JP2015063515A - Metallocene compounds, olefin polymerization catalyst components and olefin polymerization catalysts containing the same, and olefin polymer production methods using olefin polymerization catalysts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: metallocene compounds allowing production of ethylenic polymers with sufficient numbers of long chain branches having sufficient length introduced to improve molding processability of metallocene polyethylene; olefin polymerization catalyst components and olefin polymerization catalysts containing the compounds; and methods of producing olefin polymers (particularly ethylenic polymers) using those olefin polymerization catalysts.SOLUTION: The present invention provides, e.g., metallocene compounds represented by the general formula (1) in the figure.

Description

  The present invention relates to a metallocene compound, an olefin polymerization catalyst component containing the metallocene compound, an olefin polymerization catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst, and more particularly, a sufficient number and length. Metallocene compounds capable of producing ethylene polymers with chain branching, olefin polymerization catalyst components and olefin polymerization catalysts containing the same, and olefin polymers (particularly ethylene polymers) using these olefin polymerization catalysts It relates to the manufacturing method.

  In general, methods for improving the molding processability of metallocene polyethylene, which has poor molding processability, include blending high-density low-density polyethylene with metallocene polyethylene and polymerizing reaction using specific metallocenes to form long-chain branches in polyethylene. The method of introduction is known. The former requires a blending process and thus increases the manufacturing cost. Moreover, although the obtained blend is excellent in molding processability, the mechanical strength which is an advantage of the metallocene polyethylene is lowered. On the other hand, a method using a bridged bisindenyl compound (see, for example, Patent Document 1) or a geometrically constrained half metallocene (see, Patent Document 2) is known as a specific metallocene for introducing the latter long-chain branch. The number of terminal double bonds and long chain branches in the polymer is small, and the effect of improving molding processability is not yet sufficient.

Patent Document 3 discloses that branched polyethylene can be produced by homopolymerization of ethylene by solution polymerization using asymmetric metallocene and methylaluminoxane in which a cyclopentadienyl group and an indenyl group are carbon-bridged. However, the length of the branch is described as having 1 to 20 carbon atoms, and the length of the branch is too short to exhibit the effect of improving the moldability as a long chain branch.
Patent Document 4 reports the polymerization of propylene by a polymerization catalyst in combination with an asymmetric metallocene compound in which a cyclopentadienyl group having a specific substituent and an indenyl group are cross-linked and methylaluminoxane. There is no description that long chain branching is generated when applied to the polymerization, and no improvement in molding processability is expected.
Further, Patent Document 5 discloses a macromonomer using a metallocene having a methyl group at positions 2, 4, and 7 of an indenyl group and a modified clay compound among asymmetric metallocenes in which a cyclopentadienyl group and an indenyl group are silicon-bridged. Although a catalyst system for producing an ethylene polymer and an ethylene / butene copolymer useful as the above has been reported, there is no description that the polymer has few terminal double bonds and long chain branching is generated by this catalyst alone.

  Recently, the present inventors have disclosed in Patent Document 6 that there is no substituent other than the crosslinking group on the cyclopentadienyl group in the asymmetric metallocene obtained by crosslinking the cyclopentadienyl group and the indenyl group with a crosslinking group, In addition, the supported catalyst for olefin polymerization having hydrogen or a specific substituent at the 3-position of the indenyl group and having a specific asymmetric metallocene as an essential component, and further, molding processability using the supported catalyst for olefin polymerization was improved. A production method of ethylene polymer was proposed. However, according to the present invention, an ethylene polymer having a high strain hardening degree of elongational viscosity can be obtained. Thus, although improvement in molding processability is seen as compared with conventional long-chain branched polyethylene, branching of long-chain branching is achieved. Since the index still does not reach that of the high-pressure low-density polyethylene, further improvement of the long-chain branch structure has been demanded.

  Under these circumstances, in order to improve the moldability of metallocene polyethylene, it is required to develop a metallocene polyethylene production method in which a sufficient number and length of long-chain branches are introduced at an early stage.

Japanese Patent Laid-Open No. 08-048711 Japanese Translation of National Publication No. 07-500622 JP 05-043619 A Japanese Patent Application Laid-Open No. 07-224079 JP 2008-050278 A JP 2011-137146 A

In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a metallocene capable of producing an ethylene polymer into which a sufficient number and length of long chain branches are introduced in order to improve the moldability of the metallocene polyethylene. An object of the present invention is to provide a compound, a catalyst component for olefin polymerization containing the compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer (particularly, an ethylene polymer) using the olefin polymerization catalyst.
In the present invention, polyethylene refers to a generic name of an ethylene homopolymer and a copolymer of ethylene and an olefin described later, and is also referred to as an ethylene polymer.

