JP5455354B2 - Bridged metallocene compound, olefin polymerization catalyst and olefin polymerization method using the same - Google Patents

Description

  The present invention relates to a metallocene compound useful as an olefin polymerization catalyst or catalyst component, and a method for polymerizing olefins in the presence of a catalyst containing the metallocene compound.

  A linear polymer having a polymerizable functional group at one end is expected to be used in a wide range of fields by taking advantage of its structural features. For example, a macromonomer having a vinyl group at the terminal is used for the production of a long-chain branched polymer by polymerizing simultaneously with a monomer such as ethylene, or a polymer using ethylene or propylene as a monomer is used at the terminal. If there are many heavy bonds, development to a polar resin composite material by functionalization of a vinyl group (see Patent Document 1) becomes possible.

  However, conventionally, in order to produce a low molecular weight body, for example, reaction hydrogen is introduced and the molecular weight is lowered, or a polymer produced by heat or an additive is subjected to a decomposition treatment. However, when hydrogen is inserted, although the molecular weight of the polymer to be produced can be reduced, the polymerization activity and the terminal double bond rate are lowered. Moreover, when performing a decomposition process, post-processing cost increases and it becomes difficult industrially. Therefore, a method for producing an α-olefin polymer having a high terminal double bond rate, a high activity and capable of producing a low molecular weight substance has been demanded.

  By the way, low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branching structure and thus has a high melt tension, and therefore has a good moldability such as a small neck-in. It is used for various purposes. However, the mechanical strength such as the tensile strength, tear strength, and impact strength of the molded body is still not sufficient, and there remains a problem that it is inferior in high-speed film forming workability in T-die molding.

  On the other hand, in contrast to LDPE, ethylene polymers obtained with Ziegler catalysts and metallocene catalysts have high tensile strength, tear strength, or impact strength, and therefore require mechanical strength. However, there is a problem that the melt tension is small and the molding processability is inferior.

In order to solve these problems, [1] a method of blending an LDPE and an ethylene polymer obtained using a Ziegler catalyst or a metallocene catalyst (see Patent Document 2), [2] a method of broadening the molecular weight distribution by multistage polymerization (See Patent Document 3), [3] A method of producing a long-chain branched ethylene polymer using a chromium catalyst, [4] A long-chain branched ethylene polymer using a specific metallocene catalyst (5) A method for producing a long-chain branched ethylene polymer by copolymerizing ethylene and diene using a specific metallocene catalyst (see Patent Literatures 5 and 6) Etc. have been proposed. However, the method [1] is unavoidable for a significant cost increase in preparing the blend. Further, the ethylene polymer obtained by the methods [2], [3], and [4] has a small number of long chain branches, and sufficient melt tension and moldability cannot be obtained. Furthermore, in the method [5], if a large amount of diene is introduced, there is a concern that the mechanical properties inherent to the polymer are deteriorated or gel is generated.

In recent years, for the purpose of generating more long-chain branches and improving melt tension, [6] a method of producing a long-chain branched ethylene polymer by copolymerizing a macromonomer using a specific metallocene catalyst (for example, Patent Documents 7 to 9) have been reported. However, since the macromonomer used here has a low ratio of the polymer having a vinyl group at the end and a high molecular weight, it is hardly incorporated during polymerization and has sufficient long chain branching to satisfy molding processability. Not only can the polymer having a number not be obtained, but also a large amount of unreacted macromonomer remains (see Patent Document 10), resulting in problems such as a decrease in the mechanical strength of the polymer and a complicated production process.

  Therefore, if a polymer having a vinyl group at the terminal and a relatively small molecular weight can be efficiently produced, it can be used as a macromonomer in the above macromonomer copolymerization to synthesize a polymer having many long chain branches. In addition, it can be widely applied to polar resin composite materials by functionalization of unsaturated bonds.

As a result of intensive studies in view of such circumstances, the present inventors have developed a novel bridged metallocene compound and developed it as a catalyst for olefin polymerization, thereby having a vinyl group at the terminal and a molecular weight of 5000. The present inventors have found a method for efficiently producing an olefin polymer having a relatively small size of about ˜20,000, and have completed the present invention.
WO2005 / 073282 pamphlet WO99 / 046325 pamphlet JP-A-2-53811 JP-A-4-213306 Japanese National Publication No. 1-50163 JP-T-4-506372 JP-A-8-502303 JP 2004-281676 A Special table 2001-511214 gazette WO2006 / 080578 pamphlet

  The present invention has been made in order to solve the above-mentioned problems, that is, an olefin polymer having a relatively low molecular weight and a high ratio of having a vinyl group at the terminal as compared with the case where a known metallocene compound is used. The present invention provides a bridged metallocene compound for olefin polymerization capable of producing (macromonomer), and provides a catalyst for olefin polymerization containing the bridged metallocene compound, and in the presence of a catalyst for olefin polymerization containing the bridged metallocene compound. It aims at providing the method of superposing | polymerizing efficiently.

  The bridged metallocene compound of the present invention is a bridged metallocene compound represented by the following general formula [1] or [2].

（一般式［１］または［２］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は水素原子、炭化水素基、ケイ素含有基、ヘテロ原子含有基およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴の全てが水素原子ではなく、少なくとも１つは、エチル基、または下記一般式［３］〜［８］のいずれかで表される基であり、Ｒ¹から
Ｒ⁴までの隣接した置換基は互いに結合して脂肪族環を形成していてもよく、Ｙは炭素原
子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれ、ＭはＴｉ、ＺｒおよびＨｆから選ばれ、Ｑは水素原子、ハロゲン原子、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。式［１］において、Ｒ⁵およびＲ⁶は水素原子、炭化水素基、ケイ素含有基、ヘテロ原子含有基およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよい。式［２］におけるＡは不飽和結合を含んでいてもよい炭素原子数２〜２０の二価の炭化水素基を示し、ＡはＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。）

(In the general formula [1] or [2], R ¹ , R ² , R ³ , and R ⁴ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a heteroatom-containing group, and a halogen-containing group. R ¹ , R ² , R ³ and R ⁴ are not all hydrogen atoms, and at least one of them may be represented by an ethyl group or any one of the following general formulas [3] to [8]. And adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form an aliphatic ring, Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom; May be selected from Ti, Zr and Hf, and Q may be selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair, in the same or different combinations, j is an integer of 1 to 4. In Formula [1] R ⁵ and R ⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a heteroatom-containing group, and a halogen-containing group, and may be the same or different, and A in the formula [2] is unsaturated A divalent hydrocarbon group having 2 to 20 carbon atoms which may contain a bond, and A may contain two or more ring structures including a ring formed with Y.

〔上記式［３］〜式［８］において、Ｒ⁷〜Ｒ¹⁶は、水素原子、炭化水素基、ケイ素含有
基、ヘテロ原子含有基およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよいがアリール基ではなく、ＤおよびＥは二価のヘテロ原子を示し、ＧおよびＬは三価のヘテロ原子を示し、ＴおよびＷは四価のヘテロ原子、または炭素原子を示す。〕
前記一般式［３］ではＤが酸素原子であることが好ましく、前記一般式［４］ではＥが酸素原子であることが好ましく、前記一般式［５］ではＧが窒素原子であることが好ましく、前記一般式［６］ではＬが窒素原子であることが好ましく、前記一般式［７］ではＴがケイ素原子であることが好ましく、前記一般式［８］ではＷがケイ素原子であることが好ましく、前記一般式［７］または［８］におけるＴまたはＷが炭素原子であることが好ましい。

[In the above formulas [3] to [8], R ^{7 to} R ¹⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a heteroatom-containing group, and a halogen-containing group. Although not an aryl group, D and E represent a divalent heteroatom, G and L represent a trivalent heteroatom, and T and W represent a tetravalent heteroatom or a carbon atom. ]
In the general formula [3], D is preferably an oxygen atom, in the general formula [4], E is preferably an oxygen atom, and in the general formula [5], G is preferably a nitrogen atom. In the general formula [6], L is preferably a nitrogen atom, in the general formula [7], T is preferably a silicon atom, and in the general formula [8], W is a silicon atom. Preferably, T or W in the general formula [7] or [8] is preferably a carbon atom.

The catalyst for olefin polymerization according to the present invention is characterized by including a bridged metallocene compound represented by the above general formula [1] or [2]. For example, (A) the bridged metallocene compound,
(B) (b-1) a specific organometallic compound,
(B-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with component (A) to form an ion pair,
And at least one compound selected from the group consisting of

The bridged metallocene compound represented by the general formula [1] or [2] can be used in a supported form.
The method for producing an olefin polymer according to the present invention is a method for polymerizing one or more monomers selected from ethylene and α-olefin in the presence of an olefin polymerization catalyst, wherein at least one of the monomers is ethylene or It is characterized by being propylene.

The olefin polymer obtained by the method of the present invention preferably satisfies the following requirements [1] to [3] simultaneously.
[1] Mn is 5000 or more and 20000 or less [2] α × Mn ≧ 2800
[3] Mw / Mn ≦ 3.5
(Where α is the number of vinyl ends per 1000 main chain methylene carbons of the olefin polymer, Mn is the number average molecular weight measured by GPC, and Mw is the weight average molecular weight measured by GPC.)

  By homopolymerizing or copolymerizing an olefin in the presence of the catalyst containing the bridged metallocene compound of the present invention, a low molecular weight olefin homopolymer or copolymer having a large number of vinyl ends can be obtained.

  Further, in the presence of a catalyst containing the bridged metallocene compound, the macromonomer is efficiently obtained by polymerizing a monomer that is one or more monomers selected from ethylene and α-olefin, and at least one of the monomers is ethylene or propylene. Can be manufactured.

  Hereinafter, the bridged metallocene compound represented by the general formula [1] or [2], an example of a preferable bridged metallocene compound, the method for producing the bridged metallocene compound of the present invention, and the bridged metallocene compound of the present invention are provided for an olefin polymerization catalyst. The preferred form and the method of polymerizing olephone in the presence of the olefin polymerization catalyst will be described in order.

Bridged metallocene compound The bridged metallocene compound of the present invention is represented by the following general formula [1] or [2].

一般式［１］または［２］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は水素原子、炭化水素基、ケ
イ素含有基、ヘテロ原子含有基およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよいが、全てが同時に水素ではなく、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴の内少なくとも１つは、エチル基、または下記一般式［３］〜［８］のいずれかで表される基を有している。

In the general formula [1] or [2], R ¹ , R ² , R ³ , and R ⁴ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a heteroatom-containing group, and a halogen-containing group. However, not all are hydrogen at the same time, and at least one of R ¹ , R ² , R ³ and R ⁴ is represented by an ethyl group or any one of the following general formulas [3] to [8]. It has a group.

Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms (for example, a benzyl group), and the like. For example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl (ally
l) group, n-butyl group, t-butyl group, amyl group, n-pentyl group, n-hexyl group, n
-Heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl Group, adamantyl group, benzyl group and the like.

  Examples of the silicon-containing group include hydrocarbon group-substituted silyl such as trimethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, and dimethylphenylsilyl group.

