temperature is 145 ° C, o-dichlorobenzene is used as the mobile phase, and BHT 0.3% by weight is used as the antioxidant, 1.0 ml. The sample concentration was 0.1% by weight, and a differential refractometer and a 3-capillary viscometer were used as detectors. The standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, the measured viscosity was calculated from the viscometer and the refractometer, and the weight average molecular weight (Mw), the number average molecular weight (Mn), and the ratio (Mw / Mn) were calculated from the measured universal calibration.

[Example 1]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L sufficiently nitrogen-substituted, ethylene was substituted in the system, and then 0.375 mmol of triisobutylaluminum, 10 mL of 1-hexene and the solid catalyst obtained in Preparation Example 1 were obtained. 20 mg of the component (X-1) was added as a solid content, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out under the conditions of a total pressure of 0.8 MPaG and 80 ° C. for 90 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 111.2 g of an ethylene polymer.

To the obtained ethylene polymer, 0.1% by weight of Irganox 1076 (manufactured by Chivas Specialty Chemicals Co., Ltd.) and 0.1% by weight of Irgafos168 (manufactured by Chivas Specialty Chemicals Co., Ltd.) were added as heat-resistant stabilizers, and Labplast Mill (manufactured by Chivas Specialty Chemicals Co., Ltd.) was added. Using Toyo Seiki Seisakusho), resin temperature 180 ° C., rotation speed 50 rpm. Was melt-kneaded 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 sample as a measurement sample. The results are shown in Table 9.

[Examples 2 to 9]
The polymerization reaction was carried out in the same manner as in Example 1 except that the solid catalyst component (X) was changed to the solid catalyst components (X-2) to (X-9) obtained in Preparation Examples 2 to 8, and ethylene was subjected to ethylene. A system polymer was obtained. Using the obtained ethylene-based polymer, a sample for measurement was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 9.

[Comparative Examples 1 and 2]
The polymerization reaction was carried out in the same manner as in Example 1 except that the solid catalyst component (X) was changed to the solid catalyst components (X-10) and (X-11) obtained in Preparation Examples 10 and 11, and ethylene was subjected to ethylene. A system polymer was obtained. Using the obtained ethylene-based polymer, a sample for measurement was prepared in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 9.

In Examples 1 to 9 using the components (B-1) to (B-9), [MT / η * was compared with Comparative Examples 1 and 2 using the components (B-10) and (B-11). ] Is large, it can be seen that the amount of long-chain branch introduced and the high molecular weight component are large, and the melting characteristics are excellent.

[Example 10]
In a fluidized bed type gas phase polymerization reactor having an internal volume of 1.7 m ³ , an ethylene / 1-hexene copolymer was produced using a prepolymerization catalyst component (XP-12).
According to the conditions shown in Table 10, the prepolymerization catalyst component, ethylene, nitrogen, 1-hexene and the like were continuously supplied into the reactor. The polymerization reaction product was continuously withdrawn from the reactor and dried in a drying apparatus to obtain an ethylene polymer powder.

To the obtained ethylene polymer, 850 ppm of Sumilyzer GP (manufactured by Sumitomo Chemical Co., Ltd.) and 210 ppm of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) were added as heat-resistant stabilizers, and a biaxially different direction 20 mmφ extruder (manufactured by Toyo Seiki Co., Ltd.) After melt-kneading under the conditions of a set temperature of 200 ° C. and a screw rotation speed of 100 rpm, the mixture was extruded into a strand shape and cut to obtain pellets of an ethylene polymer. Physical properties were measured using the obtained pellets as a measurement sample. The results are shown in Table 10.

<(6) Change in polymerization activity due to difference in polymerization temperature>
[Example 11-1]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L sufficiently nitrogen-substituted, and after ethylene substitution in the system, 0.375 mmol of triisobutylaluminum, 3 mL of 1-hexene and the prepolymerization obtained in Preparation Example 12 were carried out. 84 mg of the catalyst component (XP-12) was added as a solid content, and the temperature in the system was raised to 70 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out under the conditions of a total pressure of 0.8 MPaG and 70 ° C. for 90 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 31.6 g of an ethylene polymer.