  As a result of intensive studies in order to achieve the above-mentioned problems, the inventors of the present invention cross-linked a metallocene compound having a specific substituent, that is, a cyclopentadienyl ring and an indenyl ring, and further, positions 4 and 5 of the indenyl ring. When a metallocene compound having a specific substitution at the position is used as a catalyst component for olefin polymerization, a catalyst composition comprising a combination of a compound that reacts with this to form a cationic metallocene compound and a fine particle carrier, It has been found that a metallocene polyethylene having a long chain branch can be produced, and based on these findings, the present invention has been completed.

［式（１）中、Ｍは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基または炭素数１〜２０のアルコキシ基を示す。Ｑ^１およびＱ^２は、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１〜１０の炭化水素基を示し、Ｒ^１は、結合しているＱ^１およびＱ^２と一緒に環を形成していてもよい。ｍは、０または１であり、ｍが０の場合、Ｑ^１は、Ｒ^２を含む共役５員環と直接結合している。Ｒ^２およびＲ^５は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｒ^４は、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｒ^３は、次の一般式（１−ａ）で示される置換基を示す。

（式（１−ａ）中、Ａは、周期表１４族、１５族または１６族の原子を示す。Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、それぞれ独立して、水素原子、塩素原子、臭素原子、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０のアルコキシ基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、または炭素数１〜２０の炭化水素基置換シリル基を示し、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は隣接するＲ同士でそれらに結合している原子と一緒に環を形成していてもよい。ｎは、０または１であり、ｎが０の場合、Ａに置換基Ｒ^６が存在しない。ｐは、０または１であり、ｐが０の場合、Ｒ^９が結合する炭素原子は存在せず、Ｒ^８が結合する炭素原子とＲ^１０が結合する炭素原子は直接結合している。Ａが炭素原子の場合、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０のうち少なくとも１つは水素原子ではない。）］ That is, according to the first invention of the present invention, a metallocene compound represented by the following general formula (1) is provided.

[In the formula (1), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ and Q ² represent a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ and Q ² to which R ¹ is bonded. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to a conjugated 5-membered ring containing R ² . R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. R ³ represents a substituent represented by the following general formula (1-a).

(In formula (1-a), A represents an atom of Group 14, 15 or 16 of the periodic table. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. A chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, a substituted amino group having 1 to 20 carbon atoms, a carbon number 1 to 20 An alkoxy group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form a ring together with the atoms bonded to them at adjacent R. n is 0 or 1, If is 0, .p there is no substituent ^{R 6} on a is 0 or 1, p If 0, the carbon atom to which R ⁹ is attached is absent, if .A carbon atoms carbon atoms and R ¹⁰ which R ⁸ is bonded is attached is directly bonded is a carbon atom, R ^6, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are not hydrogen atoms.)]

  Moreover, according to 2nd invention of this invention, the metallocene compound shown by following General formula (2) is provided.

［式（２）中、Ｍは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基または炭素数１〜２０のアルコキシ基を示す。Ｑ^１は、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１〜１０の炭化水素基を示し、Ｒ^１は、結合しているＱ^１と一緒に環を形成していてもよい。Ｒ^２およびＲ^５は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｒ^４は、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｒ^１１は、それぞれ独立して、水素原子、塩素原子、臭素原子、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０のアルコキシ基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、または炭素数１〜２０の炭化水素基置換シリル基を示し、５つのＲ^１１のうち少なくとも１つは水素原子ではない。］

[In the formula (2), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ represents a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ to which R ¹ is bonded. R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. R ¹¹ each independently represents a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a carbon atom having 1 to 20 carbon atoms. A hydrogen group-substituted amino group, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom Represents a hydrocarbon group-substituted silyl group of ˜20, and at least one of the five R ¹¹ is not a hydrogen atom. ]

  Moreover, according to the 3rd invention of this invention, the metallocene compound shown by following General formula (3) is provided.

