JP6571965B2 - Olefin polymerization catalyst and process for producing olefin polymer using the same - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, the present invention relates to an olefin polymerization catalyst which can produce an olefin polymer excellent in molding processability and mechanical strength and excellent in particle properties, preferably an ethylene copolymer with high polymerization activity.

Olefin polymers are molded by various molding methods and used for various purposes.
For example, as a film or sheet used for packaging foodstuffs, liquids, daily commodities, etc., an extruded product of an ethylene polymer is used.

  Depending on the molding method and application, the properties required for the olefin polymer differ, but for example, when performing T-die molding, stable molding is possible even at high speed (having high-speed film forming processability). That is, it is required to have processing performance such as a small neck-in. In addition, when performing inflation molding, it is required to have processing performance such as excellent bubble stability.

  Ethylene polymers obtained with Ziegler catalysts and metallocene catalysts have a linear molecular structure and excellent mechanical strength, but have a low melt tension, compared to low-density polyethylene (LDPE) produced by high-pressure radical polymerization. However, there is a problem that molding processability is inferior.

In order to solve these problems, [1] a method of blending LDPE with an ethylene polymer obtained using a Ziegler catalyst or a metallocene catalyst (Patent Document 1), [2] a method of widening the molecular weight distribution by multistage polymerization ( Patent Document 2), [3] Method for producing long-chain branched ethylene polymer using chromium catalyst, [4] Method for producing long-chain branched ethylene polymer using specific metallocene catalyst (Patent Document 3), [5] A method of producing a long-chain branched ethylene polymer by copolymerizing a macromonomer using a specific metallocene catalyst (Patent Document 4), [6] Using a specific metallocene catalyst A method of producing a long-chain branched ethylene polymer by copolymerizing ethylene and diene (Patent Documents 5 and 6) has been proposed. However, it can be said that these methods still have problems in industrial implementation, such as significant cost increase, inadequate molding processability, and generation of gel during molding.
In recent years, methods for broadening the molecular weight distribution using two or more kinds of metallocene compounds have been reported (Patent Documents 7 and 8), but it is still difficult to say that the melt tension is sufficient.

WO99 / 046325 pamphlet JP-A-2-53811 JP-A-4-213306 JP-A-8-502303 JP-T-1-501633 JP-T-4-506372 Special Table 2002-515521 WO2006 / 045761 pamphlet

  The present invention has been made in view of the prior art as described above, and is a highly polymerized olefin polymer, preferably an ethylene copolymer, which is excellent in molding processability and mechanical strength and excellent in particle properties. Of an olefin polymerization catalyst capable of being produced in an active manner, a method of polymerizing an olefin in the presence of the catalyst, and a method of producing an olefin polymer, preferably an ethylene copolymer in the presence of the catalyst. The purpose is to provide.

  As a result of diligent research in view of the above circumstances, the present inventors have many long-chain branches by allowing two types of bridged metallocene compounds having a specific structure to coexist in the same polymerization system together with a specific promoter. To find an olefin polymerization catalyst capable of efficiently producing an olefin polymer, a method for polymerizing an olefin in the presence of the catalyst, and a method for producing an olefin polymer in the presence of the catalyst, and to complete the present invention. It came.

That is, the catalyst for olefin polymerization of the present invention is characterized by comprising the following component (A), component (B) and component (C).
Component (A) includes at least one bridged metallocene compound represented by the following general formula (I).

〔一般式（Ｉ）中、Ｒ¹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またはスズ含有基であり、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、二価の基であり、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またはスズ含有基である。Ｘは、一価の基であり、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、窒素含有基またはリン含有基であり、互いに同一でも異なっていてもよい。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）は、下記一般式（II）、（III）および（IV）から選ばれる少なくとも１種の架橋型メタロセン化合物を含む。

[In General Formula (I), R ¹ is a monovalent group, each independently 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, Phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, which may be the same or different from each other, but all are not hydrogen atoms at the same time and adjacent groups are bonded to each other to form an aliphatic ring. It may be. Q ¹ is a divalent group 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. X is a monovalent group, each independently a hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group; They may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom. ]
Component (B) contains at least one bridged metallocene compound selected from the following general formulas (II), (III) and (IV).

〔一般式（II）、（III）および（IV）中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷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またはスズ含有基であり、互いに同一でも異なっていてもよく、また、隣接した置換基は互いに結合して環を形成してもよい。Ｑ²は、二価の基であり、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またはスズ含有基であり、Ｒ³およびＱ²は、互いに結合して環を形成してもよい。Ｑ³は、二価の基であり、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またはスズ含有基であり、Ｒ³およびＱ³は、互いに結合して環を形成してもよい。Ｑ⁴は、炭素原子、ケイ素原子、ゲルマニウム原子またはスズ原子であり、Ｒ³およびＲ⁷は、互いに結合して環を形成してもよい。Ｘは、一価の基であり、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、リン含有基、ホウ素含有基またはアルミニウム含有基あり、互いに同一でも異なっていてもよい。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。Ｌは、炭素数１以上１０以下の直鎖の炭素鎖を有する炭化水素基である。Ｄ¹は、下記一般式（Ｄ-ａ）、（Ｄ-ｂ）、（Ｄ-ｃ）、（Ｄ-ｄ）、（Ｄ-ｅ）、（Ｄ-ｇ）、（Ｄ-ｈ）または（Ｄ-ｉ）である。Ｄ²は、下記一般式（Ｄ-ａ）、（Ｄ-ｂ）、（Ｄ-ｃ）、（Ｄ-ｄ）、（Ｄ-ｅ）、（Ｄ-ｇ）、（Ｄ-ｈ）または（Ｄ-ｉ）である。Ｄ³は、下記一般式（Ｄ-ｂ）、（Ｄ-ｃ）、（Ｄ-ｄ）、（Ｄ-ｆ）、（Ｄ-ｇ）、（Ｄ-ｈ）または（Ｄ-ｉ）である。

[In the general formulas (II), (III) and (IV), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are monovalent groups, each independently representing a hydrogen atom, A hydrogen 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 or a tin-containing group, which may be the same or different from each other, Adjacent substituents may be bonded to each other to form a ring. Q ² is a divalent group 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, and R ³ and Q ² are bonded to each other. To form a ring. Q ³ is a divalent group, 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, and R ³ and Q ³ are bonded to each other. To form a ring. Q ⁴ is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ³ and R ⁷ may be bonded to each other to form a ring. X is a monovalent group, and each independently represents 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, a phosphorus-containing group, or a boron-containing group. Groups or aluminum-containing groups, which may be the same or different. M is a titanium atom, a zirconium atom or a hafnium atom. L is a hydrocarbon group having a straight carbon chain having 1 to 10 carbon atoms. D ¹ is the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di). D ² represents the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di). D ³ is the following general formula (Db), (Dc), (Dd), (Df), (Dg), (Dh) or (Di). .

一般式（Ｄ-ａ）、（Ｄ-ｂ）、（Ｄ-ｃ）、（Ｄ-ｄ）、（Ｄ-ｅ）、（Ｄ-ｆ）、（Ｄ-ｇ）、（Ｄ-ｈ）および（Ｄ-ｉ）中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹³は、一価の基であり、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、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り、互いに同一でも異なっていてもよく、また、隣接した置換基は互いに結合して環を形成してもよい。Ｒ¹²は、一価の基であり、酸素含有基、窒素含有基、イオウ含有基またはリン含有基であり、Ｒ¹¹およびＲ¹²が、互いに結合して環を形成してもよく、好ましくは、Ｒ¹²は、隣接するＲ¹¹と互いに結合して環を形成してもよい。Ｃｈは酸素原子あるいは硫黄原子である。Ｐｎは窒素原子あるいはリン原子である。〕

General formulas (Da), (Db), (Dc), (Dd), (De), (Df), (Dg), (Dh) and In (Di), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹³ are monovalent groups, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, or a silicon-containing group. Group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, which may be the same or different from each other, and adjacent substitutions The groups may be bonded to each other to form a ring. R ¹² is a monovalent group and is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group or a phosphorus-containing group, and R ¹¹ and R ¹² may be bonded to each other to form a ring, preferably , R ¹² may combine with adjacent R ¹¹ to form a ring. Ch is an oxygen atom or a sulfur atom. Pn is a nitrogen atom or a phosphorus atom. ]

Component (C) is
(C-1) an organometallic compound represented by the following general formula (V), (VI) or (VII),
(C-2) an organoaluminum oxy compound, and (c-3) at least one compound selected from the group consisting of compounds that react with component (A) and component (B) to form ion pairs.
R ^a _m Al (OR ^b ) _n H _p X _q (V)
[In General 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. X represents a halogen atom. m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (VI)
In [Formula (VI), M ^a is lithium atom, sodium atom or a potassium atom. 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 (VII)
[In General Formula (VII), 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. M ^b is a magnesium atom, a zinc atom or a cadmium atom. X represents a halogen atom. r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

  In the olefin polymerization catalyst of the present invention, in the general formula (II), L is preferably a hydrocarbon group having a straight carbon chain having 1 to 3 carbon atoms. In the general formula (III), L is preferably a hydrocarbon group having a straight carbon chain having 1 to 3 carbon atoms. In the general formula (IV), L is preferably a hydrocarbon group having a straight carbon chain having 1 to 3 carbon atoms.

In the olefin polymerization catalyst of the present invention, in the general formula (II), R ⁵ is a monovalent group, and includes a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. It is preferably a group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. In the general formula (III), R ⁵ is a monovalent group and is 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, or a silicon-containing group. A germanium-containing group or a tin-containing group is preferable. In the general formula (IV), R ⁵ is a monovalent group, and is 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, or a silicon-containing group. A germanium-containing group or a tin-containing group is preferable.

In the olefin polymerization catalyst of the present invention, in the general formula (II), D ¹ is preferably the general formula (Da), (Db) or (Dc). In the general formula (III), D ² is preferably the general formula (Da), (Db) or (Dc). In the olefin polymerization catalyst of the present invention, in the general formula (IV), D ³ is preferably the general formula (Db), (Dc) or (Dd).

The olefin polymerization catalyst according to the present invention may further contain a solid support (S). As such a catalyst,
(I) Solid support (S), solid catalyst component (X-A) formed from component (C) and component (A), solid support (S), component (C) and component An olefin polymerization catalyst comprising a solid catalyst component (X-B) formed from (B);
(Ii) There is an olefin polymerization catalyst comprising a solid catalyst component (X-C) formed from the solid carrier (S), the component (A), the component (B) and the component (C).

In the olefin polymerization catalyst of the present invention, the component (C) preferably contains at least an organoaluminum oxy compound (c-2).
The method for producing an ethylene copolymer of the present invention includes a step of copolymerizing ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst. density equal to or less than 875kg / m ³ or more 945 kg / m ^3.

According to the present invention, an olefin polymer having excellent moldability and mechanical strength and excellent particle properties can be produced with high polymerization activity.
Furthermore, according to the present invention, there is provided an efficient method for producing an ethylene-based polymer having excellent processability and mechanical strength and having many long-chain branches.

  Hereinafter, the olefin polymerization catalyst according to the present invention and the polymerization method using the catalyst will be specifically described. In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. In some cases.

First, each component used in the olefin polymerization catalyst of the present invention will be described.
[Olefin polymerization catalyst]
(Ingredient (A))
Component (A) includes a bridged metallocene compound represented by the following general formula (I ′).

好ましくは、下記一般式（Ｉ）で表される架橋型メタロセン化合物を少なくとも１種含むことである。

Preferably, at least one bridged metallocene compound represented by the following general formula (I) is included.

本発明において、成分（Ａ）として、一般式（Ｉ）および（Ｉ’）で表される架橋型メタロセン化合物を複数種用いてもよい。

In the present invention, as the component (A), a plurality of bridged metallocene compounds represented by the general formulas (I) and (I ′) may be used.

In the general formulas (I) and (I ′), R ¹ is a monovalent group and is 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R ^{1 s} are independent and may be the same or different from each other, but all of R ¹ may not be simultaneously hydrogen atoms, and adjacent groups may be bonded to each other to form an aliphatic ring.

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

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

Examples of monovalent oxygen-containing groups include methoxy and ethoxy groups.
Examples of the monovalent sulfur-containing group include thiol and sulfonic acid groups.
Examples of the monovalent nitrogen-containing group include a dimethylamino group.
Examples of the monovalent phosphorus-containing group include a phenylphosphine group.
Examples of the monovalent boron-containing group include boranediyl, boranetriyl, and diboranyl groups.

  Monovalent silicon-containing groups include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl, dinaphthylsilyl, cyclodimethylene Examples include silyl, cyclotrimethylenesilyl, cyclotetramethylenesilyl, cyclopentamethylenesilyl, cyclohexamethylenesilyl, cycloheptamethylenesilyl group and the like.

Examples of the monovalent germanium-containing group or the monovalent tin-containing group include groups obtained by converting silicon into germanium or tin in the silicon-containing group.
Examples of the case where adjacent groups are bonded to each other to form an aliphatic ring include tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4-trimethyltetrahydroindenyl, 4-phenyltetrahydroindenyl, 4 -Cyclohexyltetrahydroindenyl, 2-methyl-4-phenyltetrahydroindenyl, 2-methyl-4-cyclohexyltetrahydroindenyl and the like.

A preferred group for R ¹ is a group selected from a hydrogen atom, a hydrocarbon group, and a halogen-containing group, more preferably at least one is a hydrocarbon group, and more preferably at least one has 1 to 15 carbon atoms. The following hydrocarbon groups, the remainder being a hydrocarbon group or a hydrogen atom, more preferably at least one being a hydrocarbon group having 3 to 8 carbon atoms, and the remainder being a hydrocarbon group or a hydrogen atom . The most preferable group for R ¹ has a hydrocarbon group having 3 to 8 carbon atoms at the 3-position of the cyclopentadienyl group, and the remainder is a hydrocarbon group or a hydrogen atom. 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, an alkylidene group, a halogen-containing group, A silicon-containing group, a germanium-containing group or a tin-containing group.

  Specific examples of the divalent alkylene group having 1 to 20 carbon atoms, substituted alkylene group, cycloalkylene group and alkylidene group include alkylene groups such as methylene, ethylene, propylene and butylene, isopropylidene, dimethylmethylene, diethylmethylene, Dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, Substituted alkylene groups such as dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, cyclopropylidene, Cycloalkylene groups such as clobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, ethylidene, propylidene, butylidene And alkylidene groups.

  Divalent silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolyl. Examples include silylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene group, preferably dimethylsilylene, Dibutylsilylene and diphenylsilylene.

Examples of the divalent germanium-containing group or tin-containing group include groups obtained by converting silicon into germanium or tin in the silicon-containing group.
Examples of the divalent halogen-containing group include groups in which one or more hydrogen atoms in the alkylene group, substituted alkylene group, cycloalkylene group, alkylidene group or silicon-containing group are substituted with an appropriate halogen atom, Examples thereof include bis (trifluoromethyl) methylene, 4,4,4-trifluorobutylmethylmethylene, bis (trifluoromethyl) silylene, 4,4,4-trifluorobutylmethylsilylene group and the like.

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

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

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. 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 exemplified as R ¹ above. The same thing as what was done is mentioned.
M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

  The bridged metallocene compounds represented by the general formulas (I) and (I ′) and the method for producing the same are not particularly limited as long as the effects of the present invention are exhibited. Specific examples thereof include, for example, JP-A-2006-233208. And those exemplified in JP 2009-143901 A, JP 2009-144148 A, and the like.

  In the present invention, the compounds represented by the general formulas (I) and (I ′) may be used alone, or two or more metallocene compounds having different chemical structures may be used among these compounds. Further, optical isomers having the same chemical structure may be used alone, or optical isomer mixtures having the same chemical structure (for example, meso isomer mixture or racemic mixture) may be used.

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

  The cross-linked metallocene compound represented by the general formula (I) has a high catalytic activity compared to the cross-linked metallocene compound represented by the general formula (I ′) with a low molecular weight and a large number of terminal vinyl groups. It is more preferable in the production of a polymer having a long chain branch.

(Ingredient (B))
Component (B) contains at least one bridged metallocene compound selected from the following general formulas (II), (III) and (IV).

一般式（II）、（III）および（IV）中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷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またはスズ含有基であり、互いに同一でも異なっていてもよく、また、隣接した置換基は互いに結合して環を形成してもよい。なお、本明細書において、『互いに同一でも異なってもよい』とは、メタロセン化合物中において同じ番号で記載されている置換基同士が、同一でも異なってもよく、さらに、異なるメタロセン化合物同士においても、同じ番号の置換基同士が、同一でも異なってもよいことを意味する。

In the general formulas (II), (III) and (IV), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are monovalent groups, each independently a 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 or tin-containing group, which may be the same or different from each other, The adjacent substituents may be bonded to each other to form a ring. In the present specification, “may be the same as or different from each other” means that the substituents described with the same number in the metallocene compound may be the same or different, and also in different metallocene compounds. This means that the substituents having the same number may be the same or different.

Examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, and n-undecanyl. , N-dodecanyl, n-eicosanyl, isopropyl, s-butyl, t-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, t-pentyl, thiamil, pentan-3-yl, 2-methyl Pentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl, 3-methylpentan-2-yl, 4-methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, texyl, 3-methylpentan-3-yl, 3,3-dimethylbut-2-yl, hexane-3- 2-methylpentan-3-yl, heptane-4-yl, 2,4-dimethylpentan-3-yl, 3-ethylpentane-3-yl, 4,4-dimethylpentyl, 4-methylheptane-4 A straight chain having 1 to 20 carbon atoms, such as -yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, 2,3,4-trimethylpentan-3-yl; A branched alkyl group;
Vinyl, allyl, propenyl, isopropenyl, allenyl, but-3-en-1-yl, crotyl, but-3-en-2-yl, methallyl, erythrenyl, penta-4-en-1-yl, penta-3 -En-1-yl, penta-2-en-1-yl, isopentenyl, 2-methylbut-3-en-1-yl, penta-4-en-2-yl, prenyl, 2-methyl-buta 2-en-1-yl, penta-3-en-2-yl, 2-methyl-but-3-en-2-yl, penta-1-en-3-yl, penta-2,4-diene- 1-yl, penta-1,3-dien-1-yl, penta-1,4-dien-3-yl, isoprenyl, penta-2,4-dien-2-yl, hexa-5-ene-1- Yl, hexa-4-en-1-yl, hexa-3-e -1-yl, hexa-2-en-1-yl, 4-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 2-methyl-penta-4 -En-1-yl, hexa-5-en-2-yl, 4-methyl-pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 2,3-dimethyl -But-2-en-1-yl, 2-methylpent-4-en-2-yl, 3-ethylpent-1-en-3-yl, hexa-3,5-dien-1-yl, hexa-2 , 4-Dien-1-yl, 4-methylpenta-1,3-dien-1-yl, 2,3-dimethyl-buta-1,3-dien-1-yl, hexa-1,3,5-triene -1-yl, 2- (cyclopentadienyl) propan-2-yl, 2- (cyclopentadienyl) Linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 20 carbon atoms such as ethyl;
Ethynyl, prop-2-yn-1-yl, propargyl, but-1-in-1-yl, but-2-in-1-yl, but-3-in-1-yl, penta-1-in- 1-yl, penta-2-in-1-yl, penta-3-in-1-yl, penta-4-in-1-yl, 3-methyl-but-1-in-1-yl, penta- 3-in-2-yl, 2-methyl-but-3-in-1-yl, penta-4-in-2-yl, hexa-1-in-1-yl, 3,3-dimethyl-buta 1-in-1-yl, 2-methyl-pent-3-in-2-yl, 2,2-dimethyl-but-3-in-1-yl, hexa-4-in-1-yl, hexa- A linear or branched alkynyl group or unsaturated triple bond having 2 to 20 carbon atoms, such as 5-in-1-yl; Yumoto;
Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t-butylbenzyl, 3,5 -Di-t-butylbenzyl, phenylethyl, benzhydryl, cumyl, 2- (4-methylphenyl) propan-2-yl, 2- (3,5-dimethylphenyl) propan-2-yl, 2- (4- t-butylphenyl) propan-2-yl, 2- (3,5-di-t-butylphenyl) propan-2-yl, 3-phenylpentan-3-yl, 4-phenylhepta-1,6-diene -4-yl, 1,2,3-triphenylpropan-2-yl, 1,1-diphenylethyl, 1,1-diphenylpropyl, 1,1-diphenyl-but-3-e -1-yl, 1,1,2-triphenylethyl, trityl, tri- (4-methylphenyl) methyl, 2-phenylethyl, styryl, 2- (2-methylphenyl) ethyl, 2- (4-methyl) Phenyl) ethyl, 2- (2,4,6-trimethylphenyl) ethyl, 2- (3,5-dimethylphenyl) ethyl, 2- (2,4,6-triisopropylphenyl) ethyl, 2- (4- t-butylphenyl) ethyl, 2- (3,5-di-t-butylphenyl) ethyl, 2-methyl-1-phenylpropan-2-yl, 3-phenylpropyl, 2-cinnamyl, neophyll, 3-methyl -3-phenylbutyl, 2-methyl-4-phenylbutan-2-yl, cyclopentadienyldiphenylmethyl, 2- (1-indenyl) propan-2-yl, (1- N-denyl) diphenylmethyl, 2- (1-indenyl) ethyl, 2- (tetrahydro-1-indacenyl) propan-2-yl, (tetrahydro-1-indacenyl) diphenylmethyl, 2- (tetrahydro-1-indacenyl) ethyl, 2- (1-benzoindenyl) propan-2-yl, (1-benzoindenyl) diphenylmethyl, 2- (1-benzoindenyl) ethyl, 2- (9-fluorenyl) propan-2-yl, ( 7-carbon such as 9-fluorenyl) diphenylmethyl, 2- (9-fluorenyl) ethyl, 2- (1-azurenyl) propan-2-yl, (1-azurenyl) diphenylmethyl, 2- (1-azurenyl) ethyl 20 or less aromatic-containing linear or branched alkyl group and unsaturated double bond-containing group;
Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, dimethylcyclopentadienyl, n-butylcyclopentadienyl, n-butyl-methylcyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentyl, allyl Cyclopentyl, benzylcyclopentyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, methylcyclohexyl, allylcyclohexyl, benzylcyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, methylcycloheptyl, allylcycloheptyl, benzylcycloheptyl, cyclooctyl, cyclooctenyl, Cyclooctadienyl, cyclooctatrienyl, methylcyclooctyl, allylcyclooctyl, Dicyclooctyl, 4-cyclohexyl-t-butyl, norbornyl, norbornenyl, norbornadienyl, 2-methylbicyclo [2.2.1] heptan-2-yl, 7-methylbicyclo [2.2.1] heptane -7-yl, bicyclo [2.2.2] octan-1-yl, bicyclo [2.2.2] octan-2-yl, 1-adamantyl, 2-adamantyl, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl), 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3 5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), 1- (3,5,7-triphenyladamantyl), pentarenyl Indenyl, fluorenyl, indacenyl, tetrahydropyran indanyl cell alkenyl, benzoindenyl, having 3 or more carbon atoms and 20 or less of cyclic saturated and unsaturated hydrocarbon groups such as azulenyl;
Phenyl, tolyl, xylyl, mesityl, cumenyl, duryl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, allylphenyl, (But-3-en-1-yl) phenyl, (but-2-en-1-yl) phenyl, methallylphenyl, prenylphenyl, 4-adamantylphenyl, 3,5-di-adamantylphenyl, naphthyl, biphenyl , T-phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, ferrocenyl and the like aryl groups having 6 to 20 carbon atoms;

  Among the linear or branched alkyl groups having 1 to 20 carbon atoms, preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl. , Isopropyl, s-butyl, t-butyl, isobutyl, isopentyl, neopentyl, t-pentyl, pentan-3-yl, isohexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, texyl, 3-methylpentane 3-yl, heptane-4-yl, 2,4-dimethylpentan-3-yl, 3-ethylpentane-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptane -4-yl and the like, among which methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl are particularly preferable. , Isopropyl, t- butyl.

  Among the above-mentioned linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 20 carbon atoms, vinyl, allyl, but-3-en-1-yl, crotyl, methallyl, penta -4-en-1-yl, prenyl, penta-1,4-dien-3-yl, hexa-5-en-1-yl, 2-methylpent-4-en-2-yl, 2- (cyclopenta Dienyl) propan-2-yl, 2- (cyclopentadienyl) ethyl and the like, among which vinyl, allyl, but-3-en-1-yl, and penta-4-ene-1 are particularly preferable. -Yl, prenyl, hexa-5-en-1-yl.

  Among the straight chain or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 20 carbon atoms, ethynyl, prop-2-yn-1-yl, propargyl, but-2-yne- 1-yl, but-3-yn-1-yl, penta-3-in-1-yl, penta-4-in-1-yl, 3-methyl-but-1-in-1-yl, 3, 3-dimethyl-but-1-in-1-yl, hexa-4-in-1-yl, hexa-5-in-1-yl, and the like, among which prop-2-yne- is particularly preferable. 1-yl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl.

  Among the aromatic-containing linear or branched alkyl group having 7 to 20 carbon atoms and the unsaturated double bond-containing group, benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4, 6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t-butylbenzyl, 3,5-di-t-butylbenzyl, benzhydryl, cumyl, 1,1- Diphenylethyl, trityl, 2-phenylethyl, 2- (4-methylphenyl) ethyl, 2- (2,4,6-trimethylphenyl) ethyl, 2- (3,5-dimethylphenyl) ethyl, 2- (2 , 4,6-triisopropylphenyl) ethyl, 2- (4-t-butylphenyl) ethyl, 2- (3,5-di-t-butylphenyl) ethyl, styryl 2-methyl-1-phenylpropan-2-yl, 3-phenylpropyl, 2-cinnamyl, neophyll, cyclopentadienyldiphenylmethyl, 2- (1-indenyl) propan-2-yl, (1-indenyl) diphenyl Methyl, 2- (1-indenyl) ethyl, 2- (9-fluorenyl) propan-2-yl, (9-fluorenyl) diphenylmethyl, 2- (9-fluorenyl) ethyl and the like are particularly preferable. Benzyl, benzhydryl, cumyl, 1,1-diphenylethyl, trityl, 2-phenylethyl, 3-phenylpropyl, 2-cinnamyl.

  Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 20 carbon atoms, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, methylcyclopentyl, allylcyclopentyl, benzylcyclopentyl, cyclohexyl, cyclohexenyl. , Methylcyclohexyl, allylcyclohexyl, benzylcyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, methylcycloheptyl, allylcycloheptyl, benzylcycloheptyl, cyclooctyl, cyclooctenyl, cyclooctadienyl, 4-cyclohexyl-t-butyl, Norbornyl, 2-methylbicyclo [2.2.1] heptan-2-yl, bicyclo [2.2.2] octan-1-yl, 1-adamanti , 2-adamantyl, pentalenyl, indenyl, fluorenyl and the like, particularly preferably among them, cyclopentyl, cyclopentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, 1-adamantyl.

  Among the aryl groups having 6 to 20 carbon atoms, phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, allylphenyl, prenylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, t-phenyl, binaphthyl, phenanthryl, anthracenyl, ferrocenyl, etc., among which phenyl, Tolyl, xylyl, mesityl, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, allylphenyl, 4-adamantylphenyl , Naphthyl, biphenyl, phena Tolyl, anthracenyl.

  Examples of the monovalent halogen-containing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, fluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, and heptafluoro. Propyl, 3,3,3-trifluoropropyl, nonafluorobutyl, 4,4,4-trifluorobutyl, dodecafluorohexyl, 6,6,6-trifluorohexyl, chlorophenyl, fluorophenyl, difluorophenyl, trifluoro Phenyl, tetrafluorophenyl, pentafluorophenyl, di-t-butyl-fluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethoxyphenyl, bistrifluoromethoxyphenyl, trifluoromethylthio Phenyl, bistrifluoromethylthiophenyl, fluorobiphenyl, difluorobiphenyl, trifluorobiphenyl, tetrafluorobiphenyl, pentafluorobiphenyl, di-t-butyl-fluorobiphenyl, trifluoromethylbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxybiphenyl, bistri Fluoromethoxybiphenyl, trifluoromethyldimethylsilyl, trifluoromethoxy, pentafluoroethoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy, pentafluorophenoxy, di-t-butyl-fluorophenoxy, trifluoromethylphenoxy, bistrifluoromethylphenoxy , Trifluoromethoxyphenoxy, bistrifluoromethoxypheno Si, difluoromethylenedioxyphenyl, trifluoroacetyl, pentafluorobenzoyl, fluorophenyliminomethyl, pentafluorophenyliminomethyl, trifluoromethylphenyliminomethyl, bistrifluoromethylphenyliminomethyl, trifluoromethylthio, trifuryl, nonafryl, triflate , Nonaflate, bistrifurylimide, trifluoromethylfuryl, trifluoromethylbenzofuryl, trifluoromethyldibenzofuryl, trifluoromethylpyrrolyl, pentafluorophenylpyrrolyl, fluoropyridyl, tetrafluoropyridyl, fluoroquinolyl, fluoroisoquino Ril, fluoroindolyl, trifluoromethylindolyl, bistrifluoromethylcarbazolyl, trifluoro Romethylimidazolyl, trifluoromethyloxazolyl, trifluoromethylthienyl, trifluoromethylbenzothienyl, trifluoromethyldibenzothienyl, trifluoromethylthiazolyl, trifluoromethylbenzothiazolyl and the like can be mentioned, and preferably Is fluorine atom, chlorine atom, fluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, fluoro Phenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethoxyphenyl, pentafluorobiphenyl, trifluoro Tilbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxy, pentafluorophenoxy, bistrifluoromethylphenoxy, bistrifluoromethylphenoxy, difluoromethylenedioxyphenyl, trifluoroacetyl, pentafluorobenzoyl, fluorophenyliminomethyl, pentafluorophenyliminomethyl , Trifluoromethylphenyliminomethyl, trifluoromethylthio, trifuryl, triflate, nonaflate, bistrifurylimide, trifluoromethylfuryl, trifluoromethylbenzofuryl, trifluoromethyldibenzofuryl, trifluoromethylpyrrolyl, pentafluorophenylpyrrolyl , Fluoropyridyl, tetrafluoropyridyl, trifluoromethylindolyl Bistrifluoromethylcarbazolyl, trifluoromethylthienyl, trifluoromethylbenzothienyl, trifluoromethylthiazolyl, particularly preferably trifluoromethyl, fluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethyl Phenyl, pentafluorobiphenyl, trifluoromethoxy, pentafluorophenoxy.

  Examples of the monovalent oxygen-containing group include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, methallyloxy, prenyloxy, benzyloxy, methoxymethoxy, Methoxyethoxy, phenoxy, naphthoxy, toluyloxy, isopropylphenoxy, allylphenoxy, t-butylphenoxy, methoxyphenoxy, isopropoxyphenoxy, allyloxyphenoxy, biphenyloxy, binaphthyloxy, methoxymethyl, allyloxymethyl, benzyloxymethyl, phenoxy Methyl, methoxyethyl, allyloxyethyl, benzyloxyethyl, phenoxyethyl, methoxypropyl, allyloxypropyl, benzyloxypropylene , Phenoxypropyl, methoxyvinyl, allyloxyvinyl, benzyloxyvinyl, phenoxyvinyl, methoxyallyl, allyloxyallyl, benzyloxyallyl, phenoxyallyl, formyl, acetyl, isobutyryl, pivaloyl, benzoyl, naphthoyl, adamantanecarbonyl, acetoxy, pivaloyloxy Benzoyloxy, dimethoxymethyl, diisopropoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, methyl carbonate, phenyl carbonate, dimethyldioxanyl, methyl carboxylate, ethyl carboxylate, methoxyphenyl, isopropoxyphenyl, Allyloxyphenyl, phenoxyphenyl, methylenedioxyphenyl, furyl, methylfuryl, teto Hydrofuryl, pyranyl, tetrahydropyranyl, furofuryl, benzofuryl, dibenzofuryl and the like can be mentioned, preferably methoxy, ethoxy, isopropoxy, allyloxy, n-butoxy, t-butoxy, prenyloxy, benzyloxy, phenoxy, naphthoxy , Toluyloxy, isopropylphenoxy, allylphenoxy, t-butylphenoxy, methoxyphenoxy, biphenyloxy, binaphthyloxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, formyl, Acetyl, isobutyryl, pivaloyl, benzoyl, naphthoyl, dimethoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxani Dimethyldioxanyl, methylcarboxylate, ethylcarboxylate, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylenedioxyphenyl, furyl, methylfuryl, tetrahydropyranyl, furofuryl, benzofuryl, dibenzofuryl Yes, particularly preferably methoxy, isopropoxy, allyloxy, phenoxy, formyl, acetyl, benzoyl, dimethoxymethyl, dioxolanyl, methylcarboxylate, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, furyl, methylfuryl, benzofuryl Dibenzofuryl.

  Examples of the monovalent nitrogen-containing group include cyano, dimethylamino, diethylamino, allylamino, diallylamino, didecylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, morpholyl, azepinyl, formamide, acetamide, pivalamide, benzamide, naphthamide , Adamantanecarboxamide, iminomethyl, iminoethyl, phenyliminomethyl, phenyliminoethyl, dimethylhydrazonomethyl, pyrrolidinyliminomethyl, imide, uril, methyluril, dimethyluril, guanidinyl, dimethylguanidinyl, methylformimidamide, phenyl Formimidamide, carbamoyl, N-methylcarbamoyl, N-benzylcarbamoyl, N, N-dimethylcarbamoyl, pylori Nylcarbamoyl, N-phenylcarbamoyl, carbamoyloxy, N-methylcarbamoyloxy, N-benzylcarbamoyloxy, N, N-dimethylcarbamoyloxy, pyrrolidinylcarbamoyloxy, N-phenylcarbamoyloxy, dimethylaminomethyl, dibenzylaminomethyl , Pyrrolidinylmethyl, dimethylaminoethyl, benzylaminomethyl, benzylaminoethyl, pyrrolidinylethyl, dimethylaminovinyl, benzylaminovinyl, pyrrolidinylvinyl, dimethylaminopropyl, benzylaminopropyl, pyrrolidinylpropyl, dimethyl Aminoallyl, benzylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl, dimethylaminophenyl Pyrrolidinylphenyl, pyrrolylphenyl, pyridylphenyl, quinolylphenyl, isoquinolylphenyl, indolinylphenyl, indolylphenyl, carbazolylphenyl, di-t-butylcarbazolylphenyl, pyrrolyl, methylpyrrolyl, phenylpyrrolyl , Pyridyl, quinolyl, tetrahydroquinolyl, isoquinolyl, tetrahydroisoquinolyl, indolyl, indolinyl, carbazolyl, di-t-butylcarbazolyl, imidazolyl, dimethylimidazolidinyl, benzimidazolyl, oxazolyl, oxazolidinyl, benzooxa Zolyl and the like, preferably cyano, dimethylamino, diethylamino, allylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, morpholyl, Formamide, acetamide, benzamide, iminomethyl, iminoethyl, phenyliminomethyl, phenyliminoethyl, dimethylhydrazonomethyl, pyrrolidinyliminomethyl, carbamoyl, N-methylcarbamoyl, N-benzylcarbamoyl, N, N-dimethylcarbamoyl, pyrrolidini Rucarbamoyl, N-phenylcarbamoyl, carbamoyloxy, N-methylcarbamoyloxy, N, N-dimethylcarbamoyloxy, dimethylaminomethyl, benzylaminomethyl, pyrrolidinylmethyl, dimethylaminoethyl, pyrrolidinylethyl, dimethylaminopropyl, Pyrrolidinylpropyl, dimethylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl, dimethyl Minophenyl, pyrrolidinylphenyl, pyrrolylphenyl, carbazolylphenyl, di-t-butylcarbazolylphenyl, pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, isoquinolyl, tetrahydroisoquinolyl, indolyl, indolinyl, carbazolyl, di -T-butylcarbazolyl, imidazolyl, dimethylimidazolidinyl, benzimidazolyl, oxazolyl, oxazolidinyl, benzoxazoly, particularly preferably dimethylamino, diethylamino, pyrrolidinyl, dimethylaminophenyl, pyrrolidinylphenyl, pyrrolyl, Pyridyl, carbazolyl and imidazolyl.