  Examples of the hetero atom-containing group include alkoxy groups such as methoxy group, ethoxy group, phenoxy group, N-methylamino group, N, N-dimethylamino group, and N-phenylamino group, aryloxy group, and amino group.

  Examples of halogen-containing groups include halogen atoms such as fluoro group, chloro group, bromo group, iodo group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, trifluorobutyl group, and trichlorobutyl group, and halogen-substituted alkyl groups. Etc.

The adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form an aliphatic ring. Such substituted cyclopentadienyl groups include tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4-trimethyltetrahydroindenyl, 4-phenyltetrahydroindenyl, 2-methyl-4-phenyltetrahydroindenyl. And a substituted cyclopentadienyl group in which R ³ and R ⁴ are cyclically bonded with a tetramethylene group and R ¹ and R ² are cyclically bonded with a tetramethylene group.

R ^{7 to} R ¹⁶ in the following general formulas [3] to [8] are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a heteroatom-containing group, and a halogen-containing group, and may be the same or different. Is not an aryl group. Examples of the hydrocarbon group, silicon-containing group, heteroatom-containing group and halogen-containing group are the same as those described above.

  D and E are selected from divalent heteroatoms. Examples of the divalent hetero atom include an oxygen atom and a sulfur atom. G and L are selected from trivalent heteroatoms. Examples of the trivalent hetero atom include a nitrogen atom and a phosphorus atom. T and W are selected from tetravalent hetero atoms and carbon atoms. Examples of the tetravalent hetero atom include a silicon atom.

上記一般式［３］で表される基としては、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｔ−ブトキシ基、ｎ−ペンチルオキシ基、２−ネオペンチルオキシ基ｎ−ヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、ｎ−ノニル
オキシ基、ｎ−デカニルオキシ基、３，３，３−トリフルオロプロポキシ基、４−フェニルブトキシ基、エチルスルファニル基、ｎ−プロピルスルファニル基、ｎ−ブチルスルファニル基、イソブチルスルファニル基、ｔ−ブチルスルファニル基、ｎ−ペンチルスルファニル基、２−ネオペンチルスルファニル基、ｎ−ヘキシルスルファニル基、ｎ−ヘプチルスルファニル基、ｎ−オクチルスルファニル基、ｎ−ノニルスルファニル基、ｎ−デカニルスルファニル基、３，３，３−トリフルオロプロピルスルファニル基、４−フェニルブチルスルファニル基などが挙げられる。

Examples of the group represented by the general formula [3] include ethoxy group, n-propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, and 2-neopentyloxy group n-hexyl. Oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decanyloxy group, 3,3,3-trifluoropropoxy group, 4-phenylbutoxy group, ethylsulfanyl group, n-propylsulfanyl Group, n-butylsulfanyl group, isobutylsulfanyl group, t-butylsulfanyl group, n-pentylsulfanyl group, 2-neopentylsulfanyl group, n-hexylsulfanyl group, n-heptylsulfanyl group, n-octylsulfanyl group, n -Nonylsulfanyl group, n-decanylsulfanyl group, 3,3, - trifluoropropyl sulfanyl group, a 4-phenylbutyl sulfanyl group.

  Examples of the group represented by the general formula [4] include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, t-butoxymethyl group, and n-pentyloxymethyl. Group, 2-neopentyloxymethyl group n-hexyloxymethyl group, n-heptyloxymethyl group, n-octyloxymethyl group, n-nonyloxymethyl group, n-decanyloxymethyl group, 3, 3, 3 -Trifluoropropoxymethyl group, 4-phenylbutoxymethyl group, methylsulfanylmethyl group, ethylsulfanylmethyl group, n-butylsulfanylmethyl group, isobutylsulfanylmethyl group, t-butylsulfanylmethyl group, n-pentylsulfanylmethyl group, 2-Neopentylsulfanylmethyl group n-hex Sulfanylmethyl group, n-heptylsulfanylmethyl group, n-octylsulfanylmethyl group, n-nonylsulfanylmethyl group, n-decanylsulfanylmethyl group, 3,3,3-trifluoropropylsulfanylmethyl group, 4-phenylbutyl Examples thereof include a sulfanylmethyl group.

Examples of the group represented by the general formula [5] include N-ethyl-N-methylamino group, N- (n-propyl) -N-methylamino group, (ethyl) (methyl) phosphinomethyl group, N -(N-butyl) -N-methylamino group, N- (isobutyl) -N-methylamino group, N- (t-butyl) -N-methylamino group, N- (n-pentyl) -N-methyl Amino group, N- (2-neopentyl) -N-methylamino group, N- (n-hexyl) -N-methylamino group, N- (n-heptyl) -N-methylamino group, N- (n- Octyl) -N-methylamino group, N- (n-nonyl) -N-methylamino group, N- (n-decanyl) -N-methylamino group, N- (3,3,3-trifluoropropyl) -N-methylamino group, N- (4-phenylbutyl) -N-methyl Amino group, (ethyl) (methyl) phosphino group, diethylphosphino group, (n-propyl) (methyl) phosphino group, (n-butyl) (methyl) phosphino group, n-propyl) (methyl) phosphino group, ( n-butyl) (methyl) phosphino group, (isobutyl) (methyl) phosphino group, (t-butyl) (methyl) phosphino group, (n-pentyl) (methyl) phosphino group, (2-neopentyl) (methyl) phosphino Group, (n-hexyl) (methyl) phosphino group, (n-heptyl) (methyl) phosphino group, (n-octyl) (methyl) phosphino group, (n-nonyl) (methyl) phosphino group, (n-decanyl) ) (Methyl) phosphino group, (3,3,3-trifluoropropyl) (methyl) phosphino group, (4-phenylbutyl) (methyl Such as phosphino group, and the like.

Examples of the group represented by the general formula [6] include N, N-dimethylaminomethyl group, N-ethyl-N-methylaminomethyl group, N- (n-propyl) -N-methylaminomethyl group, Ethyl) (methyl) phosphinomethyl group, N- (n-butyl) -N-methylaminomethyl group, N- (isobutyl) -N-methylaminomethyl group, N- (t-butyl) -N-methylamino Methyl group, N- (n-pentyl) -N-methylaminomethyl group, N- (2-neopentyl) -N-methylaminomethyl group, N- (n-hexyl) -N-methylaminomethyl group, N- (N-heptyl) -N-methylaminomethyl group, N- (n-octyl) -N-methylaminomethyl group, N- (n-nonyl) -N-methylaminomethyl group, N- (n-decanyl) -N-methylaminomethyl Group, N- (3,3,3-trifluoropropyl) -N-methylaminomethyl group, N- (4-phenylbutyl) -N-methylaminomethyl group, (ethyl) (methyl) phosphinomethyl group, Diethylphosphinomethyl group, (n-propyl) (methyl) phosphinomethyl group, (n-butyl) (methyl) phosphinomethyl group, n-propyl) (methyl) phosphinomethyl group, (n-butyl) ( Methyl) phosphinomethyl group, (isobutyl) (methyl) phosphinomethyl group, (t-butyl) (methyl) phosphinomethyl group, (n-pentyl) (methyl) phosphinomethyl group, (2-neopentyl) ( Methyl) phosphinomethyl group, (n-hexyl) (methyl) phosphinomethyl group, (n-heptyl) (methyl) phosphinomethyl group, (n-octyl) Methyl) phosphinomethyl group, (n-nonyl) (methyl) phosphinomethyl group, (n-decanyl) (methyl) phosphinomethyl group, (3,3,3-trifluoropropyl) (methyl) phosphinomethyl Group, (4-phenylbutyl) (methyl) phosphinomethyl group and the like.

Examples of the group represented by the general formula [7] include n-propyl group, n-butyl group, isobutyl group , n -pentyl group, 2-neopentyl group, n-hexyl group, n-heptyl group, and n-octyl. Group, n-nonyl group, n-decanyl group, 4,4,4-trifluorobutyl group, 4-phenylbutyl group, ethyldimethylsilyl group, n-propyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethyl Silyl group, t-butyldimethylsilyl group, n-pentyldimethylsilyl group, 2-neopentyldimethylsilyl group, n-hexyldimethylsilyl group, n-heptyldimethylsilyl group, n-octyldimethylsilyl group, n-nonyldimethyl Silyl group, n-decanyldimethylsilyl group, 3,3,3-trifluoropropyldimethylsilyl group, 4-phenylbutene Examples thereof include a tildimethylsilyl group.

Examples of the group represented by the general formula [8] include n-propyl group, n-butyl group, isobutyl group , n -pentyl group, 2-neopentyl group , n-hexyl group, n-heptyl group, and n-octyl. Group, n-nonyl group, n-decanyl group, 4,4,4-trifluorobutyl group, 4-phenylbutyl group, ethyldimethylsilylmethyl group, n-propyldimethylsilylethyl group, n-butyldimethylsilylethyl group , Isobutyldimethylsilylethyl group, t-butyldimethylsilylethyl group, n-pentyldimethylsilylethyl group, 2-neopentyldimethylsilylethyl group, n-hexyldimethylsilylethyl group, n-heptyldimethylsilylethyl group, n- Octyldimethylsilylethyl group, n-nonyldimethylsilylethyl group, n-decanyldimethylsilyl Butyl group, 3,3,3-trifluoropropyl dimethyl silyl ethyl group, and 4-phenyl-butyldimethylsilyl ethyl group.

  In the bridged metallocene compound represented by the general formula [2], A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, Y binds to this A, It constitutes a 1-silacyclopentylidene group and the like. In the present specification, the 1-silacyclopentylidene group represents the following formula [9].

（上記式［９］において、●は、式［２］における置換シクロペンタジエニル基およびシクロペンタジエニル基との結合点を表す。）
また、ＡはＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。

(In the above formula [9], ● represents the point of attachment to the substituted cyclopentadienyl group and cyclopentadienyl group in formula [2].)
A may include two or more ring structures including a ring formed with Y.

M is selected from Ti, Zr and Hf.
Q is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.

Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above.
Specific examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as aryloxy group, acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

  Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. At least one Q is preferably a halogen atom or an alkyl group.

Among them, in general formula [1] or [2], at least one of R ¹ , R ² , R ³ and R ⁴ is an ethyl group, a group represented by general formula [7] and general formula [8]. It is preferably a group selected from the groups represented. More preferably, ^one of R ¹ , R ² , R ³ and R ⁴ is an ethyl group, a group selected from the group represented by the general formula [7] and the group represented by the general formula [8], R ²
R ³ is more preferably a group selected from an ethyl group, a group represented by the general formula [7], and a group represented by the general formula [8]. Among them, R ³ is an ethyl group, a group selected from the group represented by the general formula [7] and the group represented by the formula [8], and R ¹ , R ² and R ⁴ are all hydrogen atoms. Is particularly preferred.