［式（３）中、Ｍは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示す。Ｘ^１およびＸ^２は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基または炭素数１〜２０のアルコキシ基を示す。Ｑ^１は、炭素原子、ケイ素原子またはゲルマニウム原子を示す。Ｒ^１は、それぞれ独立して、水素原子または炭素数１〜１０の炭化水素基を示し、Ｒ^１は、結合しているＱ^１と一緒に環を形成していてもよい。Ｒ^２およびＲ^５は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｒ^４は、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示す。Ｚは、酸素原子または硫黄原子を示す。Ｒ^１３、Ｒ^１４、Ｒ^１５は、それぞれ独立して、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、酸素を含む炭素数１〜２０の炭化水素基または炭素数１〜２０の炭化水素基置換シリル基を示し、Ｒ^１３、Ｒ^１４およびＲ^１５は隣接するＲ同士でそれらが結合している炭素原子と
一緒に環を形成していてもよい。］

[In the formula (3), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ represents a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ to which R ¹ is bonded. R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. Z represents an oxygen atom or a sulfur atom. R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, carbon A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, wherein R ¹³ , R ¹⁴ and R ¹⁵ are adjacent to each other. A ring may be formed together with the carbon atom to which they are bonded with each other. ]

According to a fourth invention of the present invention, in any one of the first to third inventions, M is Zr or Hf in the general formula (1), (2) or (3). A metallocene compound is provided.
According to a fifth aspect of the present invention, there is provided the metallocene compound according to the fourth aspect, wherein M is Zr.

According to a sixth aspect of the present invention, there is provided an olefin polymerization catalyst component comprising the metallocene compound according to any one of the first to fifth aspects.
According to a seventh aspect of the present invention, there is provided an olefin polymerization catalyst comprising the metallocene compound according to any one of the first to fifth aspects.

According to the eighth aspect of the present invention, there is provided an olefin polymerization catalyst comprising the following essential components (A), (B) and (C).
Component (A): Metallocene compound according to any one of claims 1 to 5 Component (B): Compound that reacts with component (A) to form a cationic metallocene compound Component (C): Fine particle carrier

According to a ninth aspect of the present invention, there is provided an olefin polymerization catalyst according to the eighth aspect, wherein the component (B) is an aluminoxane.
According to a tenth aspect of the present invention, there is provided an olefin polymerization catalyst according to the eighth or ninth aspect, wherein the component (C) is silica.
Moreover, according to the eleventh aspect of the present invention, there is provided an olefin polymerization catalyst characterized by further comprising the following component (D) in any one of the eighth to tenth aspects.
Component (D): Organoaluminum compound

According to a twelfth aspect of the present invention, there is provided a method for producing an olefin polymer, characterized by polymerizing an olefin using the olefin polymerization catalyst according to any one of the seventh to eleventh aspects. The
According to a thirteenth aspect of the present invention, there is provided the method for producing an olefin polymer according to the twelfth aspect, wherein the olefin contains at least ethylene.
Furthermore, according to a fourteenth aspect of the present invention, there is provided the method for producing an olefin polymer according to the thirteenth aspect, wherein the olefin polymer is an ethylene polymer.

  By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a long chain branch having a sufficient number and length is introduced and the molding processability is further improved as compared with conventional metallocene compounds. (Especially an ethylene polymer) can be obtained.

It is a figure explaining the baseline and section of a chromatogram in GPC. It is a graph which shows the relationship between the branching index (g ') calculated from GPC-VIS measurement, and molecular weight (M).

  Hereinafter, the metallocene compound of the present invention, an olefin polymerization catalyst component containing the metallocene compound, an olefin polymerization catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst will be described in detail for each item.

1. Metallocene Compound The metallocene compound of the present invention crosslinks a cyclopentadinier ring and an indenyl ring represented by the following general formula (1), and is further specified at the 4-position (R ³ ) and 5-position (R ⁴ ) of the indenyl ring. It is characterized by having a substituent of

  In the general formula (1), M represents a transition metal of Ti, Zr or Hf, preferably Zr or Hf, more preferably Zr.

In the general formula (1), X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or carbon. A hydrocarbon group-substituted amino group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms is shown.