Examples of the monovalent boron-containing group include boranediyl, boranetriyl, diboranyl and the like.
Examples of the monovalent sulfur-containing group include methylthio, ethylthio, benzylthio, phenylthio, naphthylthio, methylthiomethyl, benzylthiomethyl, phenylthiomethyl, naphthylthiomethyl, methylthioethyl, benzylthioethyl, phenylthioethyl, and naphthylthio. Ethyl, methylthiovinyl, benzylthiovinyl, phenylthiovinyl, naphthylthiovinyl, methylthiopropyl, benzylthiopropyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, Methylthiophenyl, thienylphenyl, methylthienylphenyl, benzothienylphenyl, dibenzothienylphenyl, benzodithienylphenyl, methyl Sulfinyl, t-butylsulfinyl, phenylsulfinyl, mesyl, benzenesulfonyl, tosyl, methanesulfonate, 4-methylbenzenesulfonate, thiouryl, methylthiouryl, bis (methylthio) methyl, thienyl, tetrahydrothienyl, methylthienyl, thienofuryl, thienothienyl Benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, dithiolanyl, dithianyl, oxathiolanyl, oxathianyl, thiazolyl, benzothiazolyl, thiazolidinyl, and the like, preferably thienyl, methylthienyl, thienofuryl, thienothienyl, benzothienyl, Dibenzothienyl, thienobenzofuryl, benzodithienyl, thiazolyl, benzothiazolyl.

Examples of the monovalent phosphorus-containing group include a phenylphosphine group.
Examples of the monovalent silicon-containing group include trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, triphenylsilyl, tris (trimethylsilyl) silyl, and cyclopentadi. Enyldimethylsilyl, di-n-butyl (cyclopentadienyl) silyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, di-n-butyl (indenyl) silyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, Di-n-butyl (fluorenyl) silyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 4-t-butyldiphenylsilylphenyl Nyl, 4-triphenylsilylphenyl, 4-tris (trimethylsilyl) silylphenyl and the like, preferably trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, triphenylsilyl, cyclopentadienyl Dimethylsilyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 4-triphenylsilylphenyl, particularly preferably trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethyl Silyl phenyl, 4-triisopropylsilyl phenyl.

Examples of the monovalent germanium-containing group or tin-containing group include groups obtained by converting silicon into germanium or tin in the monovalent silicon-containing group.
R ² and R ³ may form a 5- to 8-membered saturated or unsaturated hydrocarbon group fused to the cyclopentadienyl ring portion, preferably a 5- or 6-membered ring, The structure combined with the cyclopentadienyl part of the mother nucleus includes indene, 2-methylindene, 2-methyl-4-phenylindene, 2-methylbenzoindene, 4,5,6,7-tetrahydroindene, 2-methyl -1,5,6,7-tetrahydro-s-indacene, 6,7-dihydro-5H-s-indacene, 6,7-dihydro-8H-as-indacene, 1H-benz [f] indene, 5,6 , 7,8-tetrahydro-1H-benz [f] indene, 3H-benz [e] indene, 6,7,8,9-tetrahydro-3H-benz [e] indene, 5,7-dihydro-4H-cycl Penta [e] acenaphthylene, 1,1,3-trimethyl-1,9-dihydrocyclopenta [b] fluorene, 1,1,3,6,8,8-hexamethyl-8,10-dihydro-1H-dicyclopenta [ b, h] fluorene, 1,3,3-trimethyl-3,9-dihydrocyclopenta [b] fluorene, 1,3,3,6,6,8-hexamethyl-6,10-dihydro-3H-dicyclopenta [ b, h] fluorene, 6,6-dimethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 4,4,7,7-tetramethyl-2,3,4,7,8 , 9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 6,6,9,9-tetramethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 1, 1, 4 4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 1,2,2,4-tetra Methyl-2,10-dihydro-1H-indeno [1,2-g] quinoline, 1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H- Examples include cyclopenta [1,2-g: 5,4-g ′] diquinoline, azulene and the like.

In general formula (II), R ² , R ³ and R ⁴ are preferably all hydrogen atoms. In general formula (III), R ² , R ³ and R ⁴ are preferably all hydrogen atoms. In general formula (IV), R ² , R ³ and R ⁴ are preferably all hydrogen atoms.

R ⁵ and R ⁶ may form a 5- or 8-membered saturated or unsaturated hydrocarbon group fused to the fluorene ring moiety, and preferably a 5- or 6-membered ring, As a structure combined with a fluorenyl moiety, 1,1,3-trimethyl-1,9-dihydrocyclopenta [b] fluorene, 1,1,3,6,8,8-hexamethyl-8,10-dihydro-1H— Dicyclopenta [b, h] fluorene, 1,3,3-trimethyl-3,9-dihydrocyclopenta [b] fluorene, 1,3,3,6,6,8-hexamethyl-6,10-dihydro-3H- Dicyclopenta [b, h] fluorene, 6,6-dimethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 4,4,7,7-tetramethyl-2,3,4,7 , 8, 9, 10, 12 -Octahydro-1H-dibenzo [b, h] fluorene, 6,6,9,9-tetramethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 1,1,4,4 7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 1,2,2,4-tetramethyl-2 , 10-dihydro-1H-indeno [1,2-g] quinoline, 1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,4-g ′] diquinoline and the like, and these are preferable structures.

Formula (II), in (III) or (IV), when R ⁵ and R ⁶ do not form a saturated or unsaturated hydrocarbon group of 5-8 membered ring condensed to the fluorene ring moiety, as R ⁵ Is a monovalent group, which is a 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 or tin-containing group. It is preferable. In this case, R ⁶ is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a hydrogen atom.

Q ² and Q ³ are divalent groups that bind two ligands, and each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group, or tin It is a containing group. Examples of these groups include the same substituents as those described above for Q ¹ . Both Q ² and Q ³ are preferably an alkylene group, a substituted alkylene group, an alkylidene group, or a silicon-containing group. More preferably, an alkylene group such as methylene, ethylene, propylene, butylene, isopropylidene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, Dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, etc. A substituted alkylene group.

Q ² or Q ³ may form a ^3- to 8-membered ring containing Q ² or Q ^3, and is preferably a 5- to 6-membered ring. In this case, the structure includes cyclopentane, cyclohexane, silolane, silinan A ring etc. are mentioned.
Q ⁴ is a carbon atom, a silicon atom, a germanium atom or a tin atom, and preferably a carbon atom or a silicon atom.

In the general formula (IV), R ⁷ is a monovalent group, and is 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, It is preferably a germanium-containing group or a tin-containing group, more preferably a hydrocarbon group or a halogen-containing group, a linear or branched alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms. And more preferably an aromatic-containing linear or branched alkyl group and an unsaturated double bond-containing group or an aryl group having 6 to 20 carbon atoms.

R ³ and Q ² , R ³ and Q ³ , or R ³ and R ⁷ may be bonded to each other to form a ring. Such a ring structure includes a saturated 5-membered ring or a bicyclic saturated group. Specific examples include a 5-membered ring, and specific examples include a cyclopentane ring mother skeleton, an octahydroindene ring mother skeleton, and an octahydropentalene ring mother skeleton.

  X is a monovalent group, and each independently represents 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, a phosphorus-containing group, or a boron-containing group. Group or aluminum-containing group, which may be the same or different.

In X, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.
In X, examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, s-butyl, t -Butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, cyanyl, isohexyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, texyl, 4,4- Linear or branched alkyl groups such as dimethylpentyl;
Vinyl, allyl, propenyl, isopropenyl, allenyl, but-3-en-1-yl, crotyl, but-3-en-2-yl, methallyl, erythrenyl, penta-4-en-1-yl, penta-3 Linear or branched such as -en-1-yl, penta-2-en-1-yl, isopentenyl, 2-methylbut-3-en-1-yl, penta-4-en-2-yl, prenyl An alkenyl group or an unsaturated double bond-containing group;
Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, propargyl;
Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t-butylbenzyl, 3,5 -Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups such as di-t-butylbenzyl, phenylethyl, benzhydryl;
Cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, 2-adamantyl;
Phenyl, tolyl, xylyl, mesityl, cumenyl, duryl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, naphthyl, biphenyl , Aryl groups such as t-phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, ferrocenyl;
A conjugated diene divalent derivative group capable of forming a metallocyclopentene group, such as 1,3-butadienyl, isoprenyl, piperenyl, 2,4-hexadienyl, 1,4-diphenyl-1,3-pentadienyl, cyclopentadienyl; Can be mentioned.

  Among the above hydrocarbon groups, methyl, isobutyl, neopentyl, cyanyl, benzyl, phenyl, tolyl, xylyl, mesityl, cumenyl, 1,3-butadienyl, isoprenyl, piperenyl, 2,4-hexadienyl, 1,4- Diphenyl-1,3-pentadienyl.

  In X, examples of the monovalent halogen-containing group include fluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetra Fluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, hexachloroantimonate anion and the like can be mentioned, and pentafluorophenyl is preferable.

  In X, examples of the monovalent silicon-containing group include trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, triphenylsilyl, tris (trimethylsilyl) silyl, Examples thereof include trimethylsilylmethyl, and trimethylsilylmethyl is preferable.

  In X, examples of the monovalent oxygen-containing group include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, benzyloxy, methoxymethoxy, phenoxy, 2,6-dimethylphenoxy, 2,6-diisopropylphenoxy, 2,6-di-t-butylphenoxy, 2,4,6-trimethylphenoxy, 2,4,6-triisopropylphenoxy, acetoxy, pivaloyloxy, benzoyloxy , Trifluoroacetoxy, perchlorate anion, periodate anion, and the like. Preferred are methoxy, ethoxy, isopropoxy, and t-butoxy.

  In X, examples of the monovalent sulfur-containing group include mesyl, phenylsulfonyl, tosyl, trifuryl, nonafryl, mesylate, tosylate, triflate, nonaflate, and preferably triflate.

  In X, examples of the monovalent nitrogen-containing group include amino, cyano, methylamino, dimethylamino, ethylamino, diethylamino, allylamino, diallylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, morpholyl, pyrrolyl, Examples thereof include bistrifurylimide, and preferred are dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl, and bistrifurylimide.

In X, examples of the monovalent phosphorus-containing group include a hexafluorophosphate anion.
In X, examples of the monovalent boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, (benzyl) ( Tris (pentafluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is hydrogen, alkyl group, aryl group optionally having substituent or halogen An atom or the like).

In X, examples of the monovalent aluminum-containing group include (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring, or (M-hydrocarbon group-aluminum atom-hydrocarbon group) four-membered ring. AlR ₄ (wherein R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like) can be used. M is M in the general formula (II), (III) or (IV).

  In the general formula (II), (III) or (IV), M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, particularly preferably a zirconium atom.

  L is a hydrocarbon group having a straight carbon chain having 1 to 10 carbon atoms, and preferably a hydrocarbon group having a straight carbon chain having 1 to 3 carbon atoms. Specifically, for example, methylene bridge, 1,2-ethane bridge, 1,3-propane bridge, 1,4-butane bridge, 1,5-pentane bridge, 1,6-hexane bridge, 1,7-heptane Crosslinks, 1,8-octane crosslinks, 1,9-nonane crosslinks, 1,10-decane crosslinks and the like are preferable, preferably methylene crosslinks, 1,2-ethane crosslinks, 1,3-propane crosslinks, 1,4 -Butane crosslinking.

D ¹ is the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di), preferably (Da), (Db), (Dc) or (Dd), more preferably (Da), (Db). Or (D-c), particularly preferably (D-a).

D ² represents the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di), preferably (Da), (Db), (Dc) or (Dd), more preferably (Da), (Db). Or (D-c), particularly preferably (D-a).

D ³ is the following general formula (Db), (Dc), (Dd), (Df), (Dg), (Dh) or (Di) , (Db), (Dc) or (Dd), more preferably (Db) or (Dc), particularly preferably (Db). is there.

前記一般式（Ｄ-ｂ）、（Ｄ-ｃ）、（Ｄ-ｄ）、（Ｄ-ｅ）、（Ｄ-ｆ）および（Ｄ-ｇ）中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹³は、一価の基であり、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、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り、互いに同一でも異なっていてもよく、また、隣接した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、上記Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷で挙げたものと同様な置換基が挙げられる。

In the general formulas (Db), (Dc), (Dd), (De), (Df) and (Dg), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹³ are monovalent groups, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, or a sulfur-containing group. , A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, which may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring. Examples of these groups include the same substituents as those described above for R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ .

In the general formula (Db), adjacent R ⁸ may be bonded to each other to form a 3- to 8-membered ring containing an unsaturated bond as a mother skeleton, preferably a 5- to 6-membered ring, Examples of the structure in this case include cyclopentene, cyclohexene, cyclooctene, cyclopentadiene, cyclohexadiene, and cyclooctadiene. R ⁸ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or methyl. Particularly preferably, all are hydrogen atoms.

In the general formula (Dc), Ch is an oxygen atom or a sulfur atom, preferably an oxygen atom. R ⁹ is a monovalent group, a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic-containing linear or branched alkyl group having 7 to 20 carbon atoms, and unsaturated. It is preferably a double bond-containing group or an aryl group having 6 to 20 carbon atoms, more preferably methyl, ethyl, isopropyl, t-butyl, benzyl or allyl.

In the general formula (Dd), Pn is a nitrogen atom or a phosphorus atom, preferably a nitrogen atom. R ¹⁰ may be bonded to each other to form a 3- to 8-membered ring containing a nitrogen atom, preferably a 5- to 6-membered ring. In this case, pyrrolidine, pyrrole, piperidine, morpholine, indoline, Indole and the like. R ¹⁰ is preferably methyl, ethyl, isopropyl, t-butyl, benzyl, allyl.

In the general formulas (De) and (Df), R ¹¹ is a monovalent group, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing group. A hydrocarbon group, a silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a sulfur-containing hydrocarbon group or a nitrogen-containing hydrocarbon group is preferred. R ¹¹ may be the same or different, and in a combination of one or more adjacent groups, the adjacent substituents are bonded to each other and saturated with a 5- to 8-membered ring fused to the benzene ring portion that is the mother skeleton. Alternatively, an unsaturated hydrocarbon group may be formed, and a 5- or 6-membered ring is preferable. Examples of the structure combined with the benzene ring portion of the mother nucleus include indacene, indene, naphthalene, benzofuran, benzothiophene, indole, quinoline and the like.

In R ¹¹ , the halogen atom is the same as described above, and is preferably a fluorine atom or a chlorine atom.
In R ¹¹ , examples of the hydrocarbon group having 1 to 20 carbon atoms include the same substituents as those described above for the hydrocarbon group, preferably methyl, ethyl, isopropyl, t-butyl, vinyl, allyl. , Prenyl and phenyl.

In R ¹¹ , the halogen-containing hydrocarbon group includes the same substituents as those described above for the halogen-containing group, and is preferably trifluoromethyl.
In R ¹¹ , examples of the silicon-containing hydrocarbon group include the same substituents as those described above for the silicon-containing group, and trimethylsilyl is preferable.
In R ¹¹ , examples of the oxygen-containing hydrocarbon group include the same substituents as those described above for the oxygen-containing group, and methoxy and furyl groups are preferable.
In R ¹¹ , examples of the sulfur-containing hydrocarbon group include the same substituents as those described above for the sulfur-containing group, preferably methylthio and thienyl.
In R ¹¹ , examples of the nitrogen-containing hydrocarbon group include the same substituents as those described above for the nitrogen-containing group, preferably cyano, dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl, pyridyl, indolyl, carbazolyl, imidazolyl. It is.

In the general formula (Df), R ¹² is a monovalent group, and is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. Examples of these groups include the same substituents as those described for R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ . R ¹² may be bonded to adjacent R ¹¹ to form a ring, preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Examples of the structure in this case include indoline, indole, benzofuran, benzothiophene, and quinoline. R ¹² is preferably an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a sulfur-containing hydrocarbon group or a phosphorus-containing hydrocarbon group, particularly preferably methoxy, ethoxy, isopropoxy, t-butoxy, furyl, cyano, Dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl, pyridyl, indolyl, carbazolyl, imidazolyl, methylthio, thienyl, diphenylphosphino.
In the general formula (Dg), R ¹³ is preferably methyl, isopropyl, t-butyl, phenyl or trimethylsilyl.