In the above general formulas [1] and [2], Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom, preferably a carbon atom or a silicon atom, and particularly preferably a silicon atom. The two substituents R ⁵ and R ⁶ bonded to Y in the general formula [1] are selected from the hydrogen atom, hydrocarbon group, silicon-containing group, heteroatom-containing group and halogen-containing group, and are identical to each other. But it can be different. Examples of the hydrocarbon group, silicon-containing group, heteroatom-containing group and halogen-containing group are the same as those described above. Among the hydrocarbons, methyl group, chloromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl It is preferably a group selected from a group, a phenyl group, an m-tolyl group and a p-tolyl group, and particularly preferably selected from a methyl group, a chloromethyl group, an n-butyl group, an n-pentyl group and a phenyl group. .

Bridged metallocene compounds and examples thereof As preferred bridged metallocene compounds of the present invention,
Dimethylsilylene (2-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropylcyclopentadiene) Enyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (3-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalbutylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-butylcyclopentadienyl) (cyclopentadienyl) Zirconium dichloride, dimethylsilylene (3-iso
-Butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-sec-butylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (2-neopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-neopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normaloctylcyclo Pentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-normaloctylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalicosylcyclopentadienyl) (cyclopenta Dienyl) zirconium dichloride, dimethylsilylene (3-normalicosylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-icosylsilane) Clopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-iso-icosylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (4-fluoropropyl) cyclopenta Dienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4-fluoropropyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (4,4-difluoropropyl) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4,4-difluoropropyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (2- (4,4,4-trifluorobutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4,4,4-trifluorobutyl) cyclopentadienyl ) (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (8,8,8-trifluorooctyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (8,8, 8-trifluorooctyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-perfluorobutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-perfluorobutyl) Cyclopentadienyl) (cyclopentadi) Enyl) zirconium dichloride, dimethylsilylene (2- (20,20,20-trifluoroicosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (20,20,20-trifluoroicosyl) ) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (4-chloropropyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4-chloropropyl) ) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (4,4-dichloropropyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4, 4-dichloropropyl) cyclope Tajieniru) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2
-(4,4,4-trichlorobutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (4,4,4-trichlorobutyl) cyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (2-
(8,8,8-trichlorooctyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (8,8,8-trichlorooctyl) cyclopentadienyl) (cyclopentadienyl) Zirconium dichloride,
Dimethylsilylene (2- (20,20,20-trichloroicosyl) cyclopentadienyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (20,20,20-trichloroicosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methoxymethylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-methoxymethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-ethoxymethylcyclopentadienyl) (cyclopentadienyl) zirconium Dichloride, dimethylsilylene (3-ethoxymethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methoxyethylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (3-methoxyethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-ethoxyethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3 -Ethoxyethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-ethoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethoxycyclopentadienyl) (cyclo Pentadienyl) zirconium dichloride, dimethylsilylene (2-propoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-propylene) Cycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-butoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-butoxycyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride,

Dimethylsilylene (2- (N, N-dimethylamino) methylcyclopentadienyl) (
Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (N, N-dimethylamino) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (N-ethyl-N-methylamino) ) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (N
-Ethyl-N-methylamino) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (N, N-diethylamino) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethyl Silylene (3- (N, N-diethylamino) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (N, N-diisopropylamino)
Methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3- (N, N-diisopropylamino) methylcyclopentadienyl) (
Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-ethyldimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyldimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium Dichloride, dimethylsilylene (2-normalpropyldimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-normalpropyldimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyldimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-iso-propyldimethyl) Lil cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2- (trimethylsilyl) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (3- (trimethylsilyl) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene ( 3-ethyl-5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3 -Ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium di Rorido, dimethylsilylene (3-ethyl -5-iso
-Butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5 -T butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-normalpentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5 -Iso-pentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (3-ethyl-5- (2-methylbutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (3-
Methylbutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-neopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- Normal hexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-iso-hexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5 -Normal heptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-iso-heptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethyldimethyl Rylene (3-ethyl-5-normal octylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-iso-octylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, Dimethylsilylene (3-ethyl-5-octadecylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (16-methyloctadecyl) cyclopentadienyl) (cyclopentadienyl) Zirconium dichloride, dimethylsilylene (3-ethyl-5-icosylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (3-ethyl-5- (fluoromethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (difluoromethyl) cyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (3-ethyl-5- (trifluoromethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (2
, 2,2-trifluoroethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (3,3,3-trifluoropropyl) cyclopentadienyl) (cyclo Pentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (4,4,4-trifluorobutyl) cyclopentadienyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (5,5,5-trifluoropentyl) cyclopentadienyl) (cyclopentadienyl)
Zirconium dichloride, dimethylsilylene (3-ethyl-5- (6,6,6-trifluorohexyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (7,7 , 7-trifluoroheptyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (8,8,8-trifluorooctyl) cyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride,
Dimethylsilylene (3-ethyl-5- (20,20,20-trifluoroicosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3
-Ethyl-5- (3-methyl-20,20,20-trifluoroicosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (chloromethyl) cyclopentadi Enyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (dichloromethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (trichloromethyl) ) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (2,2,2-trichloroethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (3-ethyl-5- (3,3,3-trichloropropyl) Clopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (4,4,4-trichlorobutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene ( 3-ethyl-5- (5,5,5-trichloropentyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (6,6,6-trichlorohexyl) cyclo Pentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (7,7,7-trichloroheptyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3 -Ethyl-5- (8,8,8-trichlorooctyl) cyclopenta Enyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-
Ethyl-5- (20,20,20-trichloroicosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (3-methyl-20,20,20-trichloro Icosyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) normal Propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) iso-propylcyclopentadienyl) (cyclopentadienyl)
Zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N- Dimethylamino) iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) sec-butylcyclopentadienyl) (
Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) pentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- ( N, N-dimethylamino) hexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) heptylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-dimethylamino) octylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene (3-ethyl-5- (N, N-diethylamino) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) methylcyclopentadiene Enyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5 -(N, N-diethylamino) normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) iso-propylcyclopentadienyl) (cyclo Pentadienyl) zirconium di Chloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, Dimethylsilylene (3-ethyl-5- (N, N-diethylamino) pentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) hexylcyclopenta Dienyl) (cyclopentadiene Nyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) heptylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diethylamino) octylcyclopentadiene Enyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N- Diisopropylamino) methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (3-tyl-5- (N, N-diisopropylamino) ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3
-Ethyl-5- (N, N-diisopropylamino) normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) iso-propylcyclo Pentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3 -Ethyl-5- (N, N-diisopropylamino) iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) sec-butyl Cyclopentadienyl) Ropentajieniru) zirconium dichloride,
Dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) pentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) hexyl Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (N, N-diisopropylamino) heptylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- ( N, N-diisopropylamino) octylcyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-methoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-ethoxy) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-propoxy-cyclopentadienyl) (cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (3-ethyl-5-butoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (methoxymethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride , Dimethylsilylene (3-ethyl-5- (methoxyethyl) ethoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (methoxypropyl) cyclopentadienyl) (cyclopenta Dienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (methoxybutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (ethoxymethyl) cyclopentadienyl (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (ethoxyethyl) ethoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (ethoxypropyl)) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (ethoxybutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (Propoxymethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (propoxyethyl) ethoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride Dimethylsilylene (3-ethyl-5- (propoxypropyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (propoxybutyl) cyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (3-ethyl-5- (butoxymethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (3-ethyl-5- (butoxyethyl) ethoxycyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (butoxypropyl) cyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride, dimethylsilylene (3-ethyl-5- (butoxybutyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-2-methylcyclopentadienyl) (cyclopenta Dienyl) zirconium dichloride, dimethylsilylene (3-ethyl-2-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-2-normalpropylcyclopentadienyl) (cyclopenta Enyl) zirconium dichloride, dimethylsilylene (3-ethyl -2-an iso-propyl cyclopentadienyl) (cyclopentadienyl)
Zirconium dichloride, dimethylsilylene (3-ethyl-2-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3
-Ethyl-2-iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-2-sec-butylcyclopentadienyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-2-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-methylcyclopentadienyl) ( Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-normalpropylcyclopentadienyl) (cyclo Pentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-normalbutylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (3-ethyl-4-iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium Dichloride, dimethylsilylene (3-ethyl-4-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methyl-3-ethyl-5-methylcyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride, dimethylsilylene (2
-Methyl-3-ethyl-5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-5-normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethyl Silylene (2-
Methyl-3-ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methyl-3-ethyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dichloride, dimethylsilylene (2-methyl-3-ethyl-5-iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methyl-3-ethyl-5)
-Sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methyl-3-ethyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene ( 2-methyl-3-ethyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-5-methylcyclopentadienyl) (
Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-5-normalpropylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (2,3-ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-5-methylcyclopentadiene) Enyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3,5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-) 5-normalpropylcyclo Pentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl- 3-ethyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-
N-propyl-3-ethyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-5-methylcyclopentadienyl) (cyclopentadienyl) Enyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3,5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-5-normalpropyl) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2 -Iso-propyl-3-ethyl-5-norma Butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,

Dimethylsilylene (2-iso-propyl-3-ethyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4,5-methyl-3-ethyl-cyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-methyl-3,5-ethyl-cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-ethyl-4-methyl-) 5-normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-methyl-3-ethyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, Dimethylsilylene (2,4-methyl-3-ethyl-5-normalbutylcyclo Pentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-methyl-3-ethyl-5-iso-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4- Methyl-3-ethyl-5-sec-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-methyl-3-ethyl-5-normalbutylcyclopentadienyl) (cyclopenta Dienyl) zirconium dichloride, dimethylsilylene (2,4-methyl-3-ethyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-4,5- Methylcyclopentadienyl) (cyclopentadienyl) zirconium dichlorine , Dimethylsilylene (2,3,5-ethyl-4-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-4-methyl-5-normalpropylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl-4-methyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3-ethyl) -4-methyl-5-normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (2,3-ethyl-4-methyl-5-tbutylcyclopentadienyl) (
Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-4-methyl-5-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-4) -Methyl-3
, 5-ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-4-methyl-5-normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium Dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-4-methyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2
-Normalpropyl-3-ethyl-4-methyl-5-normalbutylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-normalpropyl-3-ethyl-4-methyl-5-tbutyl) Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-4-methyl-5-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3,5-ethyl-4-methyl-cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-4-methyl-5- Normalpropylcyclopentadienyl) (cyclopentadienyl) zirconium di Loride, dimethylsilylene (2-iso-propyl-3-ethyl-4-methyl-5-iso-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl) -4-methyl-5-normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-4-methyl-5
-Normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene (2-iso-propyl-3-ethyl-4-methyl-5-tbutylcyclopentadienyl) (cyclopentadienyl) zirconium Examples thereof include a crosslinked asymmetric metallocene compound having a silicon-containing group such as dichloride at a crosslinking site. In the present invention, “bridged asymmetric metallocene” is defined as a bridged metallocene comprising a cyclopentadienyl group and a cyclopentadienyl derivative group.