[Examples 11-2 and 11-3]
The polymerization reaction was carried out in the same manner as in Example 11-1 except that the amount of the prepolymerization catalyst component (XP-12) added and the polymerization reaction temperature were changed as shown in Table 11, to obtain an ethylene polymer. .. The catalytic activity ratios of 70 ° C. and 90 ° C. with respect to the polymerization reaction temperature of 80 ° C. are shown in FIG.

[Examples 12-1, 12-2, 12-3]
The prepolymerization catalyst component (XP) was changed to the prepolymerization catalyst component (XP-13) obtained in Preparation Example 13, and the amount of the prepolymerization catalyst component (XP-13) added and the polymerization reaction temperature are shown in Table 11. The polymerization reaction was carried out in the same manner as in Example 11-1 except that the results were as follows, to obtain an ethylene-based polymer. The catalytic activity ratios of 70 ° C. and 90 ° C. with respect to the polymerization reaction temperature of 80 ° C. are shown in FIG.

[Comparative Examples 3-1, 3-2, 3-3]
The prepolymerization catalyst component (XP) was changed to the prepolymerization catalyst component (XP-14) obtained in Preparation Example 14, and the amount of the prepolymerization catalyst component (XP-14) added and the polymerization reaction temperature are shown in Table 11. The polymerization reaction was carried out in the same manner as in Example 11-1 except that the results were as follows, to obtain an ethylene-based polymer. The catalytic activity ratios of 70 ° C. and 90 ° C. with respect to the polymerization reaction temperature of 80 ° C. are shown in FIG.

In Examples 11 and 12 using the components (B-2) and (B-4), the variation in catalytic activity due to the difference in the polymerization reaction temperature is smaller than that in Comparative Example 3 using the component (B-11). I understand. From this, if the catalyst of the present invention is used, even if the polymerization temperature fluctuates temporarily, the fluctuation of the polymerization activity is small, the melt aggregation of the polymer particles and the adhesion to the wall surface of the polymer are unlikely to occur, and the long-term stable operation is performed. It is expected to be an advantageous catalyst.

Claims (8)

A catalyst for olefin polymerization containing the following components (A), component (B) and component (C).
Component (A); A crosslinked metallocene compound represented by the following general formula (I).

[In general formula (I),
R ¹ , R ² , R ³ and R ⁴ contain hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group and germanium. It may be selected from a group and a tin-containing group and may be the same or different from each other, but not all of them may be hydrogen atoms at the same time, and adjacent groups may be bonded to each other to form an aliphatic ring.
Q ¹ is an alkylene group that is methylene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene. , Methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, and substituted alkylene groups selected from dinaphthylmethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptilidene, bicyclo [ 33.1] Cycloalkylene group selected from nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, and dihydroindanilidene, alkylidene group selected from ethylidene, propylidene and butylidene, silylene, methylsilylene, dimethylsilylene, diisopropyl Sirylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylcilylene, diphenylcilylene, ditrilcilylene, methylnaphthylcilylene, dinaphthylcilylene, cyclodimethylenesilylene, cyclotrimethylene. A silicon-containing group selected from silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene and cycloheptamethylene silylene, a group obtained by converting silicon into germanium or tin in the silicon-containing group, or the alkylene group, said. A substituted alkylene group, the cycloalkylene group, the alkylidene group, or a group in which one or more hydrogen atoms in the silicon-containing group are substituted with halogen atoms.
X is a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group, and M is a group. , Titanium atom, zirconium atom or hafnium atom. ]
Component (B); At least one crosslinked metallocene compound selected from the group represented by the following general formulas (II-α), (II-β) and (II-γ).