Particularly preferred examples of the 4-position substituent of the fluorene ring represented by L-D ¹ and the 3-position substituent of the cyclopentadienyl ring represented by L-D ² are n-propyl, n-butyl, n -Pentyl, n-hexyl, n-heptyl, n-octyl, allyl, ω-butenyl, ω-pentenyl, ω-hexenyl, ω-heptenyl, ω-octenyl, 3-methoxypropyl, 4-methoxybutyl, 5-methoxy Pentyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 2-methoxybenzyl, 2-methoxyphenethyl, 2-vinylbenzyl, 2-vinylphenethyl, 2-allylbenzyl, 2-allylphenethyl. Since ω represents the terminal of the substituent, it means that it has a terminal unsaturated bond.

Particularly preferred examples of the bridging moiety substituent represented by L-D ³ are allyl, ω-butenyl, ω-pentenyl, ω-hexenyl, ω-heptenyl, ω-octenyl, 3-methoxypropyl, 4-methoxybutyl. 5-methoxypentyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 2-methoxybenzyl, 2-methoxyphenethyl, 2-vinylbenzyl, 2-vinylphenethyl, 2-allylbenzyl, 2-allylphenethyl. Since ω represents the terminal of the substituent, it means that it has a terminal unsaturated bond.

  The method for producing the metallocene compound represented by the general formulas (II), (III) and (IV) is not particularly limited as long as the metallocene compound exhibiting the effects of the present invention is obtained, and can be produced by a known method. An example of a typical synthesis route is shown below, but the production method is not particularly limited.

  The substituted cyclopentadiene compound as a starting material can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include JP-A-2006-233208, JP-A-2009-143901, and JP-A-2009-144148.

  The substituted fluorene compound can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, “J. Org. Chem. 2000, 65, 3858.”, WO 2001/027124, WO 2004/029062, and WO 2006/126608 by the present applicant.

  The brominated product of the substituted fluorene compound and the coupling reaction product of the brominated substituted fluorene compound and the boron compound can be produced by a known method, and the production method is not particularly limited. As a known production method, for example, US Pat. No. 7,470,759 can be mentioned.

  A precursor compound (ligand) of a metallocene compound represented by the general formula (II), (III) or (IV) is a substituted cyclopentadiene compound, the substituted fluorene compound, a substituted carbonyl compound or a halogenated substituted silicon compound. Can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, WO2009 / 045301 and WO2004 / 029062 and JP2009-143901 by the present applicant.

  The metallocene compound represented by the general formula (II), (III) or (IV) can be produced by a known method using the precursor compound (ligand), and the production method is particularly limited. Do not mean. As a known production method, for example, WO 2004/029062 by the present applicant can be cited.

  Specific examples of the metallocene compound represented by the general formula (II), (III) or (IV) according to the present invention are shown below, but the scope of the present invention is not particularly limited thereby. In the present invention, at least one metallocene compound selected from the general formulas (II), (III) and (IV) is used as the component (B), and the general formulas (II), (III) and (IV) are used. Two or more metallocene compounds having different chemical structures may be used. In addition, optical isomers having the same chemical structure may be used alone or in a mixture of optical isomers having the same chemical structure (for example, a meso isomer mixture or a racemic mixture).

Among the metallocene compounds represented by the general formula (II), for the sake of convenience, the ligand structure excluding MX ₂ (metal portion) of the metallocene compound is represented by a cyclopentadienyl ring portion, a bridge portion structure (Q ² ), a fluorenyl ring. divided in four 1,2,3,5,6,7,8-position substituent (R ⁴ to R ⁶⁾ and 4-position substituent of the fluorenyl ring (L-D ^1). The abbreviation of the cyclopentadienyl ring moiety is II-α, the abbreviation of the structure of the bridge portion is II-β, the abbreviation of the combined structure of the cyclopentadienyl ring and the bridge portion is II-γ, and 2,3,6 of the fluorenyl ring The abbreviations of the combination structure of the 7-position substituents are II-δ, the abbreviations of the combination structure of the 4-position substituents of the fluorenyl ring are II-ε, and the abbreviations of the substituents are shown in Tables 1 to 5 below.

According to the above notation, the cyclopentadienyl ring portion is II-α-6 in Table 1, the bridging portion is II-β-3 in Table 2, and the fluorenyl ring portion is II-δ-9 in Table 4. In the case where the 4-position substituent of the fluorenyl ring is composed of a combination of II-ε-6 in Table 5 and MX _{2 of} the metal moiety is ZrCl ₂ , the following compound (II-1) is exemplified.

また、シクロペンタジエニル環部分が表１中のII−α−３、架橋部分が表２中のII−β−１２、フルオレニル環部分が表４中のII−δ−５、フルオレニル環の４位置換基が表５中のII−ε−８の組み合わせで構成され、金属部分のＭＸ₂がＨｆＣｌ₂の場合は、下記化合物（II−２）を例示している。

Further, the cyclopentadienyl ring part is II-α-3 in Table 1, the bridging part is II-β-12 in Table 2, the fluorenyl ring part is II-δ-5 in Table 4, and 4 of the fluorenyl ring. When the positional substituent is composed of a combination of II-ε-8 in Table 5 and MX _{2 of} the metal part is HfCl ₂ , the following compound (II-2) is exemplified.

また、シクロペンタジエニル環部分が表１中のII−α−１、架橋部分が表２中のII−β−１７、フルオレニル環部分が表４中のII−δ−１３、フルオレニル環の４位置換基が表５中のII−ε−１６の組み合わせで構成され、金属部分のＭＸ₂がＺｒ（ＮＭｅ₂）₂の場合は、下記化合物（II−３）を例示している。

Further, the cyclopentadienyl ring part is II-α-1 in Table 1, the bridging part is II-β-17 in Table 2, the fluorenyl ring part is II-δ-13 in Table 4, and 4 of the fluorenyl ring. When the positional substituent is composed of a combination of II-ε-16 in Table 5 and MX _{2 of} the metal part is Zr (NMe ₂ ) ₂ , the following compound (II-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表３中のII−γ−８、フルオレニル環部分が表４中のII−δ−１９、フルオレニル環の４位置換基が表５中のII−ε−２３の組み合わせで構成され、金属部分のＭＸ₂がＨｆ（Ｍｅ）₂の場合は、下記化合物（II−４）を例示している。

The combined structure of the cyclopentadienyl ring and the bridging moiety is II-γ-8 in Table 3, the fluorenyl ring part is II-δ-19 in Table 4, and the 4-position substituent of the fluorenyl ring is in Table 5. When it is composed of a combination of II-ε-23 and MX _{2 of} the metal part is Hf (Me) ₂ , the following compound (II-4) is exemplified.

一般式（III）で表されるメタロセン化合物のうち、便宜上、メタロセン化合物のＭＸ₂（金属部分）を除いたリガンド構造を、シクロペンタジエニル環の２，３あるいは４，５位の置換基（Ｒ²，Ｒ³）、架橋部分の構造（Ｑ³）、フルオレニル環部分の構造およびシクロペンタジエニル環の３あるいは４位の置換基（Ｌ−Ｄ²）の４つに分ける。シクロペンタジエニル環の２，３あるいは４，５位の置換基の組み合わせ構造の略称をIII−α、架橋部分の構造の略称をIII−β、シクロペンタジエニル環と架橋部分の組み合わせ構造の略称をIII−γ、フルオレニル環部分構造の略称をIII−δ、シクロペンタジエニル環の３あるいは４位置換基の組み合わせ構造の略称をIII−εとし、各置換基の略称を表６〜表１０に示す。

Among the metallocene compounds represented by the general formula (III), for the sake of convenience, the ligand structure excluding MX ₂ (metal portion) of the metallocene compound is substituted with a substituent at the 2, 3 or 4, 5 position of the cyclopentadienyl ring ( R ² , R ³ ), the structure of the bridging moiety (Q ³ ), the structure of the fluorenyl ring part, and the substituent at the 3 or 4 position of the cyclopentadienyl ring (LD ² ). The abbreviation of the combined structure of the substituents at the 2, 3 or 4, 5 position of the cyclopentadienyl ring is III-α, the abbreviation of the structure of the bridging portion is III-β, and the combined structure of the cyclopentadienyl ring and the bridging portion is The abbreviation is III-γ, the abbreviation of the fluorenyl ring partial structure is III-δ, the abbreviation of the combined structure of 3- or 4-position substituents of the cyclopentadienyl ring is III-ε, and the abbreviations of each substituent are shown in Tables 6 to 10 shows.

According to the above notation, the cyclopentadienyl ring portion is III-α-2 in Table 6, the bridging portion is III-β-1 in Table 7, and the fluorenyl ring portion is III-δ-10 in Table 9. When the 3- or 4-position substituent of the cyclopentadienyl ring is composed of the combination of III-ε-1 in Table 10 and MX _{2 of} the metal moiety is ZrCl ₂ , the following compound (III-1) is exemplified. doing.

また、シクロペンタジエニル環部分が表６中のIII−α−５、架橋部分が表７中のIII−β−１６、フルオレニル環部分が表９中のIII−δ−１７、シクロペンタジエニル環の３あるいは４位置換基が表１０中のIII−ε−２０の組み合わせで構成され、金属部分のＭＸ₂がＨｆ（ＮＭｅ₂）₂の場合は、下記化合物（III−２）を例示している。

Further, the cyclopentadienyl ring part is III-α-5 in Table 6, the bridging part is III-β-16 in Table 7, the fluorenyl ring part is III-δ-17 in Table 9, and cyclopentadienyl. When the 3- or 4-position substituent of the ring is composed of a combination of III-ε-20 in Table 10 and MX _{2 of} the metal moiety is Hf (NMe ₂ ) ₂ , the following compound (III-2) is exemplified. ing.

また、シクロペンタジエニル環部分が表６中のIII−α−１、架橋部分が表７中のIII−β−２０、フルオレニル環部分が表９中のIII−δ−１４、シクロペンタジエニル環の３あるいは４位置換基が表１０中のIII−ε−２５の組み合わせで構成され、金属部分のＭＸ₂がＴｉＣｌ₂の場合は、下記化合物（III−３）を例示している。

Further, the cyclopentadienyl ring portion is III-α-1 in Table 6, the bridging portion is III-β-20 in Table 7, the fluorenyl ring portion is III-δ-14 in Table 9, and cyclopentadienyl. When the 3- or 4-position substituent of the ring is composed of a combination of III-ε-25 in Table 10 and MX _{2 of} the metal moiety is TiCl ₂ , the following compound (III-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表８中のIII−γ−１、フルオレニル環部分が表４中のIII−δ−１９、フルオレニル環部分が表９中のIII−δ−２０、シクロペンタジエニル環の３あるいは４位置換基が表１０中のIII−ε−３０の組み合わせで構成され、金属部分のＭＸ₂がＺｒＭｅ₂の場合は、下記化合物（III−４）を例示している。

Further, the combined structure of the cyclopentadienyl ring and the bridging portion is III-γ-1 in Table 8, the fluorenyl ring portion is III-δ-19 in Table 4, and the fluorenyl ring portion is III-δ- in Table 9. 20. When the 3- or 4-position substituent of the cyclopentadienyl ring is composed of a combination of III-ε-30 in Table 10 and MX _{2 of} the metal moiety is ZrMe ₂ , the following compound (III-4) is obtained: Illustrated.

一般式（IV）で表されるメタロセン化合物のうち、便宜上、メタロセン化合物のＭＸ₂（金属部分）を除いたリガンド構造を、シクロペンタジエニル環部分、架橋部分の構造（Ｒ⁷−Ｑ⁴）、フルオレニル環部分の構造および架橋部分の置換基（Ｌ−Ｄ³）の４つに分ける。シクロペンタジエニル環部分の構造の略称をIV−α、架橋部分の構造の略称をIV−β、シクロペンタジエニル環と架橋部分の組み合わせ構造の略称をIV−γ、フルオレニル環部分構造の略称をIV−δ、架橋部分の置換基の組み合わせ構造の略称をIV−εとし、各置換基の略称を表１１〜表１５に示す。

Of the metallocene compounds represented by the general formula (IV), for the sake of convenience, the ligand structure excluding MX ₂ (metal portion) of the metallocene compound is represented by a cyclopentadienyl ring portion and a bridge portion structure (R ⁷ -Q ⁴ ). , The structure of the fluorenyl ring moiety and the substituent (LD ³ ) of the bridging moiety. Abbreviation of the structure of the cyclopentadienyl ring moiety is IV-α, the abbreviation of the structure of the bridge is IV-β, the abbreviation of the combined structure of the cyclopentadienyl ring and the bridge is IV-γ, the abbreviation of the fluorenyl ring partial structure Is IV-δ, the abbreviation of the combined structure of the substituents in the cross-linking portion is IV-ε, and the abbreviations of the substituents are shown in Tables 11 to 15.

According to the above notation, the cyclopentadienyl ring portion is IV-α-4 in Table 11, the bridged partial structure is IV-β-2 in Table 12, and the fluorenyl ring portion is IV-δ- in Table 14. 1. When the substituent of the bridging moiety is composed of a combination of IV-ε-2 in Table 15, and MX _{2 of} the metal moiety is Ti (η ⁴ -1,3-pentadienyl), the following compound (IV-1 ).

また、シクロペンタジエニル環部分が表１１中のIV−α−１、架橋部分構造が表１２中のIV−β−９、フルオレニル環部分が表１４中のIV−δ−７、架橋部分の置換基が表１５中のIV−ε−１１の組み合わせで構成され、金属部分のＭＸ₂がＨｆＢｎ₂の場合は、下記化合物（IV−２）を例示している。

Further, the cyclopentadienyl ring portion is IV-α-1 in Table 11, the bridge portion structure is IV-β-9 in Table 12, the fluorenyl ring portion is IV-δ-7 in Table 14, and the bridge portion is When the substituent is composed of a combination of IV-ε-11 in Table 15 and MX _{2 of} the metal moiety is HfBn ₂ , the following compound (IV-2) is exemplified.

また、シクロペンタジエニル環部分が表１１中のIV−α−８、架橋部分構造が表１２中のIV−β−１６、フルオレニル環部分が表１４中のIV−δ−１６、架橋部分の置換基が表１５中のIV−ε−２５の組み合わせで構成され、金属部分のＭＸ₂がＺｒ（ＯｉＰｒ）₂の場合は、下記化合物（IV−３）を例示している。

Further, the cyclopentadienyl ring part is IV-α-8 in Table 11, the bridge part structure is IV-β-16 in Table 12, the fluorenyl ring part is IV-δ-16 in Table 14, and the bridge part is When the substituent is composed of a combination of IV-ε-25 in Table 15 and MX _{2 of} the metal portion is Zr (OiPr) ₂ , the following compound (IV-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表１３中のIV−γ−５、フルオレニル環部分が表１４中のIV−δ−１８、架橋部分の置換基が表１５中のIV−ε−２７の組み合わせで構成され、金属部分のＭＸ₂がＺｒＢｒ₂の場合は、下記化合物（IV−４）を例示している。

The combined structure of the cyclopentadienyl ring and the bridging moiety is IV-γ-5 in Table 13, the fluorenyl ring moiety is IV-δ-18 in Table 14, and the substituent of the bridging moiety is IV- in Table 15. When composed of a combination of ε-27 and the metal part MX ₂ is ZrBr ₂ , the following compound (IV-4) is exemplified.