  In addition, a bridged asymmetric metallocene obtained by changing the dimethylsilylene group in the above bridged metallocene compound to a substituted alkylene group (for example, isopropylidene group, di-n-butylmethylene group, etc.), and the dimethylsilylene bridge group is di-n- A bridged asymmetric metallocene compound changed to a butylsilylene bridge group, a bridged asymmetric metallocene compound changed from a silicon atom to a germanium atom and a tin atom, and a bridged asymmetric metallocene compound changed from one or more hydrogen atoms in the bridge to a halogen atom And a bridged asymmetric metallocene compound in which one or more hydrogen atoms of a substituent bonded to the cyclopentadienyl ring are changed to a halogen atom. Moreover, although the metallocene compound etc. whose center metal of the said compound is titanium or hafnium are mentioned, it is not limited to these.

Preferred metallocene compounds include a bridged asymmetric metallocene having a silicon-containing group such as a dimethylsilylene group at the crosslinking site, or a bridged asymmetric metallocene having a carbon-containing group such as a dimethylmethylene group at the crosslinking site. (Cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n -Butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylsilane) Lopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, tri Fluoromethylbutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, tri Fluoromethylbutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dimethylsilylene [3- (trifluorobutyl) cyclopentadienyl] (cyclope Tadienyl) zirconium dichloride, (pentyl) (methyl) silylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (chloromethyl) (methyl) silylene (3-n-butylcyclopentadienyl) ) (Cyclopentadienyl) zirconium dichloride and dimethylmethylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride are particularly preferred compounds.
However, the bridged metallocene compound of the present invention is not limited to the above exemplary compounds, and includes all compounds that satisfy the requirements described in the claims.

Method for Producing Bridged Metallocene Compound The method for producing the bridged metallocene compound of the present invention is not particularly limited, and for example, the method described in the pamphlet of WO01 / 027124 by the present applicant can be referred to. For example, the compounds of general formula [1] and general formula [2] can be produced by the following steps.

First, the precursor compounds (10) and (19) of the general formulas [1] and [2] can be produced by a method such as the production method [A] or [C].
When Y is carbon, the precursor compounds (10) and (19) of the general formulas [1] and [2] can be produced by a method such as the production method [B] or [D].

（式中、Ｒ¹〜Ｒ⁶、Ｙは前記一般式［１］と同一であり、Ｌはアルカリ金属またはアルカリ土類金属である。Ｚ¹、Ｚ²はハロゲンまたはアニオン配位子であり、これらは同一でも、または異なる組合せでもよい。また、（１０）および（１９）はそれぞれシクロペンタ
ジエニル環における２重結合の位置のみが異なる異性体の存在を考えることができ、それらのうちの一種のみ例示してあるが、シクロペンタジエニル環における２重結合の位置のみが異なる他の異性体であっても良く、またはそれらの混合物であっても良い。）

Wherein R ^{1 to} R ⁶ and Y are the same as those in the general formula [1], L is an alkali metal or an alkaline earth metal. Z ¹ and Z ² are halogen or anionic ligands, These may be the same or different combinations, and (10) and (19) can be considered the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl ring, (Only one type is illustrated, but it may be another isomer that differs only in the position of the double bond in the cyclopentadienyl ring, or a mixture thereof.)

  Examples of the alkali metal used in the reactions of the general formulas [A] to [D] include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium and calcium. Examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

Next, examples of producing a metallocene compound from the precursor compounds of the general formulas (10) and (19) are shown in the general formulas [E] and [F], but this does not limit the scope of the invention. It may be produced by any known method.

一般式［Ａ］〜［Ｄ］の反応で得られた一般式（１０）、（１９）の前駆体化合物は、有機溶媒中でアルカリ金属、水素化アルカリ金属または有機アルカリ金属と、反応温度が−８０℃〜２００℃の範囲で接触させることで、ジアルカリ金属塩とする。

The precursor compounds of the general formulas (10) and (19) obtained by the reactions of the general formulas [A] to [D] have an alkali metal, an alkali metal hydride or an organic alkali metal in an organic solvent and a reaction temperature. It is set as a dialkali metal salt by making it contact in the range of -80 degreeC-200 degreeC.

Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin, or aromatic hydrocarbons such as benzene, toluene, and xylene, or THF, di-n-butyl ether, and cyclopentylmethyl. Examples thereof include ethers such as ether, dioxane and 1,2-dimethoxyethane, and halogenated hydrocarbons such as dichloromethane and chloroform.

  Examples of the alkali metal used in the above reaction include lithium, sodium, and potassium. Examples of the alkali metal hydride include sodium hydride and potassium hydride. Examples of the organic alkali metal include methyl lithium and butyl. Examples include lithium and phenyl lithium.

Next, the dialkali metal salts (28) and (30) can be used as they are for the next reaction, but purification is more preferable. Examples of the purification solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin, or aromatic hydrocarbons such as benzene, toluene, and xylene, or THF, di-n-butyl ether, dioxane, 1,
Examples thereof include ethers such as 2-dimethoxyethane, and halogenated hydrocarbons such as dichloromethane and chloroform. Of these, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and decalin are more preferable.

Subsequently, the dialkali metal salt (28), (30) is represented by the general formula (32).
MZ _k (32)
(Wherein, M is a metal selected from titanium, zirconium and hafnium, and Z may be selected from halogen, anionic ligand or neutral ligand capable of coordinating with a lone pair in the same or different combinations. , K is an integer of 3 to 6.) By reacting with a compound represented by formula (1) in an organic solvent, a bridged metallocene compound represented by the general formulas [1] and [2] can be synthesized. . In order to suppress the formation of by-products, the organic solvent is preferably an aliphatic hydrocarbon such as pentane, hexane, heptane, cyclohexane, decalin, or a mixed solvent of 50% by weight or more of aliphatic hydrocarbon and ether, pentane, Aliphatic hydrocarbons such as hexane, heptane, cyclohexane and decalin are particularly preferred.

Preferred specific examples of the compound represented by the general formula (32) include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide, tetravalent zirconium fluoride, chloride, bromide and iodide, tetra Mention may be made of divalent hafnium fluorides, chlorides, bromides and iodides or their complexes with ethers such as THF, di-n-butyl ether, dioxane or 1,2-dimethoxyethane.

  Moreover, as an organic solvent used, the same thing as the above can be mentioned. The reaction between the dialkali metal salt and the compound represented by the general formula (32) is preferably carried out by an equimolar reaction and carried out in the above organic solvent at a reaction temperature in the range of −80 ° C. to 200 ° C. it can.

The metallocene compound obtained by the reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. Moreover, the bridge | crosslinking metallocene compound of this invention obtained by such a method is identified by using analytical methods, such as a proton nuclear magnetic resonance spectrum, < ¹³ > C nuclear magnetic resonance spectrum, mass spectrometry, and elemental analysis.

Preferred embodiment when the crosslinked metallocene compound is used as a catalyst for olefin polymerization Next, a preferred embodiment when the crosslinked metallocene compound of the present invention is used as an olefin polymerization catalyst will be described.

When the bridged metallocene compound of the present invention is used as an olefin polymerization catalyst, the catalyst component is an organic compound represented by the aforementioned bridged metallocene compound (B) (b-1) represented by the following general formula (III), (IV) or (V): At least one compound selected from a metal compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and further necessary Depending on,
(C) It is comprised from a particulate support.

Hereinafter, each component will be specifically described.
Ingredient (B)
Component (B) comprises (b-1) an organometallic compound represented by the following general formula (III), (IV) or (V), (b-2) an organoaluminum oxy compound, and (b-3) a bridge. It is at least one compound selected from compounds that react with the metallocene compound (A) to form ion pairs.
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 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 ... (IV}} )
[In General Formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (V)
[In General Formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b is selected from Mg, Zn and Cd; X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

(B-1) Organometallic compound represented by general formula (III), (IV) or (V) As the organometallic compound represented by general formula (III), (IV) or (V), The organoaluminum compound represented by the formula (III) is preferable. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and the like. ;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride Alkyl aluminum hydrides such as di-sec-nonyl aluminum hydride;
Examples thereof include dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide.

Examples of the organometallic compound represented by the general formula (IV) or (V) include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄ , methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl Examples include magnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.
These are used singly or in combination of two or more.

(B-2) Organoaluminum oxy compound The (b-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.

(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, n-butyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-1).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The organoaluminum compounds as described above are used singly or in combination of two or more.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred. These organoaluminum oxy compounds (b-2) are used singly or in combination of two or more.

(B-3) Compound that reacts with transition metal compound to form ion pair Compound (b-3) that reacts with bridged metallocene compound (A) of the present invention to form ion pair (b-3) (
Hereinafter, it is also referred to as “ionized ionic compound”. Are disclosed in JP-A-1-501950, JP-A-1-503636, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704. Gazette, USP
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in No. -53221106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (b-3) are used singly or in combination of two or more.

When the bridged metallocene compound of the present invention is used as an olefin polymerization catalyst, when it is used in combination with an organoaluminum oxy compound (b-2) such as methylaluminoxane as a promoter component, it exhibits a particularly high polymerization activity with respect to the olefin compound.

Further, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (b-1) an organometallic compound represented by the general formula (III), (IV) or (V), (b-2) A support (C) can be used as needed together with at least one compound (B) selected from (ii) an organoaluminum oxy compound and (b-3) an ionized ionic compound.

(C) Carrier The carrier (C) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among these, the inorganic compound is preferably an inorganic halide such as a porous oxide or inorganic chloride, clay, clay mineral, or ion-exchangeable layered compound.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, eg natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those mainly composed of SiO ₂ and / or Al ₂ O ₃ are preferred, and SiO ₂ is particularly preferably used. Such porous oxides are
Although the properties vary depending on the type and production method, the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m. Desirably, the pore volume is in the range of ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such carriers can be 100-1000 as needed.
Baked at a temperature of 150 ° C, preferably 150 to 700 ° C.

Examples of inorganic halides such as inorganic chlorides include MgCl ₂ , MgBr ₂ , MnCl ₂ , M
nBr ₂ or the like is used. The inorganic halide may be used as it is, a ball mill,
You may use after grind | pulverizing with a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein 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. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, 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 halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Z.
r (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn
_{(HPO 4) 2 · H 2} O, γ-Zr (HPO 4) 2, γ-Ti (HPO 4) 2, γ-Ti (NH 4 PO 4) crystalline polyvalent metals such ₂ · H ₂ O Examples include acid salts. 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 and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

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 TiCl ₄ , Zr
Cationic inorganic compounds such as Cl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (O
H) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolysis of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene is produced as a main component (
Examples thereof include (co) polymers, (vinyl) cyclohexane, (co) polymers produced mainly from styrene, and modified products thereof.

The catalyst for olefin polymerization according to the present invention comprises the bridged metallocene compound (A) of the present invention, (b-1
) At least one compound selected from organic metal compounds represented by general formula (III), (IV) or (V), (b-2) organoaluminum oxy compounds, and (b-3) ionized ionic compounds. (B) The carrier (C) is included as necessary.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on a carrier (C) is added to a polymerization vessel.

In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.
In the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.

  The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.
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. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.

In general, when a metallocene compound forms an ion pair with the aforementioned component ( B ) and functions as an olefin polymerization catalyst, a metallocene compound having substituents on both cyclopentadienyl rings has a high catalytic activity and a high molecular weight. Gives a polymer with high and low double bonds at the ends.