[In the general formulas (II-α), (II-β) and (II-γ),
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups and boron-containing groups. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group, which may be the same or different from each other, and adjacent groups are bonded to each other to form an aliphatic ring. You may be. However, in the general formulas (II-α), (II-β) and (II-γ), at least one group among ^{R 17} , R ¹⁸ , R ¹⁹ and R ^{20 is a hydrocarbon group.}
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are hydrogen atoms, hydrocarbon groups, A group selected from a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, which may be the same or different from each other. Also, a plurality of substituents adjacent to each other or in the vicinity may be bonded to each other to form a ring. Here, the term "neighborhood" means a distance at which a 5- to 7-membered ring can be formed when a plurality of groups are bonded to each other.
Q ² is methylene alkylene group, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene. , Methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, and substituted alkylene groups selected from dinaphthylmethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptilidene, bicyclo [ 33.1] Cycloalkylene group selected from nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, and dihydroindanilidene, alkylidene group selected from ethylidene, propylidene and butylidene, silylene, methylsilylene, dimethylsilylene, diisopropyl Sirylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylcilylene, diphenylcilylene, ditrilcilylene, methylnaphthylcilylene, dinaphthylcilylene, cyclodimethylenesilylene, cyclotrimethylene. A silicon-containing group selected from silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene and cycloheptamethylene silylene, a group obtained by converting silicon into germanium or tin in the silicon-containing group, or the alkylene group, said. A substituted alkylene group, the cycloalkylene group, the alkylidene group, or a group in which one or more hydrogen atoms in the silicon-containing group are substituted with halogen atoms.
M is selected from titanium atom, zirconium atom and hafnium atom, and X is independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group and nitrogen-containing group. A group selected from a group and a phosphorus-containing group. ]
Component (C); At least one component selected from the group consisting of the following (c-1), (c-2) and (c-3).
(C-1) Organometallic compound represented by the following formula (III), (IV) or (V) (c-2) Organoaluminium oxy compound (c-3) Reaction with component (A) and component (B) and compound to form an ion pair _{^{R a m Al (ОR b)}} n H p X q ··· (III)
[In formula (III), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦. 3, n is the number of 0 ≦ n <3, p is the number of 0 ≦ p <3, q is the number of 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ··· (IV}} )
Wherein (IV), M ^a represents a Li, Na or K, R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t・ ・ ・ (V)
[In formula (V), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b represents Mg, Zn or Cd, and X represents Mg, Zn or Cd. , R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ] The catalyst for olefin polymerization according to claim 1, wherein at least one of ^{R 1} , R ² , R ³ and R ⁴ is a hydrocarbon group in the general formula (I). ^{Q 1} in the general formula (I) is the alkylene group, the substituted alkylene group, the cycloalkylene group, the alkylidene group, the silicon-containing group, or one or more hydrogen atoms in these groups are halogen atoms. Substituted group,
^{1 or claim 1, wherein Q 2} in the general formulas (II-α), (II-β) and (II-γ) is the alkylene group, the substituted alkylene group, the alkylidene group, or the silicon-containing group. 2. The catalyst for olefin polymerization according to 2. Q ¹ in the general formula (I) is a dimethylsilylene, Jibuchirushiriren, diphenyl silylene or a group in which one or more are substituted with halogen atoms of the hydrogen atoms in these groups,
^{Q 2} in the general formulas (II-α), (II-β) and (II-γ) is methylene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene. , Methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, dimethylsilylene, dibutylsilylene, or diphenylcilylene, claim Item 2. The catalyst for olefin polymerization according to Item 1 or 2. The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein the component (C) contains at least the above (c-2). The catalyst for olefin polymerization according to any one of claims 1 to 5, which comprises a solid carrier (S). The catalyst for olefin polymerization according to claim 6, wherein the solid support (S) is a porous oxide. A method for producing an ethylene-based polymer, which polymerizes ethylene or ethylene with an olefin having 3 or more and 20 or less carbon atoms in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 7.

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