金属部分ＭＸ₂の具体的な例示としては、ＴｉＦ₂、ＴｉＣｌ₂、ＴｉＢｒ₂、ＴｉＩ₂、Ｔｉ（Ｍｅ）₂、Ｔｉ（Ｂｎ）₂、Ｔｉ（Ａｌｌｙｌ）₂、Ｔｉ（ＣＨ₂−ｔＢｕ）₂、Ｔｉ（η⁴−１，３−ブタジエニル）、Ｔｉ（η⁴−１，３−ペンタジエニル）、Ｔｉ（η⁴−２，４−ヘキサジエニル）、Ｔｉ（η⁴−１，４−ジフェニル−１，３−ペンタジエニル）、Ｔｉ（ＣＨ₂−Ｓｉ（Ｍｅ）₃）₂、Ｔｉ（ＯＭｅ）₂、Ｔｉ（ＯｉＰｒ）₂、Ｔｉ（ＮＭｅ₂）₂、Ｔｉ（ＯＭｓ）₂、Ｔｉ（ＯＴｓ）₂、Ｔｉ（ＯＴｆ）₂、ＺｒＦ₂、ＺｒＣｌ₂、ＺｒＢｒ₂、ＺｒＩ₂、Ｚｒ（Ｍｅ）₂、Ｚｒ（Ｂｎ）₂、Ｚｒ（Ａｌｌｙｌ）₂、Ｚｒ（ＣＨ₂−ｔＢｕ）₂、Ｚｒ（η⁴−１，３−ブタジエニル）、Ｚｒ（η⁴−１，３−ペンタジエニル）、Ｚｒ（η⁴−２，４−ヘキサジエニル）、Ｚｒ（η⁴−１，４−ジフェニル−１，３−ペンタジエニル）、Ｚｒ（ＣＨ₂−Ｓｉ（Ｍｅ）₃）₂、Ｚｒ（ＯＭｅ）₂、Ｚｒ（ＯｉＰｒ）₂、Ｚｒ（ＮＭｅ₂）₂、Ｚｒ（ＯＭｓ）₂、Ｚｒ（ＯＴｓ）₂、Ｚｒ（ＯＴｆ）₂、ＨｆＦ₂、ＨｆＣｌ₂、ＨｆＢｒ₂、ＨｆＩ₂、Ｈｆ（Ｍｅ）₂、Ｈｆ（Ｂｎ）₂、Ｈｆ（Ａｌｌｙｌ）₂、Ｈｆ（ＣＨ₂−ｔＢｕ）₂、Ｈｆ（η⁴−１，３−ブタジエニル）、Ｈｆ（η⁴−１，３−ペンタジエニル）、Ｈｆ（η⁴−２，４−ヘキサジエニル）、Ｈｆ（η⁴−１，４−ジフェニル−１，３−ペンタジエニル）、Ｈｆ（ＣＨ₂−Ｓｉ（Ｍｅ）₃）₂、Ｈｆ（ＯＭｅ）₂、Ｈｆ（ＯｉＰｒ）₂、Ｈｆ（ＮＭｅ₂）₂、Ｈｆ（ＯＭｓ）₂、Ｈｆ（ＯＴｓ）₂、Ｈｆ（ＯＴｆ）₂などが挙げられる。Ｍｅはメチル基、Ｂｎはベンジル基、ｔＢｕはｔｅｒｔ−ブチル基、Ｓｉ（Ｍｅ）₃はトリメチルシリル基、ＯＭｅはメトキシ基、ＯｉＰｒはｉｓｏ−プロポキシ基、ＮＭｅ₂はジメチルアミノ基、ＯＭｓはメタンスルホナート基、ＯＴｓはｐ−トルエンスルホナート基、ＯＴｆはトリフルオロメタンスルホナート基である。

Specific examples of the metal portion MX ₂ include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , Ti (Me) ₂ , Ti (Bn) ₂ , Ti (Allyl) ₂ , and 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 (OMe) 2, Ti (OiPr) 2, Ti (NMe 2) 2, Ti (OMs) 2, Ti (OTs) 2, Ti (OTf) 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 (η ⁴ -1,3- Pentajieni ), Zr (η ⁴ -2,4- hexadienyl), Zr (η ⁴ -1,4- _{diphenyl-1,3-pentadienyl), Zr (CH 2 -Si (} Me) 3) 2, Zr (OMe) 2 _{, Zr (OiPr) 2, Zr} (NMe 2) 2, Zr (OMs) 2, Zr (OTs) 2, Zr (OTf) 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 (η 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 (OMe) ₂ , Hf (OiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (OMs) ₂ , Hf (OTs) ₂ , H f (OTf) _{2 and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and OMs is methanesulfonate Group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

(Ingredient (C))
Component (C) is
(C-1) an organometallic compound represented by the following general formula (V), (VI) or (VII),
(C-2) an organoaluminum oxy compound, and (c-3) at least one compound selected from the group consisting of compounds that react with component (A) and component (B) to form ion pairs. These compounds may be used alone or in combination of two or more.

R ^a _m Al (OR ^b ) _n H _p X _q (V)
In general formula (V), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same as or different from each other, X represents a halogen atom, m Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.

M ^a AlR ^a ₄ (VI)
In general formula (VI), M ^a represents a lithium atom, a sodium atom or a potassium atom, and 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 (VII)
In general formula (VII), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, and M ^b represents a magnesium atom, zinc An atom or a cadmium atom, X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2.

  Among the organometallic compounds (c-1) represented by the general formula (V), (VI) or (VII), the organometallic compound represented by the general formula (V) is preferable. Specific examples of the organometallic compounds shown include, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, dimethylaluminum chloride, Dialkylaluminum halides such as diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride Alkyl aluminum sesquihalides such as lolide, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, dimethyl aluminum hydride, Diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-s c- heptyl hydride, alkyl aluminum hydride such as di -sec- nonyl hydride, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropylaluminum methoxide and dialkylaluminum alkoxide such as diisobutylaluminum ethoxide and the like.

These compounds are used alone or in combination of two or more.
Examples of general formula (VI) include lithium aluminum hydride.
Moreover, as an example of general formula (VII), the dialkyl zinc compound etc. which were described in Unexamined-Japanese-Patent No. 2003-171212 etc. are mentioned, It can also use in combination with a phenol compound etc.

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

  As the compound (c-3) which reacts with the component (A) and the component (B) to form an ion pair, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005 Lewis acids, ionic compounds, borane compounds and carborane compounds, and heteropoly compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. 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, the olefin compound exhibits not only very high polymerization activity but also active hydrogen in the solid support. The component (C) preferably contains at least the organoaluminum oxy compound (c-2) because a solid support component that reacts and contains a promoter component can be easily prepared.

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

The order of adding each component is arbitrary, but as a preferred order, for example,
(I) Method of adding component (C), component (A), and component (B) to the polymerization system in this order (ii) Component (C), component (B), and component (A) in the polymerization system in this order (Iii) Method of adding component (A) and component (C) in contact with mixing to the polymerization system, and then adding component (B) to the polymerization system (iv) Component (B) ) And component (C) are mixed and contacted and added to the polymerization system, and then component (A) is added to the polymerization system. (V) component (C) is added to the polymerization system, Method of adding a contact product obtained by mixing and contacting component (A) and component (B) into the polymerization system (vi) Adding component (C), component (A), and component (B) to the polymerization system in this order. (Vii) Component (C), component (B) and component (A) are added to the polymerization system in this order, and component (C) is added again to the polymerization system. Add to Method (viii) A contact product obtained by mixing and contacting the component (A) and the component (C) is added to the polymerization system, and then the component (B) is added to the polymerization system, and then the component (C) is again added to the polymerization system. (Ix) A contact product obtained by mixing and contacting the component (B) and the component (C) is added to the polymerization system, and then the component (A) is added to the polymerization system, and then the component (C )) In the polymerization system (x) After adding the component (C) to the polymerization system and then adding the contact product obtained by mixing and contacting the component (A) and the component (B) into the polymerization system, The method of adding a component (C) in a polymerization system again etc. is mentioned. Among these, particularly preferable contact order includes the above (i), (ii) and (v).

  The second olefin polymerization catalyst according to the present invention contains a solid catalyst component (X) comprising the following solid carrier (S) in addition to the component (A), the component (B) and the component (C). It becomes. Examples of such a catalyst include a solid catalyst component (X-A) formed from the solid carrier (S), component (C) and component (A), and a solid carrier (S) and component (C). And a catalyst for olefin polymerization comprising a solid catalyst component (X-B) formed from component (B), and solid support (S), component (A), component (B) and component (C). There is an olefin polymerization catalyst comprising a solid catalyst component (X-C), and an olefin polymerization catalyst comprising the solid catalyst component (X-C) is preferred.

Although the contact order of each component is arbitrary, as a preferable method, for example,
(Xi) The component (C) and the solid support (S) are brought into contact, and then the component (A) is brought into contact with the solid catalyst component (X-A), the component (C), and the component (S) brought into contact with each other. Then, the method using the solid catalyst component (X-B) prepared by contacting the component (B) (xii) The component (A) and the component (C) are mixed and contacted, and then the solid support (S) is contacted The method using the solid catalyst component (XB) prepared by bringing the solid catalyst component (X-A), the component (B) and the component (C) into contact with each other and then contacting the component (S) (xiii) ) Solid catalyst component (X-A), component (C) and solid prepared by bringing component (C) into contact with the solid carrier (S) and then contacting the contact product of component (A) with component (C) The solid catalyst component (S) prepared by contacting the carrier (S) and then contacting the contact product of component (B) and component (C) ( -B) Method (xiv) Solid catalyst component (X) prepared by contacting component (C) with solid support (S), then contacting component (A), and again contacting component (C) Solid catalyst component (X-B) prepared by bringing -A), component (C) and solid support (S) into contact, then contacting component (B), and then contacting component (C) again Method (xv) Solid catalyst component (X-C) prepared by bringing component (C) into contact with solid support (S) and then contacting component (A) and then contacting component (B). Method used (xvi) Solid catalyst component (X-C) prepared by bringing the component (C) into contact with the solid support (S) and then contacting the component (B) and then contacting the component (A) (Xvii) The component (C) is mixed and contacted with the solid carrier (S), and then the component (A) and A method of using a partial (B) a solid catalyst component prepared by contacting a contact mixture of the (X-C),
(Xviii) A method using the solid catalyst component (X-C) prepared by bringing the component (A) and the component (B) into contact with each other, then contacting with the component (C), and subsequently contacting with the solid support (S). ,
(Xix) A solid catalyst component prepared by bringing the component (C) into contact with the solid support (S), further contacting the component (C), and then contacting the component (A) and the component (B) in this order. (Xx) Method using (X-C) (xx) The component (C) is brought into contact with the solid carrier (S), and the component (C) is further brought into contact, and then in the order of the component (B) and the component (A). Method using solid catalyst component (X-C) prepared by contacting (xxi) After contacting component (C) with solid support (S), further contacting component (C), then component (A) Using the solid catalyst component (X-C) prepared by contacting a contact mixture of the component (B) and the component (B) (xxii) The component (C) is mixed and contacted with the solid support (S), and then the component (A) and Method using solid catalyst component (X-C) prepared by contacting a contact mixture of component (B) and component (C) xxiii) Solid catalyst component (C) prepared by bringing component (C) into contact with the solid support (S), then contacting the contact mixture of component (A) and component (C), and then contacting component (B). (Xxiv) The component (C) is mixed and contacted with the solid carrier (S), then the contact mixture of the component (B) and the component (C) is contacted, and the component (A) is further contacted. (Xxv) The component (C) is brought into contact with the solid support (S), and the component (C) is further brought into contact with the solid catalyst component (X-C). Method of using solid catalyst component (X-C) prepared by contacting a contact mixture of component (C) and a contact mixture of component (B) and component (C) in this order (xxvi) component on solid support (S) After contacting (C) and further contacting component (C), then component (B) and component (C ), A method using a solid catalyst component (X-C) prepared by contacting a contact mixture of component (A) and component (C) in this order (xxvii) component (C) on solid support (S) Using the solid catalyst component (X-C) prepared by contacting the component (C) and then contacting the component (C) and then contacting the contact mixture of the component (A), the component (B) and the component (C) (Xxviii) A mixture of component (A) and component (C) and a mixture of component (B) and component (C) are mixed in advance, and this is brought into contact with the contact between the solid carrier (S) and component (C). (Xxix) A mixture of component (A) and component (C) and a mixture of component (B) and component (C) are mixed in advance, and this is used as a solid support. (S), component (C), and solid catalyst component prepared by bringing the component (C) into contact with the contact product Such as X-C) a method using thereof.

  When a plurality of components (C) are used, the components (C) may be the same or different. Among these, particularly preferable contact order includes (xi), (xiii), (xv), (xvi), (xvii), (xxii), (xxiii) and (xxiv).

  Examples of the solvent used for the preparation of the solid catalyst component (X) include inert hydrocarbon solvents. Specifically, aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Examples thereof 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. It is done.

  In each method showing the above contact order form, the step including the contact of the solid support (S) and the component (C), the step including the contact of the solid support (S) and the component (A), the solid support (S ) And the component (B), and in the step including the contact of the solid carrier (S), the component (A) and the component (B), (g-1) a polyalkylene oxide block as the component (G) (G-2) higher aliphatic amide, (g-3) polyalkylene oxide, (g-4) polyalkylene oxide alkyl ether, (g-5) alkyldiethanolamine, and (g-6) polyoxyalkylene alkylamine At least one compound selected from may be coexistent. By allowing the component (G) to coexist, fouling during the polymerization reaction can be suppressed, and the particle properties of the resulting polymer are improved. Among the components (G), (g-1), (g-2), (g-3), and (g-4) are preferable.

  By contacting the component (C) with the solid support (S), the reaction between the reaction site in the component (C) and the reaction site in the solid support (S) causes the component (C) and the solid support (S) to Chemically bound to form a contact between component (C) and solid support (S). The contact time between the component (C) and the solid carrier (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. It is. When the initial contact between the component (C) and the solid support (S) is abruptly performed, the solid support (S) collapses due to reaction heat generation or reaction energy, and the morphology of the resulting solid catalyst component (X) deteriorates. However, when this is used for polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, the initial contact between the component (C) and the solid carrier (S) is performed at a low temperature of −20 to 30 ° C. for the purpose of suppressing the reaction exotherm, or the reaction exotherm is controlled to set the initial contact temperature. It is preferable to react at a maintainable rate. The same applies to the case where the component (C) is brought into contact with the solid carrier (S) and the component (C) is further brought into contact. 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 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 preferred 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 Preferably, it is 0.4-2.0.

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

Next, the solid carrier (S) will be described in detail.
The solid carrier (S) that can be used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate solid.

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

Examples of the porous oxide include porous oxides having compositions such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or these compositions Or a mixture of these porous oxides, specifically, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ — Examples thereof include porous oxides having compositions such as V ₂ O ₅ , SiO ₂ —Cr ₂ O _3, and SiO ₂ —TiO ₂ —MgO. Of these, porous oxides mainly composed of SiO ₂ are preferred.

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

Such porous oxides have different properties depending on the type and production method, but 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 after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, for _{example, MgCl 2, MgBr 2, MnCl} 2, MnBr 2 and the like. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated into fine particles by a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchange layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion exchange layered compound, clay, clay mineral, ionic crystal compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, and the like.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface, a treatment that affects 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 matter treatment, and the like. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Etc. These compounds are used alone or in combination of two or more. Polymerization obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.), etc., when intercalating these compounds And colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include an oxide generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  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, (co) polymer or vinyl produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. Examples thereof include (co) polymers and reactants produced mainly from cyclohexane, styrene and divinylbenzene, and granular or fine particle solids composed of modified products thereof.

  Further, it is obtained by insolubilizing the component (C) by a method described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO2010 / 55652A1 pamphlet or the like. The solid component can also be used as a solid carrier (S). In this case, the contact with the component (C) in the preparation method of the second olefin polymerization catalyst is not essential.

The solid carrier (S) is preferably at least one selected from a porous oxide or a solid component obtained by insolubilizing the component (C) from the viewpoint of preventing foreign matters during molding.
The use ratio of the component (A) to the component (B) can be appropriately determined according to the molecular weight and molecular weight distribution of the polymer to be produced.

  For the (co) polymerization of olefin, the solid catalyst component (X) as described above can be used as it is, but the solid catalyst component (X) is prepolymerized to form a prepolymerized catalyst component (XP). It can also be used after.

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

  The prepolymerized catalyst component (XP) prepared in the inert hydrocarbon solvent is separated from the suspension, and then suspended again in the inert hydrocarbon, and the olefin is introduced into the resulting 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. Moreover, a component (C) is used as needed, and especially the organoaluminum compound shown by the said Formula (V) in (c-1) is used preferably. When the organoaluminum compound of the formula (V) is used as the component (C), the molar ratio between the aluminum atom (Al-C) in the component (C) and the transition metal compound as the components (A) and (B) (Component (C) / transition metal compound) and is usually used in an amount of 0.1 to 10,000, preferably 0.5 to 5000.

  The concentration of the solid catalyst component (X) in the prepolymerization system is usually 1 to 1000 grams / liter, preferably 10 to 500 grams / liter, in a ratio of 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 particle properties.

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

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 0.1 to 100 parts by weight of the solid catalyst component (X). 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 of 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 the preparation of 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 the hydrocarbon as a dispersion medium from the suspension of the prepolymerization catalyst obtained by filtration or the like.

  The prepolymerization catalyst component (XP) is dried by maintaining the prepolymerization catalyst component (XP) at a temperature in the range of 70 ° C. or less, preferably 20 to 50 ° C. under the flow of an inert gas. The amount of volatile components of the obtained dry prepolymerization catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dry prepolymerization catalyst is preferably as small as possible, and there is no particular lower limit, but it is practically 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature. When the amount of the volatile component of the dry prepolymerization catalyst exceeds 2.0% by weight, the fluidity of the dry prepolymerization catalyst is lowered, and it may be impossible to stably supply the polymerization reactor.

Here, the amount of volatile components 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 dried prepolymerized catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is determined and expressed as a percentage of the dried prepolymerized 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 then calculated from the GC area as weight%.

  As a method for measuring the amount of volatile components in the dry prepolymerized catalyst, when the amount of volatile components in the dry prepolymerized catalyst is about 1% by weight or more, a weight reduction method is adopted, and the amount of volatile components in the dry prepolymerized catalyst is about 1 When the content is not more than% by weight, a method using gas chromatography is employed.

  Examples of the inert gas used for drying the prepolymerization catalyst component (XP) include nitrogen gas, argon gas, and neon gas. 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 moisture 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 greatly reduced.

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

[Olefin polymer production method (polymerization method)]
Next, it describes regarding the polymerization method of the olefin polymer which concerns on this invention. An olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the above-mentioned catalyst for olefin polymerization. In the present invention, by using the olefin polymerization catalyst, it has high polymerization activity, is excellent in molding processability and mechanical strength, and can efficiently produce an ethylene copolymer having many long chain branches. Preferably, ethylene is included as the olefin. The ethylene-based polymer in the present invention refers to a polymer having an ethylene content of 10 mol% or more in the polymer.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but the solution polymerization method is preferred under the first olefin polymerization catalyst according to the present invention, Suspension polymerization and gas phase polymerization are preferred under the second olefin polymerization catalyst.

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

When the olefin polymerization is carried out using the olefin polymerization catalyst, the component (A) and the component (B) are usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 mol, per liter of reaction volume. Used in such an amount as to be ^-2 mol. Component (C) is used, and an organoaluminum compound represented by general formula (V) in (c-1) is particularly preferred and used.

Moreover, 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., particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. During polymerization, the component (G) can be present together for the purpose of suppressing fouling or improving particle properties.