This is because when a large number of substituents are introduced into the cyclopentadienyl ring, an appropriate distance is maintained between the central metal (cation) and the component ( B ) (anion) due to the steric hindrance of the substituent. As the acidity of the metal increases, the coordination and insertion of the monomer is promoted, and at the same time, the molecular weight control such as the chain transfer reaction to the monomer and the hydrogen transfer to the central metal at the β position of the polymer chain due to the steric hindrance of the substituent. This is probably because the chain transfer reaction is suppressed.

Therefore, the catalyst for olefin polymerization using the bridged metallocene compound represented by the general formula [1] or [2] used in the present invention introduces a substituent only to one cyclopentadienyl ring, An appropriate distance can be maintained between the central metal and the component ( B ) while maintaining a space capable of inducing a chain transfer reaction. Therefore, a polymer having high polymerization activity, a low molecular weight, and a large number of double bonds at the ends can be obtained. Can be manufactured.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of the reaction volume. It is used in such an amount that it becomes a mole.

Component (b-1) has a molar ratio [(b-1) / M] of the component (b-1) and all transition metal atoms (M) in the component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (b-2) has a molar ratio [(b-2) / M] of aluminum atoms in component (b-2) to all transition metals (M) in component (A), usually 10 to 10. 5000, preferably 20-
The amount used is 2000. Component (b-3) has a molar ratio [(b-3) / M] of component (b-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

In the present invention, the olefin supplied to the polymerization reaction is at least one monomer selected from ethylene and α-olefin. Of these, at least one of the monomers is preferably ethylene or propylene. As the α-olefin, a linear or branched α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 1
-Butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.

In the polymerization method of the present invention, a cyclic olefin having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1 , 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a
-Octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride , Β-unsaturated carboxylic acids such as organic compounds, and metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, n-butyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, Α, β-unsaturated carboxylic acids such as isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate Ter; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Unsaturated glycidyl and the like can be used.

Vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-n-butylstyrene, m-n- Mono- or polyalkyl styrene such as butyl styrene and p-n-butyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinyl Functional group-containing styrene derivatives such as benzene;
Polymerization can also proceed by coexisting 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like in the reaction system.

  In the polymerization method of the present invention, at least one of the monomers is ethylene or propylene. When two or more types of monomers are used, it is preferable that the skeleton concentration in the polymer (macromonomer) due to ethylene or propylene is 50 mol% or more. Further, it can be easily analogized that the same result can be obtained even if at least one of the monomers is an α-olefin such as 1-butene, 1-hexene and 1-decene.

  The polymer (macromonomer) obtained in the present invention has an unsaturated bond site such as a vinyl group at the end of the polymer, and the number average molecular weight (Mn) by GPC is 5,000 or more and 20,000 or less. It is preferably 5,000 or more and 15,000 or less, more preferably 5,000 or more and 14,000 or less.

The number of vinyl ends of the polymer (macromonomer) is ¹ H-NMR, ¹³ C-NMR or FT.
What is required by analysis such as -IR is well known to those skilled in the art, but in the present invention, it was analyzed by ¹ H-NMR or FT-IR.

Terminal vinyl ratio is
Terminal vinyl ratio (%) = α / 14000 × Mn × 100
(Where α is the number of vinyl ends per 1000 main chain methylene carbons of the polymer, Mn is the number average molecular weight, and Mw is the weight average molecular weight)
When the terminal vinyl ratio is 20%, α × Mn = 2800. When those having a terminal vinyl ratio of less than 20% are used as long-chain branching macromonomers, most of them do not contribute to the polymerization and remain unreacted. Therefore, a polymer having a small number of long-chain branches is produced, and therefore, molding processability is not satisfied. The polymer obtained by the present invention has α × Mn of 2800 or more and 14000 or less, preferably 4000 or more and 14000 or less, more preferably 5000 or more and 14000 or less. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 or more and 3.5 or less, preferably 1.5 or more and 3.5 or less, more preferably 1. 5 or more and 3 or less. A macromonomer that satisfies this property has a high terminal unsaturated bond ratio and a molecular weight that is generally smaller than that of known products, so that the uptake rate during copolymerization is increased, and melt flowability and molding processability are excellent.

  Furthermore, since the macromonomer obtained by the method of the present invention has a high number of vinyl groups at the terminal, graft modification and the like are easy. That is, the macromonomer obtained by the method of the present invention is subjected to an oxidation reaction, a graft reaction, an ene synthesis reaction, etc., so that a functionalized olefin polymer or an olefin polymer polar resin composite material (for example, an antistatic agent) is obtained. Cosmetic additives, toner release agents, pigment dispersants, vinyl chloride resin lubricants, paints, adhesives, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The structure of the compound obtained in the synthesis example is 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (FD-MS) (JEOL SX-102A), gas chromatograph-mass spectrometry (GC-MS). ) (Shimadzu GCMS-QP5050A) and the like.
The structural analysis of the polymer was determined using the following apparatus and the like.

[Weight average molecular weight (Mw), number average molecular weight (Mn)]
The gel permeation chromatography (GPC) was calculated from a molecular weight distribution curve obtained by a water permeation chromatograph (High Temperature Size Exclusion Chromatograph) of a Waters model “Alliance GPC 2000”. [Used equipment and conditions]
Measuring device: Gel permeation chromatograph allianceGPC2000 (Waters)
Analysis software: Chromatographic data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [= ODCB] (Wako Pure Chemical)
Detector: Differential refractometer (built-in device)
Column temperature; 140 ° C
Flow rate: 1.0mL / min
Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w / v)
Molecular weight calibration Monodisperse polystyrene (Tosoh Corp.) / Molecular weight 495 to molecular weight 20.6 million Molecular weight distribution and various average molecular weights are given in Z. Crubisic, P. Rempp, H. Benoit, J. Polym.
According to the general calibration procedure described in Sci., B5 , 753 (1967), the molecular weight was calculated in terms of polyethylene molecular weight.

[Intrinsic viscosity ([η])]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity η _sp is 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 is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.
[Η] = lim (η _sp / C) (C → 0)

[Quantitative analysis of terminal structure]
The terminal structure (double bond number) of the polymer was determined using ¹ H-NMR (JEOL ECA-500) or the like.

[Synthesis Example 1]
<Step.1> Synthesis of chloro (cyclopentadienyl) dimethylsilane 100 ml of THF was added to 14.3 g (110 mmol) of dimethylsilyl dichloride and cooled to -78 ° C. 38.7 ml (77.4 mmol) of 2M-sodium cyclopentadiene in THF was added dropwise over 30 minutes, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure, and the resulting chloro (cyclopentadienyl) dimethylsilane was used in the next step.

<Step.2> Synthesis of (3-ethylcyclopentadienyl) (cyclopentadienyl) dimethylsilane 7.52 g (80 mmol) of ethylcyclopentadiene was dissolved in 100 ml of THF. The mixture was cooled to −78 ° C., and 56 ml (92 mmol) of a 1.58 M-n-butyllithium / hexane solution was added dropwise. Stir at room temperature for 2 h, -78 ° C in 110 mmol chloro (cyclopentadienyl) dimethylsilane, 50 ml THF
It was dripped at. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, vacuum distillation was performed, followed by silica gel column chromatography to obtain 0.86-g of (3-ethylcyclopentadienyl) (cyclopentadienyl) dimethylsilane. The target product was identified by GC-MS. GC-MS; 216 (MS)

<Step.3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl ) zirconium dichloride (A1) Dimethylsilyl (cyclopentadienyl) (3-ethylcyclopentadienyl) 0.90g (3.9 mmol) was dissolved in 40 ml of diethyl ether. After cooling to −78 ° C., 5.09 ml (8.0 mmol) of 1.57 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 13 ml of hexane. The obtained white solid was suspended in 50 ml of hexane, and 820 mg (3.5 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filtration and washing with hexane were performed to remove insoluble parts. The filtrate was concentrated under reduced pressure and washed with pentane. The obtained solid was dried under reduced pressure to obtain 210 mg (yield 14%) of dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride (A1). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.1-6.9 (m, 2H), 6.6 (s, 1H), 6.0-5.8 (m, 3H), 5.5 (s, 1H), 2.6 (m, 2H) , 1.2 (t, 3H), 0.8-0.7ppm (d, 6H); FD-MS; 376 (MS)

[Synthesis Example 2]
<Step.1> Synthesis of chloro (cyclopentadienyl) dimethylsilane 100 ml of THF was added to 14.3 g (110 mmol) of dimethylsilyl dichloride and cooled to -78 ° C. 2M-
38.7 ml (77.4 mmol) of a THF solution of sodium cyclopentadiene was added dropwise over 30 minutes, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration under reduced pressure was performed, and sodium chloride was removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure, and the resulting chloro (cyclopentadienyl) dimethylsilane was used in the next step.

<Step.2> Dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl)
Synthesis)
100 ml of THF was added to 2.16 g (20 mmol) of n-propylcyclopentadiene and cooled to -78 ° C. 13.3 ml (22 mmol) of 1.57M-n-butyllithium / hexane solution was slowly added dropwise and stirred at room temperature for 3 hours. The reactor was cooled again to −78 ° C., and 3.97 g (25 mmol) of chloro (cyclopentadienyl) dimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. After stirring for 18 hours at room temperature, the completion of the reaction was confirmed by TLC. The reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, the solution obtained after filtration was concentrated under reduced pressure. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) and vacuum distillation, 1.73 g (yield) of dimethylsilylyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) Rate 38%). ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.0 (s, 1H), 2.9 (s, 1H), 2.3 (m, 2H), 1.6 (m, 2H) 0.9 ( t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H); GC-MS; 230 (MS)

<Step.3> Dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopenta
Synthesis of dienyl) zirconium dichloride (A2) 0.90 g (3.9 mmol) of dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) was dissolved in 40 ml of diethyl ether. After cooling to −78 ° C., 5.09 ml (8.0 mmol) of 1.57 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 13 ml of hexane. The obtained white solid was suspended in 50 ml of hexane, and 820 mg (3.5 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure and washed with pentane. The obtained solid was dried under reduced pressure to obtain 210 mg (yield 14%) of dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.1-6.9 (m, 2H), 6.6 (s, 1H), 6.0-5.8 (m, 3H), 5.5 (s, 1H), 2.6 (m, 2H) , 1.5 (m, 2H), 0.9 (t, 3H), 0.8-0.7ppm (d, 6H); FD-MS; 388 (MS)

[Synthesis Example 3]
<Step.1> Synthesis of (3-n-butylcyclopentadienyl) chlorodimethylsilane
50 ml of THF was added to 30.1 g (61.5 mmol) of 25 wt% -butylcyclopentadiene / THF solution. The solution was cooled to 0 ° C., and 38.4 ml (58.4 mol) of a 1.52 M-n-butyllithium / hexane solution was added dropwise.
The mixture was stirred at room temperature for 2 hours and added dropwise to 14.3 g (110 mmol) of dimethylsilyl dichloride and 50 ml of THF at −78 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to obtain 8.09 g (yield 64%) of (3-n-butylcyclopentadienyl) chlorodimethylsilane. The target product was identified by GC-MS. GC-MS; 214 (MS)