Examples of the halogen represented by X ¹ and X ² include a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X ¹ and X ² include a methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group and A benzyl group etc. are mentioned.
Examples of the C1-C20 hydrocarbon group containing oxygen represented by X ¹ and X ² include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, and an n-butoxymethyl group. I-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2 , 2-dimethyl-1-oxo-propyl group, phenylacetyl group, diphenylacetyl group, benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-furyl group and 2-tetrahydrofuryl Examples of the hydrocarbon group having 1 to 20 carbon atoms including nitrogen include, for example, a dimethylaminomethyl group, Ethylaminomethyl group, di-propylaminomethyl group, bis (dimethylamino) methyl group, bis (dii-propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (Methylimino) ethyl group, 1- (phenylimino) ethyl group, 1-[(phenylmethyl) imino] ethyl group and the like can be mentioned.
Examples of the alkoxy group having 1 to 20 carbon atoms represented by X ¹ and X ² include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, and t-butoxy. Group, phenoxy group and the like. Examples of the hydrocarbon group-substituted amino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, dii-propylamino group, din- Examples thereof include a butylamino group, a dii-butylamino group, a di-t-butylamino group and a diphenylamino group.

Preferred examples of X ¹ and X ² include chlorine atom, bromine atom, methyl group, n-butyl group, i-butyl group, methoxy group, ethoxy group, i-propoxy group, n-butoxy group, phenoxy group, dimethylamino group. And di-propylamino group, and among these, a chlorine atom, a methyl group, and a dimethylamino group are particularly preferable.

In the general formula (1), Q ¹ and Q ² represent a carbon atom, a silicon atom or a germanium atom, preferably a carbon atom or a silicon atom, more preferably a silicon atom.

In the general formula (1), each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ forms a ring together with the bonded Q ¹ and Q ^2. You may do it. M is 0 or 1, and when m is 0, Q ¹ is directly bonded to a conjugated 5-membered ring containing R ² .

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, Examples include n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, and phenyl group.
Further, when R ¹ forms a ring together with Q ¹ and Q ² , a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a silacyclobutyl group, a silacyclopentyl group, a silacyclohexyl group, etc. Is mentioned.

Preferable R ¹ includes a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, a cyclobutylidene group when Q ¹ or / and Q ² are carbon atoms, and Q ¹ or / and Q ^{When 2} is a silicon atom, examples thereof include a methyl group, an ethyl group, a phenyl group, and a silacyclobutyl group.

In general formula (1), R ² and R ⁵ are each independently a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing carbon atom having 1 to 18 carbon atoms including 1 to 6 silicon atoms. A hydrogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown.

Examples of the halogen represented by R ² and R ⁵ include a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, benzyl group, 2-methylphenyl group , 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, and the like.
Examples of the silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon represented by R ² and R ⁵ include a bis (trimethylsilyl) methyl group and a bis (t-butyldimethylsilyl) methyl group. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2- Bromocyclopentyl group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-trifluoromethylphenyl group, etc. It is below.
Examples of the hydrocarbon group having 1 to 20 carbon atoms containing oxygen represented by R ² and R ⁵ include a furyl group, a tetrahydrofuryl group, a 2-methylfuryl group, and the like, and a hydrocarbon having 1 to 20 carbon atoms. Examples of the group-substituted silyl group include trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, and phenyldimethylsilyl group. It is done.

R ² and R ⁵ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, or a cyclohexyl group. , Phenyl group, 2-methylfuryl group, and trimethylsilyl group. Among these, a hydrogen atom, a methyl group, an n-butyl group, a t-butyl group, a phenyl group, and a trimethylsilyl group are more preferable, and a hydrogen atom, a methyl group, a t-butyl group, a phenyl group, and a trimethylsilyl group are particularly preferable.

From the viewpoint of improving the polymerization activity, R ² and R ⁵ are each a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or a carbon number. A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is preferable.

In the general formula (1), R ⁴ is halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or a halogen containing 1 to 20 carbon atoms. A hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen, or a C1-C20 hydrocarbon group-substituted silyl group is shown.
In the metallocene compound of the present invention, the presence of these specific substituents at R ⁴ in the general formula (1) (that is, the 5-position of the indenyl ring) is sufficient as shown in Examples described later. An ethylene polymer into which a long chain branch having a number and a length is introduced can be produced.

Specific examples of the atom or group represented by R ⁴ include the same atoms and groups as those described in the above description of R ² and R ⁵ except for a hydrogen atom.
Preferred R ⁴ is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl. Group and cyclohexyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group are more preferable, and a methyl group is more preferable.

In the general formula (1), R ³ represents a substituent represented by the following general formula (1-a), preferably a phenyl (Ph) group having a specific substituent, a furyl group, or thienyl. Indicates groups.

In General Formula (1-a), A represents an atom of Group 14, 15 or 16 of the periodic table.
Preferable A includes a carbon atom, an oxygen atom, and a sulfur atom.