  Moreover, the olefin supplied to the polymerization reaction in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably one or more monomers selected from olefins having 2 to 20 carbon atoms. Specific examples of the olefin having 2 to 20 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-eicocene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4 And cyclic olefins such as 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; and the like. Specific examples of the olefin include, for example, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and the like; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid And polar monomers.

(Ethylene polymer)
The ethylene-based polymer of the present invention is obtained including a step of copolymerizing ethylene and one or more monomers selected from olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst. The ethylene polymer is not particularly limited, but usually has the following requirement (1), preferably has one or more of requirements (1) and requirements (2) to (5), more preferably Has the characteristics shown in all of the requirements (1) to (5). In addition, the measuring method of these requirements is as describing in an Example.

(1) a density of at 875kg / m ³ or more 945 kg / m ³ or less, the lower limit is preferably 885kg / m ^3, more preferably at 900 kg / m ^3, the upper limit is preferably 935 kg / m ^3, more preferably 930kg / M ³ .

  When the density is equal to or higher than the lower limit, the surface of the film formed from the ethylene polymer is less sticky and has excellent blocking resistance. When the density is equal to or lower than the upper limit, the impact of the film formed from the ethylene polymer. Strength is good, and 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-based polymer. The smaller 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 an ethylene polymer is determined by the composition ratio of α-olefin and ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)). For this reason, the ethylene polymer which has the density of the said range can be manufactured by increasing / decreasing (alpha) -olefin / ethylene.

  (2) Melt flow rate [MFR (g / 10 min)] under a load of 2.16 kg at 190 ° C. in accordance with the standard method of ASTM D1238-89 is not particularly limited, but is 0.01 to 100 g / 10 Minutes are preferred. The lower limit is more preferably 0.1 g / 10 minutes, even more preferably 0.5 g / 10 minutes, and the upper limit is more preferably 50 g / 10 minutes, even more preferably 30 g / 10 minutes.

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

(3) The ratio [MT / η * (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec, Although not particularly limited, it is preferably 6.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ . The lower limit is more preferably 1.0 × 10 ⁻⁴ , and the upper limit is more preferably 6.0 × 10 ⁻⁴ .

  MT / η * indicates the melt tension per unit shear viscosity. When this value is large, the melt tension increases with respect to the shear viscosity. That is, when MT / η * is equal to or greater than the lower limit, the ethylene polymer has a good balance between extrusion characteristics and bubble stability or neck-in. Further, when MT / η * is equal to or less than the upper limit value, high-speed moldability is good in the ethylene-based polymer.

  MT / η * is considered to depend on the long-chain branching content of the ethylene polymer. The larger the long-chain branching content, the larger MT / η *, and the smaller the long-chain branching content, the smaller MT / η *. Tend.

  (4) Intrinsic viscosity [[η] (dl / g)] measured in decalin at 135 ° C. and weight average molecular weight measured by gel permeation chromatography (GPC) -viscosity detector method (GPC-VISCO) ( Mw) is not particularly limited, but preferably satisfies the following relational expression (Eq-1).

0.48 × 10 ⁻⁴ × Mw ^0.776 ≦ [η] ≦ 2.35 × 10 ⁻⁴ × Mw ^0.776 ----- (Eq-1)
The lower limit is more preferably 0.98 × 10 ⁻⁴ × Mw ^0.776 , even more preferably 1.10 × 10 ⁻⁴ × Mw ^0.776 , and the upper limit is more preferably 2.25 × 10 ⁻⁴ × Mw ^0.776 , even more preferably Is 2.15 × 10 ⁻⁴ × Mw ^0.776 .

It is known that when long chain branching is introduced into an ethylene polymer, the intrinsic viscosity [η] (dl / g) is smaller for the molecular weight than a straight chain ethylene polymer without long chain branching. (For example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p.137 (1999)). Therefore, even in the present ethylene-based polymer, when the intrinsic viscosity [η] (dl / g) is 2.35 × 10 ⁻⁴ × Mw ^0.776 or less, it has a large number of long chain branches. Excellent fluidity.

(5) The vinylidene group content (number / 1000C) per 1000 carbon atoms determined by ¹ H-NMR is not particularly limited, but is preferably 0.23 / 1000C or less, more preferably 0.8. 20 pieces / 1000 C or less. The lower limit of the vinylidene group content is not particularly limited, but is usually 0.05 / 1000C.

  A vinylidene group is produced by, for example, a β-hydrogen elimination reaction after insertion of an α-olefin in the polymerization system, and the vinylidene group content increases as the α-olefin content increases. The fewer unsaturated bonds such as vinylidene groups, the better the weather resistance in the ethylene polymer.

  In order to suppress variation in physical property values, the ethylene polymer particles obtained by the polymerization reaction and other components added as desired are melted by an arbitrary method, kneaded, granulated, and the like.

The ethylene polymer obtained in the present invention may be pelletized by the following method.
(I) A method of mechanically blending an ethylene-based polymer and other components added as required using an extruder, a kneader or the like, and cutting the mixture into a predetermined size.

  (Ii) Dissolve the ethylene polymer and other components added as desired in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then remove the solvent. Removal and then mechanically blending using an extruder, kneader, etc. and cutting to a predetermined size.

  The ethylene polymer obtained in the present invention is a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, as long as the object of the present invention is not impaired. Additives such as dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be blended as necessary.

  The ethylene polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives are processed by general film molding, blow molding, injection molding and extrusion molding. In film molding, it can be obtained by extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multistage cooling, high-speed processing) and the like. A film obtained using the ethylene-based polymer can be used even in a single layer, but various functions can be imparted by forming a multilayer. In that case, the coextrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion by a lamination method such as extrusion lamination or dry lamination is mentioned. Production of high-functional products by multilayering by co-extrusion methods in blow molding, injection molding, and extrusion molding is possible in the same manner as film molding.

  As a 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 additives, a film, a blown infusion bag, a blow bottle, a gasoline tank, Examples include tubes, pipes, tear caps by extrusion molding, injection molded products such as daily goods, fibers, and large molded products by rotational molding.

  Furthermore, the film obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin or an additive, includes a water packaging bag, a liquid soup bag, a liquid paper container. , Lami fabric, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging packaging films, protective films, infusion bags, agriculture Suitable for materials for use. It can also be used as a multilayer film by being bonded to a base material such as nylon or polyester.

The following examples further illustrate the present invention. In addition, this invention is not limited to description of a following example.
<(1) Synthesis of Component (A)>
[Synthesis Example 1]
Dimethylsilylene-1- (3-n-propylcyclopentadienyl) -1- (cyclopentadienyl) zirconium dichloride (hereinafter referred to as component (A-1)) was synthesized by the method described in Japanese Patent No. 5455354. did.

[Synthesis Example 2-1]
In a 100 mL reactor sufficiently dried and purged with argon, 2.30 mL (19.2 mmol) of dimethylsilyl dichloride and 15 mL of tetrahydrofuran were charged and stirred. A 50 mL reactor that had been thoroughly dried and purged with argon was charged with 7.50 mL of a sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 15.0 mmol) and 8.0 mL of tetrahydrofuran and stirred. This sodium cyclopentadienide diluted solution was added dropwise to the dimethylsilyl dichloride diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 15 mL of n-hexane was added to the obtained solid to prepare a suspension, and insoluble matters were removed with Celite on a glass filter. After the solvent of the obtained solution was distilled off, 10 mL of tetrahydrofuran was added to the residue. In a 100 mL reactor thoroughly dried and purged with argon, 1.93 g (14.2 mmol) of 1-n-butyl-3-methylcyclopentadiene and 25 mL of tetrahydrofuran were charged, and 10.0 mL of n-butyllithium solution (hexane solution, 1.58M, 15.8 mmol) was added under ice cooling, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 14 hours while slowly returning to room temperature. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain (4-n-butyl-2-methylcyclopentadienyl) (cyclopentadienyl) dimethylsilane. 1.29 g of a 70:30 mixture (analyzed with a gas chromatograph mass spectrometer) of benzene and dicyclopentadienyldimethylsilane was obtained.

[Synthesis Example 2-2]
In a 100 mL reactor sufficiently dried and purged with argon, 0.52 g of the mixture obtained in Synthesis Example 2-1, 10 mL of toluene, and 0.35 mL of tetrahydrofuran were charged and stirred. To this solution, 2.60 mL of n-butyllithium solution (hexane solution, 1.58M, 4.11 mmol) was added at room temperature, and stirring was continued in an oil bath at 40 ° C. for 2 hours. After the solvent was distilled off, 18 mL of diethyl ether was added to the resulting white powder to obtain a white suspension. This solution was cooled to −78 ° C., 0.47 g (2.03 mmol) of zirconium tetrachloride was added, and stirring was continued for 22 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After distilling off the solvent of the obtained solution, 3 mL of diethyl ether was added to the obtained solid, and an ultrasonic wave was irradiated to prepare a suspension, and insoluble matters were removed with a glass filter. After distilling off the solvent of the obtained solution, 5 mL of n-hexane was added to the obtained solid, and a suspension was prepared by irradiating with ultrasonic waves, and the insoluble matter was separated by filtration with a glass filter. Was dried under reduced pressure to give a white powdery compound dimethylsilylene-1- (3-n-butyl-1-methylcyclopentadienyl) -1- (cyclopentadienyl) represented by the following formula (A-2) ) 0.07 g of zirconium dichloride (hereinafter referred to as component (A-2)) was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.05 (1H, dt, J = 3.3 and 1.8 Hz, Cp—H), 6.93 (1 H, dt, J = 3.1 and 1.9 Hz, Cp—H ), 6.36 (1H, d, J = 2.3 Hz, Cp-H), 5.95 (1H, dt, J = 2.7 and 1.9 Hz, Cp-H), 5.78 (1H, dt, J = 2.7and1.9Hz, Cp-H) , 5.38 (1H, d, J = 2.3Hz, Cp-H), 2.74-2.47 (2H, m, Cp-CH 2 -) 2.14 (3H, d, J = 0.4 Hz, Cp—CH ₃ ), 1.57-1.25 (4H, m, —CH ₂ —CH ₂ —), 0.90 (3H, t, _{J = 7.2Hz, -CH 3),} 0.82 (3H, t, J = 3.6Hz, Si-CH 3), 0.70 (3H, t, J = 3.4 z, Si-CH ₃₎ ppm
FD-mass spectrometry (field desorption mass spectrometry) (M ⁺ ): 418

[Synthesis Example 3]
Bis (n-butylcyclopentadienyl) zirconium dichloride (hereinafter referred to as component (A-3)) was purchased from Wako Pure Chemical Industries and used as it was.

<Synthesis of (2) Component (B)>
[Synthesis Example 4-1]
1.11 g (3.32 mmol) of 2,7-di-tert-butyl-4-n-butylfluorene synthesized by a method described in JP-A No. 2014-196274 in a 200 mL reactor thoroughly dried and substituted with argon , 25 mL of tert-butyl methyl ether was charged. 2.20 mL of n-butyllithium solution (hexane solution, 1.64 M, 3.61 mmol) was added to this solution at room temperature. The mixture was stirred at room temperature for 15 hours and then ice-cooled. A solution of 0.32 g (3.00 mmol) of 6,6-dimethylfulvene purchased from Aldrich was diluted with 10 mL of tert-butyl methyl ether, and heated to reflux for 1 hour in an oil bath. did. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution 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 the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and 2- (cyclopentadienyl) -2- (9 represented by the following formula (B-1L) was obtained. -(2,7-di-tert-butyl-4-n-butylfluorenyl))-propane (hereinafter referred to as ligand (B-1L)) is 0.96 g (yield 73%) isomer Obtained as a mixture.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.68-7.28 (2H, m, Ar—H), 7.24-6.93 (3H, m, Ar—H), 6.69-6. 41 (2H, m, C = CH-CH =), 6.12-5.84 (1H, m, CH = CH-CH 2), 4.10-4.00 (1H, m, Ar-CH- Ar), 3.20-3.02 (2H, m , -CH 2 -), 3.02-2.92 (2H, m, Ar-CH 2 -), 1.77-1.62 (2H, m, —CH ₂ —), 1.55-1.44 (2H, m, —CH ₂ —), 1.31-1.26 (18H, m, —C (CH ₃ ) ₃ ), 1.07 _{-0.93 (9H, m, -CH 3} ) ppm

[Synthesis Example 4-2]
In a 100 mL reactor sufficiently dried and purged with argon, 0.22 g (0.50 mmol) of the ligand (B-1L) obtained in Synthesis Example 4-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. . To this solution, 0.61 mL of n-butyllithium solution (hexane solution, 1.64 M, 1.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. The solution was cooled to −30 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued for 16 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 8 mL of dichloromethane was added to the obtained solid to prepare a suspension, and insolubles were removed with Celite on a glass filter. After distilling off the solvent of the obtained solution, 2 mL of n-hexane was added to the obtained solid, and a suspension was prepared by irradiating with ultrasonic waves. Insoluble matter was filtered off with a glass filter, and the residue Was dried under reduced pressure to give orange powdery isopropylidene (cyclopentadienyl) (9- (2,7-di-tert-butyl-4-n-butylfluorene) represented by the following formula (B-1). Nil)) zirconium dichloride (hereinafter referred to as component (B-1)) 0.15 g (yield 49%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 8.85 (1H, d, J = 9.1 Hz, Ar—H), 7.80 (1H, s, Ar—H), 7.67-7.60 ( 2H, m, Ar-H), 7.36 (1H, s, Ar-H), 6.28 (2H, t, J = 2.7 Hz, Cp-H), 5.65 (2H, t, J = 2.7Hz, Cp-H), 3.10 (2H, t, J = 7.7Hz, Ar-CH 2 -), 2.42 (6H, d, J = 3.3Hz, -CH 3), _{1.90-1.70 (2H, m, -CH 2} -), 1.70-1.55 (2H, m, -CH 2 -), 1.35 (18H, d, J = 4.6Hz, _{-C (CH 3) 3),} 0.99 (3H, t, J = 7.3Hz, -CH 3) ppm
FD-mass spectrometry (M ⁺ ): 600

[Synthesis Example 5-1]
In a fully dry, argon-substituted 300 mL reactor, 11.70 g of n-butylcyclopentadiene solution (tetrahydrofuran solution, 25 wt%, 24.0 mmol) and 40 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., 16.3 mL of n-butyllithium solution (hexane solution, 1.60 M, 26.0 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. To this solution, 1.34 g (14.1 mmol) of magnesium chloride was added, and the mixture was heated to reflux for 2 hours in an oil bath. The reaction solution was cooled in an ice bath, 2.33 mL (20.0 mmol) of acetophenone was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours, and then stirred at room temperature for 18 hours. A 2.0 M aqueous hydrochloric acid solution was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 6-phenyl-6- (2-methoxyethyl) fulvene represented by the following formula (B-2F). (Hereinafter referred to as compound (B-2F)) was obtained as an isomer mixture of 0.51 g (yield 11%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.42-7.31 (5H, m, Ar—H), 6.62 (0.5H, dd, J = 5.3 and 2.1 Hz, C = CH—C ), 6.46 (0.5 H, dd, J = 5.2 and 1.3 Hz, C = CH—C), 6.37 (0.5 H, dd, J = 5.0 and 1.1 Hz, C = CH—C) ), 6.28 (0.5 H, t, J = 1.5 Hz, C = CH—C), 6.14 (0.5 H, dd, J = 5.2 and 2.1 Hz, C = CH—C), 5.84 (0.5 H, t, J = 1.5 Hz, C = CH—C), 2.49 (3 H, s, —CH ₃ ), 2.43 (1 H, t, J = 7.9 Hz, _{-CH 2 -C 3 H 7),} 2.35 (1H, t, J = 7.7Hz, -CH 2 -C 3 H 7), 1.68-1.20 (4H, m, -CH 2 - C _{2 4 -CH 3), 1.00-0.82 (3H} , m, -C 3 H 6 -CH 3) ppm

[Synthesis Example 5-2]
In a 300 mL reactor thoroughly dried and purged with argon, Synthesis 1984, 335. 1.46 g (5.24 mmol) of 2,7-di-tert-butylfluorene synthesized by the method described above and 25 mL of tert-butyl methyl ether were charged. 3.44 mL of n-butyllithium solution (hexane solution, 1.60 M, 5.50 mmol) was added to this solution and stirred at room temperature for 18 hours. This solution was ice-cooled, a diluted solution of 1.12 g (4.99 mmol) of the compound (B-2F) obtained in Synthesis Example 5-1 in 10 mL of tert-butyl methyl ether was added, and the mixture was heated to reflux for 1 hour in an oil bath. did. After cooling this solution to room temperature, a saturated aqueous ammonium chloride solution was added, and the soluble portion was extracted with n-hexane. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was washed with methanol, and 1- (3-n-butylcyclopentadienyl) -1- represented by the following formula (B-2L) An isomer mixture of 1.21 g (yield 48%) of (9- (2,7-di-tert-butylfluorenyl))-1-phenylethane (hereinafter referred to as ligand (B-2L)) As obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75-7.16 (10H, m, Ar—H), 6.92-6.73 (1H, m, Ar—H), 6.38-5. 90 (2H, m, C = CH-C), 4.94-4.85 (1H, m, Ar-CH-Ar), 3.34-2.80 (2H, m, C-CH 2 -CH =), 2.54-2.25 (2H, m , -CH 2 -C 3 H 7), 1.67-1.30 (4H, m, -CH 2 -C 2 H 4 -CH 3), _{1.54 (3H, s, -CH 3} ), 1.28-1.20 (9H, m, Ar-C (CH 3) 3), 1.06-0.98 (9H, m, Ar-C _{(CH 3) 3), 0.98-0.87} (3H, m, -C 3 H 6 -CH 3) ppm

[Synthesis Example 5-3]
In a 100 mL reactor sufficiently dried and purged with argon, 0.25 g (0.50 mmol) of the ligand (B-2L) obtained in Synthesis Example 5-2, 5 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. . To this solution, 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 45 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 5 mL of diethyl ether was added to the obtained solid. This solution was slowly added to a suspension of 0.11 g (0.49 mmol) of zirconium tetrachloride cooled to 0 ° C. in diethyl ether, followed by stirring at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, 10 mL of n-hexane was added and the mixture was irradiated with ultrasonic waves to prepare a suspension, and insolubles were filtered off with a glass filter. After distilling off the solvent of the obtained solution, 10 mL of n-hexane was added to the obtained solid, and a suspension was prepared by irradiating with ultrasonic waves. Insoluble matter was filtered off with a glass filter, and the residue By drying under reduced pressure, an orange powdery phenylethylidene (cyclopentadienyl) (9- (2,7-di-tert-butylfluorenyl)) zirconium dichloride represented by the following formula (B-2) Hereinafter, component (B-2)) was obtained as an isomer mixture of 0.03 g (yield 8%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 8.10-7.30 (10 H, m, Ar—H), 6.07 (0.5 H, t, J = 2.7 Hz, Cp—H), 6. 06 (0.5H, m, Ar-H), 6.02 (0.5H, m, Ar-H), 5.95 (0.5H, t, J = 2.5 Hz, Cp-H), 5 .72 (0.5H, t, J = 3.1 Hz, Cp-H), 5.51 (0.5H, t, J = 3.0 Hz, Cp-H), 5.47 (0.5H, t , J = 2.7 Hz, Cp-H), 5.27 (0.5 H, t, J = 2.7 Hz, Cp-H), 2.53 (1.5 H, s, -CH ₃ ), 2. _{50 (1.5H, s, -CH 3} ), 2.48-2.17 (4H, m, -CH 2 -C 3 H 7), 1.56-1.18 (4H, m, -CH 2 _{-C 2 H 4 -CH 3),} 1.38 (9H _{s, Ar-C (CH 3} ) 3), 0.97 (9H, s, Ar-C (CH 3) 3), 0.92-0.80 (3H, m, -C 3 H 6 -CH 3 ) Ppm
FD-mass spectrometry (M ⁺ ): 662

[Synthesis Example 6]
Diphenylmethylene (η ⁵ -3-n-butylcyclopentadienyl) {η ^5- (2,7-di-tert-butylfluorenyl)} zirconium dichloride (hereinafter referred to as component (B-3)) is It was synthesized by the method described in WO2009 / 045301.