<Step.2> Dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadiene)
Nyl) synthesis
50 ml of THF was added to 8.8 ml (16.6 mmol) of 2M-sodium cyclopentadienide in THF and cooled to -78 ° C. 1.89 g (8.8 mmol) of (3-n-butylcyclopentadienyl) chlorodimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. After stirring at room temperature for 2 hours, the mixture was stirred at 50 ° C. for 2 hours. The completion of the reaction was confirmed by TLC, and the reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, the solution obtained after filtration was concentrated under reduced pressure. Distillation under reduced pressure was performed to obtain 1.07 g (yield 50%) of dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl). ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.2 (d, 1H), 2.9 (d, 1H), 2.3 (t, 2H), 1.4 (m, 4H) 0.9 ( t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H); GC-MS; 244 (MS)

<Step.3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A3) Dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl) 0.58 g (2.38 mmol) was dissolved in 30 ml of diethyl ether. After cooling to −78 ° C., 3.16 ml (4.99 mmol) of 1.57M-nBuLi was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained white solid was suspended in 60 ml of hexane, -78 ° C
Below, 500 mg (2.15 mmol) of zirconium tetrachloride was added. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure to obtain 510 mg of a crude product. The solid obtained after washing with diethyl ether and pentane was dried under reduced pressure to obtain 190 mg (yield 20%) of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A3). It was. ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 6.9 (d, 2H), 6.6 (s, 1H), 5.9 (t, 3H), 5.5 (s, 1H), 2.6 (m, 2H), 1.4 (m , 2H), 1.3 (m, 2H), 0.9 (t, 3H), 0.8 ppm (m, 3H); FD-MS; 404 (MS)

[Synthesis Example 4]
<Step.1> Synthesis of n-octylcyclopentadienide
100 ml of THF was added to 50 ml (100 mmol) of a THF solution of 2M-sodium cyclopentadienide. The solution was cooled to −78 ° C., and a THF solution of 19.3 g (100 mmol) of 1-bromooctane was added dropwise. Further, 11.4 g (100 mol) of 1,3-dimethyl-2-imidazolidinone was added dropwise and stirred at −78 ° C. The mixture was stirred at room temperature for 24 hours and then cooled to 0 ° C. The reaction was terminated with 1N hydrochloric acid, hexane was added, and the mixture was washed successively with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solution was purified by distillation under reduced pressure to obtain 6.7 g (37.5 mmol) of n-octylcyclopentadiene as a target product. The target product was identified by GC-MS. GC-MS; 178 (MS)

<Step.2> Synthesis of dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl)
100 ml of THF was added to 5.34 g (30 mmol) of n-octylcyclopentadiene. The mixture was cooled to −78 ° C., and 18.9 ml (30 mmol) of a 1.58 M-n-butyllithium / hexane solution was added dropwise. The mixture was stirred at room temperature for 2 hours, and dropwise added to 14.3 g (110 mmol) of dimethylsilyl dichloride and 50 ml of THF at −78 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure to obtain chlorodimethyl (3-n-octylcyclopentadienyl) silane. After identifying the target product by GC-MS, 100 ml of THF was added to the reactor and cooled to -78 ° C. 15 ml (30 mmol) of 2M-sodium cyclopentadienide / THF solution was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. After confirming the progress of the reaction, water was added at 0 ° C. to stop the reaction. Extraction was performed with hexane, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic layer was dried over magnesium sulfate and filtered, and the resulting solution was concentrated under reduced pressure. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) and 3.5 g of the target product, dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl) 39%). The target product was identified by GC-MS. GC-MS; 300 (MS)

<Step.3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-n- octylcyclopentadienyl) zirconium dichloride (A4) Dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl) 3.1 g (10 mmol) was dissolved in 80 ml of diethyl ether. After cooling to −78 ° C., 13.1 ml (20.5 mmol) of a 1.57 M-n-butyllithium hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentrated under reduced pressure and washed with hexane. The obtained solid was suspended in 80 ml of hexane, and 1.96 g (8.4 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure, washed with a mixed solvent of diethyl ether and pentane, the obtained solid was dried under reduced pressure, and dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride 240 mg ( Yield 5%). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard): 7.0 (s, 1H), 6.9 (s, 1H), 6.5 (s, 1H), 5.9-5.8 (m, 3H), 5.5 (s, 1H), 2.7 (m, 2H), 1.5 (m, 2H), 1.2 (m, 10H), 0.8 (t, 3H), 0.7ppm (m, 6H); FD-MS; 458 (MS)

[Synthesis Example 5]
<Step.1> [3- (4,4,4-trifluorobutyl)] (cyclopentadienyl) chlorodimethyl
Synthesis of Rusilane 150 ml of THF was added to 1.5 g (8.5 mmol) of (4,4,4-trifluorobutyl) cyclopentadiene. After cooling to 0 ° C., 6.2 ml (1.5 mmol) of a hexane solution of 1.52M-n-butyllithium was added dropwise. Stir at room temperature for 2 hours, 0.29 g (2.3 mmol) of dimethylsilyl dichloride, -78 in 50 ml of THF.
It was dripped at ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours to obtain a transparent solution. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to remove dimethylsilyl dichloride. 100 ml of THF was added and cooled to -78 ° C. 4.7 ml (9.4 mmol) of 2M sodium cyclopentadiene in THF
Was gradually added dropwise and stirred at room temperature for 24 hours. The reaction was stopped by adding water at 0 ° C., and the organic layer was extracted with hexane. It dried with magnesium sulfate and filtered. The solution was concentrated under reduced pressure and purified by silica gel column chromatography (solvent: hexane: triethylamine = 98: 2 v / v). The target product [3- (4,4,4-trifluorobutyl)] (cyclopentadienyl) chlorodimethylsilane (1.5 g) was obtained. The target product was identified by GC-MS. GC-MS; 298 (MS)

<Step.2> Synthesis of dimethylsilylene [3- (4,4,4-trifluorobutyl) cyclopentadienyl] (cyclopentadienyl) zirconium dichloride (A5)
[3- (4,4,4-trifluorobutyl)] (cyclopentadienyl) chlorodimethylsilane
0.69 g (2.3 mmol) was dissolved in 30 ml of diethyl ether. The mixture was cooled to −78 ° C., and 3.0 ml (4.8 mmol) of a hexane solution of 1.57M-n-butyllithium was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained white solid was suspended in 60 ml of hexane, and 410 mg (1.8 mmol) of zirconium tetrachloride was added at −78 ° C.
The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filtration and washing with hexane were performed to remove insolubles. The filtrate was concentrated under reduced pressure to obtain 30 mg of dimethylsilylene [3- (4,4,4-trifluorobutyl) cyclopentadienyl] (cyclopentadienyl) zirconium dichloride (A5). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.2-5.5 (m, 7H), 2.6 (m, 2H), 2.3-1.8 (m, 4H), 1.4-0.6 ppm (m, 6H); FD-MS : 458 (MS)

[Synthesis Example 6]
<Step.1> Synthesis of 2-butyl-1,3,4-trimethylcyclopentadiene 259 g of polyphosphoric acid was added, and 50.7 g of sec-butyl methacrylate was added dropwise with stirring at 40 ° C. The mixture was stirred for 1 hour, and the temperature was raised to 80 ° C. After stirring for 1 minute, cooling was performed, and an aqueous sodium hydroxide solution was added to make the solution slowly alkaline. Extraction was performed with hexane and diethyl ether, and the organic layer was dried over sodium sulfate. The solution was concentrated under reduced pressure and purified by distillation under reduced pressure.
To 6.8 g of the obtained 2,3,5-trimethylcyclopent-2-enone, 75 ml of diethyl ether was added. Cool to -78 degrees, and add 0.5 ml of 0.84M-n-butylmagnesium chloride / THF solution
It was added dropwise over a period of minutes. The temperature was gradually raised to room temperature, the mixture was stirred for 24 hours, and saturated aqueous ammonium chloride solution was added dropwise at -10 ° C. The mixture was stirred for 10 minutes, 20% aqueous sulfuric acid solution was added, and the organic layer was extracted with diethyl ether. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and concentrated under reduced pressure. Purification by vacuum distillation and silica gel chromatography (solvent: hexane)
5.2 g of butyl-1,3,4-trimethylcyclopentadiene was obtained. The target product was identified by GC-MS. GC-MS; 164 (MS)

<Step.2> Synthesis of (2-Butyl-1,3,4-trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane
100 ml of THF was added to 1.6 g (12.9 mmol) of 2-butyl-1,3,4-trimethylcyclopentadiene. After cooling to 0 ° C., 8.6 ml (13.5 mmol) of a hexane solution of 1.57M-n-butyllithium was added dropwise. The mixture was stirred at room temperature for 2 hours, and 2.0 g (15.5 mmol) of dimethylsilyl dichloride and 50 ml of THF were added to -78.
It was dripped at ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 8 hours to obtain a transparent solution. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to remove dimethylsilyl dichloride. 100 ml of THF was added and cooled to -78 ° C. 4.7 ml (9.4 mmol) of 2M-sodium cyclopentadienide / THF solution
) Was gradually added dropwise and stirred at room temperature for 24 hours. The reaction was stopped by adding water at 0 ° C., and the organic layer was extracted with hexane. The extract was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. The solution was concentrated under reduced pressure and purified by silica gel column chromatography (solvent: hexane: triethylamine = 98: 2 v / v). The target product (3-butyl-2,4,5-
4.6 g (16.1 mmol) of trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane was obtained. The target product was identified by GC-MS. GC-MS; 286 (MS)

<Step.3> Dimethylsilylene (3-butyl-2,4,5-trimethylcyclopentadienyl)
Synthesis of ( cyclopentadienyl) zirconium dichloride (A6) (3-butyl-2,4,5-trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane 0.53 g (1.9 mmol) in 50 ml of diethyl ether Dissolved. The mixture was cooled to −78 ° C., and 0.76 ml (1.7 mmol) of a hexane solution of 1.57M-n-butyllithium was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained solid was suspended in hexane 50 ml, and zirconium tetrachloride 400 mg (1.7 mmol) at −78 ° C.
Was added. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. It was dissolved in diethyl ether, and pentane was added while stirring to precipitate gradually. 30 mg of dimethylsilylene (3-butyl-2,4,5-trimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A6) was washed with pentane and the resulting solid was dried by concentration under reduced pressure. Obtained. ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 6.9 (s, 2H), 5.6 (s, 2H), 5.6 (2H), 2.4-2.2 (m, 2H), 2.0-1.8 (m, 9H), 1.5 -1.2 (m, 4H), 0.9-0.7 (m, 9H); FD-MS; 444 (MS)

[Synthesis Example 7]
<Step.1> Synthesis of dibutylchloro (cyclopentadienyl) silane 2M-sodium cyclopentadienide / THF solution 100ml (200mmol) in THF 100ml
Was added. Cool to −78 ° C. and add 100 ml of THF. Dibutyldichlorosilane (21.3 g, 100 mmol) was gradually added dropwise. The mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and the raw material was distilled off. Used in the next step without further purification.

<Step.2> Dibutylsilyl (3-n-butylcyclopentadienyl) (cyclopentadiene)
Nyl) synthesis
6.3 g (51.5 mmol) of n-butylcyclopentadiene was dissolved in 120 ml of THF. 0 ℃
Then, 32.8 ml (51.5 mmol) of 1.58 M-n-butyllithium / hexane solution was added dropwise over 30 minutes. The mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and 20.3 g (95.2 mmol) of dibutylchloro (cyclopentadienyl) silane added with 100 ml of THF was gradually added dropwise. The mixture was stirred at room temperature for 8 hours and stirred at 45 ° C. for 8 hours. The reaction was stopped by cooling to 0 ° C. and adding water. Extraction was performed with ethyl acetate, and the organic layer was washed with a saturated aqueous sodium carbonate solution and saturated brine. It dried with magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting liquid was purified by neutral silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v). The target product, dibutylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl) (1.42 g, yield 8%) was obtained. ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-5.5 (s, 7H), 3.1-2.3 (m, 2H), 1.9-0.9 (m, 25H), GC-MS: 328 (MS)

<Step.3> Dibutylsilylene (3-n-butylcyclopentadienyl) (cyclopentadiene)
Synthesis of (enyl) zirconium dichloride (A7) 1.4 g (4.3 mmol) of dibutylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl) was dissolved in 50 ml of diethyl ether. After cooling to −78 ° C., 5.6 ml (8.8 mmol) of a 1.58 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure, washed with hexane, and filtered. The obtained solid was suspended in 80 ml of hexane, and 0.95 g (4.1 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure to obtain 1.2 g (57% yield) of dibutylsilylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A7). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-5.5 (s, 7H), 2.7 (m, 2H), 1.8-0.9 (m, 25H), FD-MS: 486 (MS)

[Synthesis Example 8]
<Step.1> Synthesis of chloro (chloromethyl) (cyclopentadienyl) (methyl) silane
100 ml of THF was added to 6 g (49 mmol) of n-butylcyclopentadiene. The solution was cooled to −78 ° C., and 29.6 ml (48.8 mmol) of a 1.65 M-n-butyllithium / hexane solution was added dropwise. The mixture was stirred at room temperature for 2 hours and cooled again to -78 ° C. Dichloro (chloromethyl) (methyl) silane (8.0 g, 49 mmol) to which 50 ml of THF was added was added dropwise. The mixture was stirred at room temperature for 3 hours, concentrated under reduced pressure, and filtered by adding hexane. The obtained solution was distilled under reduced pressure to obtain 3.43 g of the target product, chloro (chloromethyl) (cyclopentadienyl) (methyl) silane.

<Step.2> (Pentyl) (methyl) silylene (3-n-butylcyclopentadienyl) (
Synthesis of cyclopentadienyl) zirconium dichloride (A8) (3-butylcyclopentadienyl) (cyclopentadienyl) (methyl) silane with THF
100 ml was added and cooled to -78 ° C. 6.9 ml (13.8 mmol) of a 2M sodium cyclopentadienide / THF solution was added dropwise. The mixture was stirred at room temperature for 24 hours and cooled to 0 ° C. Water was added to stop the reaction, extraction was performed with hexane, and the mixture was extracted with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. After drying with magnesium sulfate, purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v), the obtained ligand 1.6 g (5.74 mmol)
Was dissolved in 50 ml of diethyl ether. The mixture was cooled to −78 ° C., and 7.12 ml (8.8 mmol) of a 1.58 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure, washed with hexane, and filtered. The obtained solid was suspended in 60 ml of hexane, and 0.88 g (5.2 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure to obtain 0.15 g (yield 6%) of (pentyl) (methyl) silylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A8). ¹ HN
The target was identified by MR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard): 7.0-6.8 (m, 2H), 6.5 (m, 1H), 5.9-5.7 (m, 3H), 5.5 (s, 1H), 2.6 (m, 2H) , 1.6-0.6 (m, 21H), FD-MS; 458 (MS)

[Synthesis Example 9]
<Step.1> (Chloromethyl) (methyl) silylene (3-n-butylcyclopentadienyl)
) Synthesis of ( cyclopentadienyl) zirconium dichloride (A9) (3-n-butylcyclopentadienyl) (chloromethyl) (cyclopentadienyl) (methyl) silane 1.3 g (4.7 mmol) in 60 ml of diethyl ether Dissolved. The mixture was cooled to −78 ° C., and 5.7 ml (9.3 mmol) of a 1.65M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at 10 ° C. for 3 hours. Concentrate under reduced pressure, suspend in 60 ml of hexane, -78 ° C
Below, 0.97 g (4.2 mmol) of zirconium tetrachloride was added. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filtration and washing with hexane were performed to remove insolubles. The filtrate was concentrated under reduced pressure and reslurried with diethyl ether and n-pentane. The supernatant was removed and washed with n-pentane. The obtained solid was concentrated to obtain 200 mg (yield 4.8%) of (chloromethyl) (methyl) silylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A9). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.1-5.5 (m, 7H), 3.4 (d, 2H), 2.6 (m, 2H), 1.6-1.2 (m, 4H), 0.9-0.7 (m, 6H), 1.6-0.6 (m, 21H), FD-MS: 436 (MS)

[Synthesis Example 10]
<Step.1> Dimethylmethylene (3-n-butylcyclopentadienyl) (cyclopentadiene)
Synthesis of enyl)
To 5 g (40.9 mmol) of n-butylcyclopentadiene, 100 ml of 1,2-dimethoxyethane was added and cooled to 0 ° C. 2.8 g (50 mmol) of potassium hydroxide was added, the temperature was gradually raised, and the mixture was stirred for 1 hour under reflux. Under 0 ° C., 4.34 g (41 mmol) of 6,6-dimethylfulvene was added and stirred for 3 hours under reflux. The mixture was cooled to 0 ° C. and quenched with 1N hydrochloric acid. Extraction was performed with hexane, and the mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) gave 3.2 g (14 mmol) of dimethylmethylene (3-n-butylcyclopentadienyl) (cyclopentadienyl). ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 6.6-5.5 (m, 7H), 3.0-2.7 (d, 2H), 2.6-2.4 (m, 2H), 1.6-0.9 (m, 13H), GC- MS: 228 (MS)

<Step.2> Dimethylmethylene (3-n-butylcyclopentadienyl) (cyclopentadiene)
Synthetic ligand 1.3 g (4.66 mmol) of enyl) zirconium dichloride (A10) was dissolved in 60 ml of diethyl ether. After cooling to −78 ° C., 5.7 ml (9.3 mmol) of 1.65M-nBuLi was added dropwise. The temperature was gradually raised and the mixture was stirred at 10 ° C. for 3 hours. The mixture was concentrated under reduced pressure, suspended in 60 ml of hexane, and 0.97 g (4.2 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filtration and washing with hexane were performed to remove insolubles. The filtrate was concentrated under reduced pressure and washed with diethyl ether and n-pentane. The supernatant was removed and washed with pentane. The obtained insoluble part was concentrated to obtain 200 mg (yield 4.8%) of dimethylmethylene (3-n-cyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A10). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.1-5.5 (m, 7H), 3.4 (d, 2H), 2.6 (m, 2H), 1.6-1.2 (m, 4H), 0.9-0.7 (m, 6H), 1.6-0.6 (m, 21H), FD-MS; 436 (MS)

[Example 1]
Polymerization 400 mL of purified toluene was put into a glass container having an internal volume of 500 mL that was sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, after raising the temperature to 75 ° C. under ethylene flow, methylaluminoxane (1.0 mmol in terms of Al) is added, then a toluene solution of metallocene compound (A1) (0.001 mmol in terms of Zr) is added, and an ethylene flow rate of 100 L Polymerization was conducted for 10 minutes at 75 ° C./hr. The obtained polymer was deashed with hydrochloric acid / methanol and vacuum-dried for 10 hours to obtain 2.41 g of a homoethylene polymer. Table 1 summarizes the complexes used, the polymerization conditions, the polymerization results, and the analysis results of the resulting polymer.

[Examples 2 to 10]
In the polymerization method shown in Example 1, it carried out by the same method as Example 1 except having changed the kind and addition amount of the complex. The complex used, the polymerization conditions, the polymerization results, and the analysis results of the obtained polymer are summarized in Table 1 as in Example 1.

[Example 11]
Preparation of solid component (S) In a reactor equipped with a stirrer with an internal volume of 260 L, 10 kg of silica (SiO ₂ : average particle size 60 μm) dried at 250 ° C. for 10 hours under a nitrogen atmosphere was suspended in 90.5 L of toluene. Cooled to 0-5 ° C. To this suspension was added a toluene solution of methylalumoxane (3.0 mmol / m in terms of Al atoms).
L) 45.5 L was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C. Continue to 0
After reacting at -5 ° C for 30 minutes, the temperature was raised to 95-100 ° C over about 1.5 hours, followed by reacting at 95-100 ° C for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene, and then toluene was added to a total volume of 129 L to prepare a toluene slurry of the solid component (S). A part of the obtained solid component was sampled and examined for concentration. As a result, slurry concentration: 96.5 g / L, Al concentration: 0.489 mo
1 / L.

Preparation of solid catalyst component (X-1) 50 mL of toluene was placed in a 200 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (S) prepared above (1.0 g in terms of solid part) was charged. Next, 12.7 mL of a toluene solution (0.002 mmol / mL in terms of Zr atom) of the metallocene compound (A1) was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with heptane to obtain a 100 ml heptane slurry (solid catalyst component X-1). A part of the resulting heptane slurry of the solid catalyst component (X-1) was collected to examine the concentration. As a result, the Zr concentration was 0.023 mg / mL and the Al concentration was 1.3 mg / mL.

In a 1-liter SUS autoclave sufficiently purged with nitrogen, 500 mL of purified heptane was placed, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, 10 mL of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and 40 mg of the solid catalyst component (X-1) was charged in terms of solid component, and the temperature was raised to 80 ° C. to 0.78 MPa · G. For 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 24.6 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the catalyst components, polymerization conditions, polymerization results, and the analysis results of the obtained polymer are summarized in Table 1.

[Examples 12 to 20]
Preparation of solid catalyst components (X-2) to (X-10) In the preparation of the solid catalyst component (X-1) of Example 11, metallocene compounds (A2) to (A10) were used instead of the metallocene compound (A1). The solid catalyst components (X-2) to (X-10) were obtained in the same manner as the solid catalyst component (X-1) except that they were used.

Polymerization In the polymerization method of Example 11, except that the solid catalyst components (X-2) to (X-10) were used instead of the solid catalyst component (X-1), and the amount of the solid catalyst used was changed, The same method as in Example 11 was used. The catalyst components, polymerization conditions, polymerization results, and analysis results of the obtained polymer are summarized in Table 1 as in Example 11.