[Synthesis Example 7-1]
Into a 200 mL reactor thoroughly dried and purged with argon, 1.34 g (14.1 mmol) of magnesium chloride and 15 mL of tetrahydrofuran were charged and stirred. To this solution was added 6.00 mL of a sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 12.0 mmol), and the mixture was heated to reflux for 2 hours in an oil bath. The reaction mixture was cooled in an ice bath, Am. Chem. Soc. 1991, 113, 9251. A 5-mL diluted solution of 1.67 g (10.2 mmol) of 3-methoxypropiophenone synthesized by the method described above was added, stirred in an oil bath at 50 ° C. for 5 hours, and then stirred at room temperature for 18 hours. A 2.0 M aqueous hydrochloric acid solution was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 6-phenyl-6- (2-methoxyethyl) fulvene represented by the following formula (B-4F). 0.75 g (yield 35%) of the compound (hereinafter referred to as compound (B-4F)) was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.42-7.35 (5H, m, Ar—H), 6.69-6.61 (1H, m, C═CH—C), 6.47 ( 1H, dt, J = 5.3 and 1.8 Hz, C = CH—C), 6.52-6.43 (1H, m, C = CH—C), 6.14-6.06 (1H, m, C = CH—C), 3.43 (2H, t, J = 7.1 Hz, —CH ₂ —CH ₂ —OCH ₃ ), 3.26 (3H, s, —CH ₂ —CH ₂ —OCH ₃ ) , 3.19 (2H, t, J = 7.2Hz, -CH 2 -CH 2 -OCH 3) ppm

[Synthesis Example 7-2]
In a 200 mL reactor thoroughly dried and purged with argon, Synthesis 1984, 335. 1.04 g (3.74 mmol) of 2,7-di-tert-butylfluorene synthesized by the method described above and 20 mL of tert-butyl methyl ether were charged. To this solution was added 2.53 mL of n-butyllithium solution (hexane solution, 1.60 M, 4.05 mmol), and the mixture was stirred at room temperature for 2 hours. This solution was ice-cooled, and a diluted solution of 0.72 g (3.38 mmol) of the compound (B-4F) obtained in Synthesis Example 7-1 in 15 mL of tert-butyl methyl ether was added, and the mixture was heated to reflux for 2 hours in an oil bath. Thereafter, the mixture was stirred at room temperature for 18 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and 1- (cyclopentadienyl) -1- (9 represented by the following formula (B-4L) was obtained. -(2,7-di-tert-butylfluorenyl))-3-methoxy-1-phenylpropane (hereinafter referred to as ligand (B-4L)) is 1.46 g (yield 88%) of isomerism Obtained as a body mixture.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.72-6.82 (11H, m, Ar—H), 6.47-5.98 (3H, m, C═CH—C), 4.97- 4.78 (1H, m, Ar- CH-Ar), 3.15-2.97 (3H, m, -OCH 3), 2.97-2.25 (6H, m, -CH 2 -CH 2 _{-OCH 3 and C-CH 2 -CH} =), 1.24-1.12 (18H, m, Ar-C (CH 3) 3) ppm

[Synthesis Example 7-3]
In a 100 mL reactor sufficiently dried and purged with argon, 0.27 g (0.55 mmol) of the ligand (B-4L) obtained in Synthesis Example 7-2, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. . To this solution, 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.11 g (0.48 mmol) of zirconium tetrachloride was added, and the mixture was stirred at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After concentration of the resulting solution under reduced pressure, 10 mL of n-hexane was added, and ultrasonic waves were applied to prepare a suspension, insoluble matters were filtered off with a glass filter, and the residue was dried under reduced pressure. An orange powdery phenyl-2-methoxyethylmethylene (cyclopentadienyl) (9- (2,7-di-tert-butylfluorenyl)) zirconium dichloride represented by the following formula (B-4) And 0.12 g (yield 37%) of the component (B-4)).

¹ H NMR (270 MHz, CDCl ₃ ) δ 8.07-7.41 (10H, m, Ar—H), 6.41 (1H, m, Cp—H), 6.27 (1H, m, Cp—) H), 6.08 (1H, m, Ar-H), 5.88 (1H, dd, J = 5.4 and 3.0 Hz, Cp-H), 5.58 (1H, dd, J = 5.4 and 3) .0Hz, Cp-H), 3.73-3.06 (4H, m, -CH 2 -CH 2 -OCH 3), 3.20 (3H, s, -OCH 3), 1.39 (9H, _{s, Ar-C (CH 3} ) 3), 0.98 (9H, s, Ar-C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 650

[Synthesis Example 8]
Phenyl-3-butenylmethylene (η ⁵ -cyclopentadienyl) {η ^5- (2,7-di-tert-butylfluorenyl)} zirconium dichloride (hereinafter referred to as component (B-5)) is J. et al. Mol. Catal. A: Chem. 2001, 165, 23. It was synthesized by the method described and the method described in Japanese Patent No. 5119160.

[Synthesis Example 9-1]
To a 500 mL reactor sufficiently dried and purged with argon, 3.20 g (23.1 mmol) of potassium tert-butoxide and 40 mL of tetrahydrofuran were charged and stirred. To this solution, 2.70 mL (20.2 mmol) of 4-methylacetophenone was slowly added under ice cooling, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added 24.0 mL of a triethylborane solution (tetrahydrofuran solution, 1.0 M, 24.0 mmol), and after stirring at room temperature for 30 minutes, 2.10 mL (24.8 mmol) of allyl bromide was slowly added. And stirred at room temperature for 13 hours. After cooling the reaction solution in an ice bath, a mixed solution of 12.0 mL of 30% aqueous hydrogen peroxide and 12.0 mL of 30 wt% aqueous sodium hydroxide was slowly added, stirred at room temperature for 30 minutes, and then ethyl acetate was added. Soluble components were extracted, and the obtained fractions were washed with 1.0 M aqueous hydrochloric acid, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and 1- (p-tolyl) -4-pentene-1 represented by the following formula (B-6K) was obtained. 1.94 g (yield 55%) of -one (hereinafter referred to as compound (B-6K)) was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.86 (2H, d, J = 8.2 Hz, Ar—H), 7.25 (2H, d, J = 8.0 Hz, Ar—H), 6. _{00-5.81 (1H, m, -CH 2} -CH 2 -CH = CH 2), 5.15-4.94 (2H, m, -CH 2 -CH 2 -CH = CH 2), 3. 04 (2H, t, J = 7.4Hz, -CH 2 -CH 2 -CH = CH 2), 2.55-2.43 (2H, m, -CH 2 -CH 2 -CH = CH 2), 2.41 (3H, s, Ar- CH 3) ppm

[Synthesis Example 9-2]
In a 100 mL reactor thoroughly dried and purged with argon, 1.40 g (14.7 mmol) of magnesium chloride and 15 mL of tetrahydrofuran were charged and stirred. To this solution was added 6.00 mL of a sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 12.0 mmol), and the mixture was heated to reflux for 2 hours in an oil bath. After cooling the reaction solution in an ice bath, a diluted solution of 1.75 g (10.0 mmol) of the compound (B-6K) obtained in Synthesis Example 9-1 in 15 mL of tert-butyl methyl ether was added, and an oil at 50 ° C was added. After stirring in the bath for 3 hours, the mixture was stirred at room temperature for 18 hours. A 1.0 M aqueous hydrochloric acid solution was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 6- (p-tolyl) -6- (3- 1.50 g (yield 67%) of butenyl) fulvene (hereinafter referred to as compound (B-6F)) was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.30-7.15 (4H, m, Ar—H), 6.61 (1H, dt, J = 5.3 and 1.7 Hz, C = CH—C), 6.56 (1H, dt, J = 5.3 and 1.8 Hz, C = CH—C), 6.47 (1 H, dt, J = 5.3 and 1.8 Hz, C = CH—C), 6.13 ( 1H, dt, J = 5.3 and 1.8 Hz, C = CH—C), 5.88-5.68 (1H, m, —CH ₂ —CH ₂ —CH═CH ₂ ), 5.03-4. _{89 (2H, m, -CH 2} -CH 2 -CH = CH 2), 2.99 (2H, t, J = 7.7Hz, -CH 2 -CH 2 -CH = CH 2), 2.39 ( _{3H, s, Ar-CH 3} ), 2.24-2.10 (2H, m, -CH 2 -CH 2 -CH = CH 2) ppm

[Synthesis Example 9-3]
In a 200 mL reactor thoroughly dried and purged with argon, Synthesis 1984, 335. 2.42 g (8.69 mmol) of 2,7-di-tert-butylfluorene synthesized by the method described above and 25 mL of tert-butyl methyl ether were charged. To this solution, 6.00 mL of n-butyllithium solution (hexane solution, 1.60 M, 9.60 mmol) was added and stirred at room temperature for 2 hours. This solution was ice-cooled, and a diluted solution of 1.79 g (8.04 mmol) of the compound (B-6F) obtained in Synthesis Example 9-2 in 15 mL of tert-butyl methyl ether was added, and the mixture was heated to reflux for 1 hour in an oil bath. did. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution 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 the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and 1- (cyclopentadienyl) -1- (9 represented by the following formula (B-6L) was obtained. 3.02 g (yield 75%) of-(2,7-di-tert-butylfluorenyl))-1- (p-tolyl) -4-pentene (hereinafter referred to as ligand (B-6L)) ) As an isomer mixture.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.49-6.94 (10H, m, Ar—H), 6.35-5.63 (4H, m, C═CH—C and —CH ₂ —CH _{2 -CH = CH 2), 5.06-4.86} (2H, m, -CH 2 -CH 2 -CH = CH 2), 4.86-4.69 (1H, m, Ar-CH-Ar ), 2.93-2.57 (2H, m, C—CH ₂ —CH═), 2.57-2.24 (5H, m, —CH ₂ —CH ₂ —CH═CH ₂ and Ar—CH _{3), 1.94-1.54 (2H, m} , -CH 2 -CH 2 -CH = CH 2), 1.26 (9H, d, J = 9.0Hz, Ar-C (CH 3) 3 ), 1.17 (9H, s, Ar-C (CH 3) 3) ppm

[Synthesis Example 9-4]
In a 100 mL reactor thoroughly dried and purged with argon, 0.25 g (0.50 mmol) of the ligand (B-6L) obtained in Synthesis Example 9-3, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. . To this solution, 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.01 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to −78 ° C., 0.11 g (0.46 mmol) of zirconium tetrachloride was added, and stirring was continued for 16 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, 10 mL of n-hexane was added and the mixture was irradiated with ultrasonic waves to prepare a suspension, and insolubles were filtered off with a glass filter. After distilling off the solvent of the obtained solution, 5 mL of n-hexane was added to the obtained solid, and a suspension was prepared by irradiating with ultrasonic waves, and the insoluble matter was separated by filtration with a glass filter. Was dried under reduced pressure to give orange powdery p-tolyl-3-butenylmethylene (cyclopentadienyl) (9- (2,7-di-tert-butylfull) represented by the following formula (B-6). Olenyl)) zirconium dichloride (hereinafter referred to as component (B-6)) was obtained in an amount of 0.17 g (yield 36%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 8.04 (1H, d, J = 9.2 Hz, Ar—H), 7.98 (1H, d, J = 8.9 Hz, Ar—H), 7. 71 (1H, dd, J = 7.9 and 2.1 Hz, Ar-H), 7.69-7.63 (2H, m, Ar-H), 7.57-7.45 (2H, m, Ar- H), 7.38 (1H, d, J = 7.9 Hz, Ar-H), 7.22 (1H, d, J = 8.0 Hz, Ar-H), 6.39 (1H, dd, J = 5.7 and 3.4 Hz, Cp-H), 6.26 (1H, dd, J = 5.6 and 3.4 Hz, Cp-H), 6.11 (1H, d, J = 0.9 Hz, Ar-H) ), 6.01-5.78 (1H, m, -CH 2 -CH 2 -CH = CH 2), 5.83 (1H, dd, J = 5.3and3.0Hz, C -H), 5.56 (1H, dd , J = 5.4and3.0Hz, Cp-H), 5.17-5.01 (2H, m, -CH 2 -CH 2 -CH = CH 2), _{3.27-3.08 (1H, m, -CH 2} -CH 2 -CH = CH 2), 2.85-2.64 (1H, m, -CH 2 -CH 2 -CH = CH 2), 2.44 (1H, s, Ar- CH 3), 2.42-2.25 (2H, m, -CH 2 -CH 2 -CH = CH 2), 1.37 (9H, s, Ar-C _{(CH 3) 3), 0.99} (9H, s, Ar-C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 660

[Synthesis Example 10-1]
Organometallics 2004, 23, 1777. In a 200 mL reactor thoroughly dried and purged with argon. 1.62 g (4.20 mmol) of octamethyloctahydrodibenzofluorene synthesized by the method described above and 30 mL of tert-butyl methyl ether were charged. 2.80 mL of n-butyllithium solution (hexane solution, 1.59 M, 4.45 mmol) was added to this solution. The mixture was stirred at room temperature for 17 hours and then ice-cooled. Mol. Catal. A: Chem. 2001, 165, 23. A 10 mL diluted solution of 0.87 g (4.19 mmol) of 6-phenyl-6- (3-butenyl) fulvene synthesized by the method described above was added to the solution, and the mixture was heated to reflux for 1 hour in an oil bath. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution 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 the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and 1- (cyclopentadienyl) -1- (9 represented by the following formula (B-7L) was obtained. -Octamethyloctahydrodibenzofluorenyl) -1-phenyl-4-pentene (hereinafter referred to as ligand (B-7L)) was obtained as an isomer mixture of 2.01 g (yield 81%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.45-6.85 (9H, m, Ar—H), 6.36-5.64 (4H, m, C═CH—C and —CH ₂ —CH _{2 -CH = CH 2), 5.06-4.84} (2H, m, -CH 2 -CH 2 -CH = CH 2), 4.82-4.65 (1H, m, Ar-CH-Ar ), 2.93-2.56 (2H, m, C—CH ₂ —CH═), 2.55-2.12 (2H, m, —CH ₂ —CH ₂ —CH═CH ₂ ), 1. 79-1.56 (10H, m, -C ( CH 3) 2 -CH 2 -CH 2 -C (CH 3) 2 - and -CH 2 -CH 2 -CH = CH 2), 1.40-0 .97 (24H, m, -C ( CH 3) 2 -) ppm

[Synthesis Example 10-2]
In a 100 mL reactor sufficiently dried and purged with argon, 0.30 g (0.50 mmol) of the ligand (B-7L) obtained in Synthesis Example 10-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. . To this solution, 0.63 mL of n-butyllithium solution (hexane solution, 1.59 M, 1.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. The solution was cooled to −30 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued for 16 hours while slowly returning to room temperature. After evaporating the solvent of the reaction solution, 5 mL of n-hexane was added to the obtained solid to prepare a suspension, and insoluble matters were removed with Celite on a glass filter. After the solvent of the obtained solution was distilled off, 5 mL of n-hexane was added to the obtained solid and cooled to −40 ° C. to crystallize an orange precipitate. The insoluble material was filtered off with a glass filter, the solvent of the resulting solution was distilled off, and the residue was dried under reduced pressure to give red powdery phenyl-3-butenylmethylene represented by the following formula (B-7). 0.11 g (yield 29%) of (cyclopentadienyl) (9-octamethyloctahydrodibenzofluorenyl) zirconium dichloride (hereinafter referred to as component (B-7)) was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 8.06 (1H, s, Ar—H), 8.01 (1H, s, Ar—H), 7.87-7.80 (1H, m, Ar— H), 7.66-7.54 (3H, m, Ar-H), 7.53-7.33 (3H, m, Ar-H), 6.38-6.30 (1H, m, Cp) -H), 6.24-6.17 (1H, m , Cp-H), 6.02-5.83 (2H, m, Ar-H and -CH 2 -CH 2 -CH = CH 2), 5.73 (1H, dd, J = 5.3 and 3.0 Hz, Cp-H), 5.46 (1 H, dd, J = 5.4 and 3.0 Hz, Cp-H), 5.17-5.02 ( _{2H, m, -CH 2 -CH 2} -CH = CH 2), 3.25-3.07 (1H, m, -CH 2 -CH 2 -CH = CH 2), 2.78-2.58 ( _{H, m, -CH 2 -CH 2} -CH = CH 2), 2.44-2.20 (2H, m, -CH 2 -CH 2 -CH = CH 2), 1.82-1.21 ( _{32H, m, -C (CH 3} ) 2 -CH 2 -CH 2 -C (CH 3) 2 -) ppm
FD-mass spectrometry (M ⁺ ): 754

[Synthesis Example 11]
Isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (hereinafter referred to as component (B-8)) is based on the method described in JP-A-4-69394. And synthesized.