[Example 21]
Polymerization 250 g of NaCl was placed in a 2 liter SUS autoclave sufficiently purged with nitrogen, and the contents were vacuum-dried at 100 ° C. for 90 minutes. Next, the inside of the autoclave was returned to normal pressure with 1-butene / ethylene mixed gas (1-butene concentration: 4 vol%), the internal temperature was set to 75 ° C., and 0.75 mmol of triisobutylaluminum was added under the mixed gas flow, Further, 25 mg of the solid catalyst component (X-2) was charged in terms of solid component and polymerized at 0.78 MPa · G and 80 ° C. for 90 minutes. The obtained contents were washed with sufficient water to completely remove NaCl, and then the polymer was vacuum-dried for 10 hours to obtain 39.5 g of an ethylene / 1-butene copolymer. Table 2 shows the GPC analysis results and various physical properties of the polymer obtained.

[Example 22]
Polymerization The polymerization method of Example 21 except that in the polymerization method of Example 21, the solid catalyst component (X-3) was used instead of the solid catalyst component (X-2), and the amount of solid catalyst used was changed. The same method was used. Table 2 shows the GPC analysis results and various physical properties of the polymer obtained.

[Example 23]
Polymerization The polymerization method of Example 21 except that, in the polymerization method of Example 21, the solid catalyst component (X-4) was used instead of the solid catalyst component (X-2), and the amount of solid catalyst used was changed. The same method was used. Table 2 shows the GPC analysis results and various physical properties of the polymer obtained.

[Example 24]
Polymerization In Example 21, the polymerization method of Example 21 except that the solid catalyst component (X-6) was used instead of the solid catalyst component (X-2), and the amount of solid catalyst used was changed. The same method was used. Table 2 shows the GPC analysis results and various physical properties of the polymer obtained.

[Comparative Example 1]
Polymerization The polymerization method shown in Example 1 was carried out in the same manner as in Example 1 except that the metallocene compound (E1) was used instead of the metallocene compound (A1). Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer. In addition, the metallocene compound (E1) used for the comparative example is shown below.
E1: Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride

〔比較例２〕
重 合
実施例１に示す重合方法において、メタロセン化合物（Ａ１）の代わりにメタロセン化合物（Ｅ２）を用い、触媒量を変更した以外は、実施例１と同様の方法で行った。得られた重合体のＧＰＣ解析結果並びに諸物性を表３に記載した。なお、比較例に使用したメタロセン化合物（Ｅ２）を下に示す。
Ｅ２；ジメチルシリレンビス（３−ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド

[Comparative Example 2]
Polymerization The polymerization method shown in Example 1 was carried out in the same manner as in Example 1, except that the metallocene compound (E2) was used instead of the metallocene compound (A1) and the amount of catalyst was changed. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer. In addition, the metallocene compound (E2) used for the comparative example is shown below.
E2: Dimethylsilylenebis (3-n-butylcyclopentadienyl) zirconium dichloride

〔比較例３〕
重 合
実施例１に示す重合方法において、メタロセン化合物（Ａ１）の代わりにメタロセン化合物（Ｅ３）を用いた以外は、実施例１と同様の方法で行った。得られた重合体のＧＰＣ解析結果並びに諸物性を表３に記載した。なお、比較例に使用したメタロセン化合物（Ｅ３）を下に示す。
Ｅ３；ジメチルシリレンビス（３−ｔｅｒｔ−ブチルシクロペンタジエニル）ジルコニウムジクロリド

[Comparative Example 3]
Polymerization The polymerization method shown in Example 1 was carried out in the same manner as in Example 1 except that the metallocene compound (E3) was used instead of the metallocene compound (A1). Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer. In addition, the metallocene compound (E3) used for the comparative example is shown below.
E3: Dimethylsilylenebis (3-tert-butylcyclopentadienyl) zirconium dichloride

〔比較例４〕
重 合
実施例１に示す重合方法において、メタロセン化合物（Ａ１）の代わりにメタロセン化合物（Ｅ４）を用い、触媒量を変更した以外は、実施例１と同様の方法で行った。得られた重合体のＧＰＣ解析結果並びに諸物性を表３に記載した。なお、比較例に使用したメタロセン化合物（Ｅ４）を下に示す。
Ｅ４；ジメチルシリレンビス（２，４−ジメチルシクロペンタジエニル）ジルコニウムジクロリド

[Comparative Example 4]
Polymerization The polymerization method shown in Example 1 was carried out in the same manner as in Example 1, except that the metallocene compound (E4) was used instead of the metallocene compound (A1) and the amount of catalyst was changed. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer. In addition, the metallocene compound (E4) used for the comparative example is shown below.
E4: Dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride

〔比較例５〕
重 合
実施例１に示す重合方法において、メタロセン化合物（Ａ１）の代わりにメタロセン化合物（Ｅ５）を用いた以外は、実施例１と同様の方法で行った。得られた重合体のＧＰＣ解析結果並びに諸物性を表３に記載した。なお、比較例に使用したメタロセン化合物（Ｅ５）を下に示す。
Ｅ５；ジメチルシリレンビス（２，３，５−トリメチルシクロペンタジエニル）ジルコニウムジクロリド

[Comparative Example 5]
Polymerization The polymerization method shown in Example 1 was carried out in the same manner as in Example 1, except that the metallocene compound (E5) was used instead of the metallocene compound (A1). Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer. In addition, the metallocene compound (E5) used for the comparative example is shown below.
E5: Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride

〔比較例６〕
固体触媒成分（ＥＸ−１）の調製
実施例１１の固体触媒成分（Ｘ−１）の調製方法において、メタロセン化合物（Ａ１）の代わりにメタロセン化合物（Ｅ１）を用いた以外は、固体触媒成分（Ｘ−１）と同様の方法で調製し固体触媒成分（ＥＸ−１）を得た。

[Comparative Example 6]
Preparation of solid catalyst component (EX-1) In the preparation method of the solid catalyst component (X-1) of Example 11, the solid catalyst component (E1) was used except that the metallocene compound (E1) was used instead of the metallocene compound (A1). A solid catalyst component (EX-1) was prepared in the same manner as in X-1).

Polymerization In the polymerization method shown in Example 11, the solid catalyst component (EX-1) was used in place of the solid catalyst component (X-1), and the amount of the solid catalyst used was changed. Went in the way. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Comparative Examples 7 to 12]
Preparation of solid catalyst components (EX-2) to (EX-7) In the preparation method of the solid catalyst component (X-1) of Example 11, metallocene compounds (E2) to (E7) instead of the metallocene compound (A1). The solid catalyst components (EX-2) to (EX-7) were obtained in the same manner as the solid catalyst component (X-1) except that was used. The metallocene compounds (E6) and (E7) used in the comparative examples are shown below.
E6; bis (cyclopentadienyl) zirconium dichloride

Ｅ７；ビス（ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド

E7: Bis (n-butylcyclopentadienyl) zirconium dichloride

重 合
実施例１１に示す重合方法において、固体触媒成分（Ｘ−１）の代わりに固体触媒成分（ＥＸ−２）〜（ＥＸ−７）を使用し、固体触媒使用量を変更した以外は、実施例１１と同様の方法で行った。比較例７〜比較例１２で得られた重合体の分析結果を比較例６と同様に表３に記載した。

Polymerization In the polymerization method shown in Example 11, except that the solid catalyst components (EX-2) to (EX-7) were used instead of the solid catalyst component (X-1), and the amount of the solid catalyst used was changed, The same method as in Example 11 was performed. The analysis results of the polymers obtained in Comparative Examples 7 to 12 are shown in Table 3 as in Comparative Example 6.

  From the above Examples and Comparative Examples, it can be seen that the crosslinked metallocene compound (component A) of the present invention can produce a polymer having a low molecular weight and a large number of terminal vinyl groups with high catalytic activity as compared with a conventionally known symmetric metallocene compound. . In addition, although the olefin polymerization catalyst shown in Comparative Example 1 satisfies this performance, its polymerization activity is extremely lower than that of the present catalyst.

Claims (9)

A bridged metallocene compound represented by the following general formula [1] or [2].

(In general formula [1] or [2],
R ^1, R ^2, R ^3, R ⁴ are selected from hydrogen atoms and alkyl groups and halogen-substituted alkyl group, each may be the same or different, even without less of R ^1, R ^2, R ³ and R ⁴ One is an ethyl group or an n-alkyl group or a halogen-substituted n-alkyl group among the groups represented by the following general formula [7 ] ,
Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom, M is selected from a titanium atom, a zirconium atom and a hafnium atom, and Q is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a lone electron You may choose from the neutral ligand which can be coordinated in a pair by the same or different combination, and j is an integer of 1-4.
In the formula [1], R ⁵ and R ⁶ are selected from a hydrogen atom, a hydrocarbon group, a hydrocarbon group-substituted silyl group, an alkoxy group, an aryloxy group, an amino group, a halogen atom and a halogen-substituted alkyl group. It may be.
A in the formula [2] represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, and A contains two or more ring structures including a ring formed with Y. You may go out. )

[Oite the above formula ^{[7], R 7 ~ R} 10 and R ¹⁵ to R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, selected from halogen atoms and halogen-substituted alkyl group, in each of the same They may be different and T represents a carbon atom. ] In the general formula [1] and [2], R ³ is a group selected group or al represented by an ethyl group, and the general formula [7], R ^1, R ² and R ⁴ are both hydrogen atoms The bridged metallocene compound according to claim 1, wherein Formula [7] according to claim 1 or 2 cross-linked metallocene compounds described R ¹⁵ and R ^16, characterized in that a hydrogen atom in the. The bridged metallocene compound according to any one of claims 1 to 3 , wherein Y in the general formula [1] or [2] is a carbon atom or a silicon atom. The catalyst for olefin polymerization containing the bridge | crosslinking metallocene compound of any one of Claims 1-4 . (A) The bridged metallocene compound according to any one of claims 1 to 4 , and
(B) (b-1) an organometallic compound represented by the following general formula (III), (IV) or (V),
(B-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with component (A) to form an ion pair,
At least one compound selected from the group consisting of:
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 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 (IV)
[In General Formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
_{^{R a r M b R b s}} X t ... (V)
[In General Formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b is selected from Mg, Zn and Cd; X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
An olefin polymerization catalyst comprising: The olefin polymerization catalyst according to claim 5 or 6 , wherein the bridged metallocene compound represented by the general formula [1] or [2] is used in a supported form. A method for polymerizing one or more monomers selected from ethylene and α-olefin in the presence of the olefin polymerization catalyst according to any one of claims 5 to 7 , wherein at least one of the monomers is ethylene. Or the manufacturing method of the olefin polymer characterized by being propylene. The manufacturing method of Claim 8 which manufactures the olefin polymer which satisfies the following requirements [1]-[3] simultaneously.
[1] Mn is 5000 or more and 20000 or less [2] α × Mn ≧ 2800
[3] Mw / Mn ≦ 3.5
(Where α is the number of vinyl ends per 1000 main chain methylene carbons of the olefin polymer, Mn is the number average molecular weight measured by GPC, and Mw is the weight average molecular weight measured by GPC.)