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

  Subsequently, after making it contact at 0-5 degreeC for 30 minutes, the system temperature was heated up to 95 degreeC over 1.5 hours, and it was made to contact at 95 degreeC continuously for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 115 liters of a solid support (S-1) toluene slurry was prepared. When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 122.6 g / L.

[Preparation Example 2]
The solid carrier (S-2) was prepared according to the method described in WO2010 / 55652 (Preliminary Experiment 1 and Example 5). However, in consideration of safety such as ignition of trimethylaluminum, the concentration was about 1/6 times the condition disclosed in the document.

  Specifically, 100 mL of a toluene solution of trimethylaluminum prepared at 0.5 mol / L was charged into a glass reactor having a stirring device. This solution was cooled to 15 ° C., and 2.18 g of benzoic acid was slowly added thereto at such a rate that the temperature of the solution was 25 ° C. or lower. Thereafter, heat aging was performed at 50 ° C. for 1 hour. At this time, the molar ratio of trimethylaluminum to benzoic acid was 1.40. The reaction solution was heated at 70 ° C. for 4 hours, then heated at 60 ° C. for 6 hours, and then cooled to room temperature once. Subsequently, it heated at 100 degreeC for 8 hours, and the solid component was deposited. After cooling the solution to 30 ° C. or lower, 100 mL of hexane was added with stirring for washing. After standing for 30 minutes, 150 mL of the supernatant was removed, and 150 mL of hexane was further added with stirring. After standing for 15 minutes, 150 mL of the supernatant was removed, and 150 mL of hexane was further added with stirring. Finally, after standing for 15 minutes, 180 mL of the supernatant was removed, and hexane was added so that the total amount was 42 mL to prepare a hexane slurry of the solid carrier (S-2).

A part of the obtained slurry component was sampled and the concentration was examined. The slurry concentration was 14.2 g / L and the Al concentration was 0.202 mol / L. Further, when the particles of the obtained solid carrier (S-2) were observed with a scanning electron microscope, the average particle diameter was 6.8 μm, and the specific surface area was 18.1 m ² / mmol-Al.

<(4) Preparation of solid catalyst component>
[Preparation Examples 3 to 10]
A reactor equipped with a stirrer with an internal volume of 200 mL sufficiently purged with nitrogen was charged with 30 mL of toluene and 8.2 mL of the solid support (S-1) slurry obtained in Preparation Example 1 (solid content weight 1.0 g). . Next, a toluene solution of each of component (A) and component (B) shown in Table 16 (0.002 mmol / mL in terms of Zr atoms) was added and contacted at a system temperature of 20 to 25 ° C. for 1 hour. After the liquid was removed by decantation and further washed twice with heptane, a total amount of 50 mL of solid catalyst component (X-1) to (X-8) slurry was prepared.

[Preparation Example 11]
A reactor equipped with a stirrer with an internal volume of 200 mL sufficiently purged with nitrogen was charged with 30 mL of toluene and 14.1 mL of the solid carrier (S-2) slurry obtained in Preparation Example 2 (solid content weight 0.2 g). . Next, a toluene solution of each of component (A) and component (B) shown in Table 16 (0.002 mmol / mL in terms of Zr atoms) was added and contacted at a system temperature of 20 to 25 ° C. for 1 hour. After the liquid was removed by decantation and further washed twice with heptane, a total amount of 40 mL of solid catalyst component (X-9) slurry was prepared.

[Preparation Example 12]
200 mL of toluene and 245 mL of the solid carrier (S-1) slurry obtained in Preparation Example 1 (solid content weight: 30 g) were charged into a reactor equipped with a stirrer with an internal volume of 1 L that was sufficiently purged with nitrogen. Next, 0.18 mmol of the component (A-1) as the component (A) and 0.56 mmol of the component (B-5) as the component (B) in toluene (each 0.005 mmol / mL in terms of Zr atom) were added, After contact with the system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and further washed twice with heptane, and then a total amount of 600 mL of solid catalyst component slurry was prepared.

  After cooling the solid catalyst component slurry obtained above to 10 ° C., 57 mmol of diisobutylaluminum hydride (DiBAl—H) was added. Further, ethylene was continuously fed into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 8.0 mL of 1-hexene was added. After the addition of 1-hexene, the system temperature was raised to 35 ° C., and 3 equivalents of ethylene was polymerized in terms of weight with respect to the solid catalyst component. Thereafter, the supernatant was removed by decantation, washed 4 times with hexane, and then hexane was added to make a total volume of 600 mL. Next, after raising the temperature inside the system to 35 ° C., 2.2 g of a hexane solution of Chemistat (registered trademark) 2500 (manufactured by Sanyo Chemical Industries, Ltd.) was added as a component (G) and contacted for 2 hours. . Thereafter, the supernatant was removed by decantation and washed four times with hexane. Next, the hexane slurry obtained above was transferred to a glass filter, and 120 g of prepolymerized catalyst component (XP-10) was obtained by distilling off hexane by filtration and drying under reduced pressure.

[Preparation Example 13]
Except for using 0.29 mmol of component (A-1) as component (A) and 0.44 mmol of toluene solution (each 0.005 mmol / mL in terms of Zr atom) as component (B), A prepolymerized catalyst component (XP-11) was obtained in the same manner as in Preparation Example 12.

[Preparation Example 14]
Except for using 0.10 mmol of the component (A-1) as the component (A) and 0.63 mmol of the toluene solution (0.005 mmol / mL in terms of Zr atom respectively) of the component (B-8) as the component (B), A prepolymerization catalyst component (XP-12) was obtained in the same manner as in Preparation Example 12.

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

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

(3) Intrinsic viscosity (η, dL / g)
For the intrinsic viscosity, about 20 mg of a measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 as shown in the following formula (Eq-2) was expressed as the intrinsic viscosity [η] (unit: dl / g ).
[Η] = lim (η _sp / 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: Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The conditions are a resin temperature of 190 ° C., a melting time of 6 minutes, a barrel diameter of 9.55 mmφ, an extrusion speed of 15 mm / minute, a winding speed of 24 m / minute (if the molten filament breaks, the winding speed is 5 m / minute at a time. The nozzle diameter was 2.095 mmφ and the nozzle length was 8 mm.

(5) Shear viscosity (η *, P) at 200 ° C. and 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 measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a parallel plate of 25 mmφ was used as a sample holder, and the sample thickness was about 2.0 mm. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for the shear viscosity measurement was a press molding machine manufactured by Shinfuji Metal Industry, with a preheating temperature of 190 ° C., a preheating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kgf / cm ² , and a cooling temperature of 20 The measurement sample was produced by press-molding to a thickness of 2 mm under conditions of a cooling time of 5 minutes and a cooling pressure of 100 kgf / cm ² .

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

(7) Vinylidene group content (pieces / 1000C)
The vinylidene group content was determined by ¹ H-NMR. An ECA-500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used for measurement, and the conditions were as follows: measurement nucleus 1H (500 MHz), measurement solvent orthodichlorobenzene-d4, sample concentration 30 mg / 0.6 mL, measurement temperature 120 The temperature was set to 0 ° C. and 1210 times. The chemical shift standard was orthodichlorobenzene (6.9 ppm), and it was calculated from the intensity integral ratio of the vinylidene group-derived peak (4.7 ppm) with respect to the integrated sum of the peaks appearing in the range of 0 to 6 ppm.

[Example 1]
A stainless steel autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum, 10 mL of 1-hexene, and the solid catalyst obtained in Preparation Example 3 Component (X-1) was added, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 ° C. The polymer was collected by filtration, and dried at 80 ° C. for 10 hours under reduced pressure to obtain an ethylene polymer.

  Irganox (registered trademark) 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1% by weight, Irgafos (registered trademark) 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1% by weight as the heat-resistant stabilizer in the obtained ethylene polymer % Was added and melt kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm using a Laboplast Mill (Toyo Seiki Seisakusho). Further, this molten polymer was cooled using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd.) under conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm 2. Physical properties were measured using the sample as a measurement sample. The results are shown in Table 17.

[Examples 2 to 7]
The solid catalyst component (X-1) obtained in Preparation Example 3 was changed to the solid catalyst components (X-2) to (X-7) obtained in Preparation Examples 4 to 9, respectively, as the solid catalyst component. In the same manner as in Example 1, an ethylene polymer was obtained. Using the obtained ethylene-based polymer, a measurement sample was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 17.

Example 8
An ethylene polymer was obtained in the same manner as in Example 1 except that the solid catalyst component (X-9) obtained in Preparation Example 11 was used as the solid catalyst component and the 1-hexene addition amount was changed to 3 mL. It was. Using the obtained ethylene-based polymer, a measurement sample was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 17.

[Comparative Example 1]
An ethylene polymer was obtained in the same manner as in Example 1, except that the solid catalyst component (X-8) obtained in Preparation Example 10 was used as the solid catalyst component. Using the obtained ethylene-based polymer, a measurement sample was prepared in the same manner as in Example 1, and physical properties were measured. The results are shown in Table 17.
Examples 1 to 8 using the component (A-1) or (A-2) are [MT / η *] and [[η] / Mw as compared with Comparative Example 1 using the component (A-3). ^Since the value of ^0.776 ] is high, it can be seen that the amount of long-chain branch introduction is large and the molding characteristics are excellent.

Example 9
Using a fluidized bed gas phase polymerization reactor having an internal volume of 1.0 m ^3, the prepolymerization catalyst component (XP-10) obtained in Preparation Example 12 in the reactor under the polymerization conditions shown in Table 18, ethylene, 1 -Hexene, hydrogen, Chemistat (registered trademark) 2500 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) are continuously supplied, the polymerization reaction product is continuously withdrawn from the reactor, dried in a drying apparatus, and an ethylene polymer is obtained. Obtained.

  To the obtained ethylene-based polymer, 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3, 2] Dioxaphosphepin-6-yl) oxy) propyl] -2-methylphenol (Sumilyzer (registered trademark) GP: manufactured by Sumitomo Chemical Co., Ltd.) 680 ppm, calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) 170 ppm Using a twin-shaft 46mmφ extruder (manufactured by Ikegai Co., Ltd.), melt-kneaded at a set temperature of 200 ° C, a screw rotation speed of 300 rpm, and a feeder rotation speed of 30 rpm, extruded into a strand shape, cut into an ethylene polymer pellet Got. Physical properties were measured using the obtained pellets as measurement samples. The results are shown in Table 18.

Example 10
An ethylene-based polymer was obtained in the same manner as in Example 9, except that the prepolymerization catalyst component (XP-11) obtained in Preparation Example 13 was used under the polymerization conditions shown in Table 18.
Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 18.

[Comparative Example 2]
An ethylene polymer was obtained in the same manner as in Example 9, except that the prepolymerization catalyst component (XP-12) obtained in Preparation Example 14 was used under the polymerization conditions shown in Table 18.
Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 18.
It can be seen that Examples 9 and 10 using the component (B-5) or (B-7) have a small amount of vinylidene and excellent weather resistance as compared with Comparative Example 2 using the component (B-8).

Claims (8)

An olefin polymerization catalyst comprising the following component (A), component (B) and component (C).
Component (A) includes at least one bridged metallocene compound represented by the following general formula (I).

[In General Formula (I), R ¹ is a monovalent group, each independently 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, Phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, which may be the same or different from each other, but all are not hydrogen atoms at the same time and adjacent groups are bonded to each other to form an aliphatic ring. It may be. Q ¹ is a divalent group 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. X is a monovalent group, each independently a hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group; They may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom. ]
Component (B) contains at least one bridged metallocene compound selected from the following general formulas (II), (III) and (IV).

[In the general formulas (II), (III) and (IV), R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are monovalent groups, and each independently represents a hydrogen atom, a 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 or tin-containing group, which may be the same or different from each other and adjacent to each other The substituted groups may be bonded to each other to form a ring. R ⁴ is a hydrogen atom. Q ² is a divalent group 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, and R ³ and Q ² are bonded to each other. To form a ring. Q ³ is a divalent group, 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, and R ³ and Q ³ are bonded to each other. To form a ring (provided that Q ³ does not include -LD ³ ) . Q ⁴ is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and R ³ and R ⁷ may be bonded to each other to form a ring. X is a monovalent group, and each independently represents 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, a phosphorus-containing group, or a boron-containing group. Group or aluminum-containing group, which may be the same or different. M is a titanium atom, a zirconium atom or a hafnium atom. L is a hydrocarbon group having a straight carbon chain having 1 to 10 carbon atoms. D ¹ is the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di). D ² represents the following general formula (Da), (Db), (Dc), (Dd), (De), (Dg), (Dh) or ( Di). D ³ is the following general formula (Db), (Dc), (Dd), (Df), (Dg), (Dh) or (Di). .

General formulas (Da), (Db), (Dc), (Dd), (De), (Df), (Dg), (Dh) and In (Di), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹³ are monovalent groups, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, or a silicon-containing group. Group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, which may be the same or different from each other, and adjacent substitutions The groups may be bonded to each other to form a ring. R ¹² is a monovalent group, and is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group or a phosphorus-containing group, and may be bonded to adjacent R ¹¹ to form a ring. Ch is an oxygen atom or a sulfur atom. Pn is a nitrogen atom or a phosphorus atom. ].
Component (C) is
(C-1) an organometallic compound represented by the following general formula (V), (VI) or (VII),
(C-2) an organoaluminum oxy compound, and (c-3) at least one compound selected from the group consisting of compounds that react with component (A) and component (B) to form ion pairs.
R ^a _m Al (OR ^b ) _n H _p X _q (V)
[In General 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. X represents a halogen atom. m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (VI)
In [Formula (VI), M ^a is lithium atom, sodium atom or a potassium atom. 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 (VII)
[In General Formula (VII), 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. M ^b is a magnesium atom, a zinc atom or a cadmium atom. X represents a halogen atom. r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ] In the general formula (III), Q ^Three Are dimethylmethylene, dibenzylmethylene, diphenylmethylene, di (4-methylphenyl) methylene, di (4-tert-butylphenyl) methylene, di (4-trimethylsilylphenyl) methylene, di (4-methoxyphenyl) methylene, Di (4-dimethylaminophenyl) methylene, di (4-pyrrolidinylphenyl) methylene, di (4-fluorophenyl) methylene, di (4-chlorophenyl) methylene, 1,1-cyclopentanylene, 1,1- Cyclohexanylene, (methyl) (phenyl) methylene, (methyl) (4-methylphenyl) methylene, (methyl) (4-methoxyphenyl) methylene, dimethylsilylene, diphenylsilylene, di (4-methylphenyl) silylene, tri (Methylene) silylene, tetra (methylene) silylene Fine penta (methylene) olefin polymerization catalyst according to claim 1, which is a divalent group selected from the group consisting of silylene. Formula (II), in (III) or (IV), L is, according to claim 1 or 2 characterized in that it is a hydrocarbon radical having a carbon chain of straight chain having 1 to 3 carbon atoms Olefin polymerization catalyst. In the general formula (II), (III) or (IV), R ⁵ is a monovalent group, and is a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, or a sulfur-containing group. The catalyst for olefin polymerization according to any one of claims 1 to 3, which is a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. In the general formula (II), D ¹ is the general formula (Da), (Db) or (Dc),
In the general formula (III), D ² is the general formula (Da), (Db) or (Dc),
In Formula (IV), D ³ is the general formula (D-b), (D -c) or in any one of claims 1 to 4, characterized in that a (D-d) The catalyst for olefin polymerization as described. The solid catalyst component (X-C) formed from the solid carrier (S), the component (A), the component (B), and the component (C), according to any one of claims 1 to 5. Item 4. The catalyst for olefin polymerization according to item. The said component (C) contains an organoaluminum oxy compound (c-2) at least, The catalyst for olefin polymerization as described in any one of Claims 1-6 characterized by the above-mentioned. A density of 875 kg / m ³ or more and 945 kg / m including a step of copolymerizing ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to any one of claims 1 to 7. The manufacturing method of the ethylene-type copolymer which is ³ or less.