In the general formula (1-a), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, oxygen Or a C1-C20 hydrocarbon group containing nitrogen, a C1-C20 hydrocarbon group-substituted amino group, a C1-C20 alkoxy group, a C1-C18 silicon containing a C1-C6 silicon And a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms.

Specific examples other than a hydrogen atom and a halogen represented by each of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 containing oxygen or nitrogen With respect to ˜20 hydrocarbon group, C1-C20 hydrocarbon group-substituted amino group or C1-C20 alkoxy group, the same groups as those described above for X ¹ and X ² can be mentioned. About 1 to 18 carbon-containing silicon-containing hydrocarbon group, 1 to 20 carbon-containing halogen-containing hydrocarbon group, or 1 to 20 carbon-containing hydrocarbon group-substituted silyl group. The same groups as those described above for R ² and R ⁵ can be given.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form a ring together with the atoms bonded to each other at adjacent Rs.

In the general formula (1-a), n is 0 or 1, and when n is 0, there is no substituent R ^{6 in} A. p is 0 or 1, and when p is 0, there is no carbon atom to which R ⁹ is bonded, and the carbon atom to which R ⁸ is bonded and the carbon atom to which R ¹⁰ is bonded are directly bonded.
When A is a carbon atom, at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is not a hydrogen atom.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 hydrocarbon group substituted silyl groups can be mentioned. Among these, a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an i-propyl group, a t-butyl group, a methoxy group, and a trimethylsilyl group are more preferable.

Specific examples of the substituent R ³ include 4-trimethylsilylphenyl group, 4- (t-butyldimethylsilyl) phenyl group, 3,5-bistrimethylsilylphenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3, 5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 2-furyl group, 2- ( 5-methyl) furyl group, 2- (5-t-butyl) furyl group, 2- (5-trimethylsilyl) furyl group, 2- (4,5-dimethyl) furyl group, 2-benzofuryl group, 2-thienyl group 2- (5-methyl) thienyl group, 2- (5-t-butyl) thienyl group, 2- (5-trimethylsilyl) thienyl group, 2- (4,5-dimethyl) Examples include thienyl group.

  Among the compounds represented by the above general formula (1), the metallocene compound of the present invention is preferably the one represented by the following general formula (2).

In the metallocene compound represented by the general formula (2), M, X ¹ , X ² , Q ¹ , R ¹ , R ² and R ⁵ are shown in the description of the metallocene compound represented by the general formula (1). Configurations similar to atoms and groups can be selected.
Moreover, in General formula (2), R <^11> is respectively independently a hydrogen atom, a chlorine atom, a bromine atom, a C1-C20 hydrocarbon group, a C1-C20 hydrocarbon containing oxygen or nitrogen. Group, C1-C20 hydrocarbon group-substituted amino group, C1-C20 alkoxy group, C1-C18 silicon-containing hydrocarbon group including C1-C6, C1-C20 halogen And a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and at least one of the five R ¹¹ is not a hydrogen atom.
As R ¹¹ , a structure similar to the atoms and groups of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ shown in the description of the substituent R ³ represented by the general formula (1-a) is selected. can do.
Preferred examples of R ¹¹ include a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. Among these, a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an i-propyl group, a t-butyl group, a methoxy group, and a trimethylsilyl group are more preferable.

  Moreover, as for the metallocene compound part of this invention, what is shown by following General formula (3) among the compounds represented by the said General formula (1) is also preferable similarly to the said General formula (2).

In the metallocene compound represented by the general formula (3), M, X ¹ , X ² , Q ¹ , R ¹ , R ² and R ⁵ are shown in the description of the metallocene compound represented by the general formula (1). Configurations similar to atoms and groups can be selected.
Moreover, in General formula (3), Z shows an oxygen atom or a sulfur atom, R < ¹³ >, R <^14> , R <^15> is respectively independently a hydrogen atom, a halogen, a C1-C20 hydrocarbon group, C1-C18 silicon-containing hydrocarbon group containing 1 to 6 silicon, C1-C20 halogen-containing hydrocarbon group, C1-C20 hydrocarbon group containing oxygen, or C1-C20 A hydrocarbon group-substituted silyl group, wherein R ¹³ , R ¹⁴ and R ¹⁵ may form a ring together with the carbon atoms to which they are bonded to each other adjacent R;
As R ¹³ , R ¹⁴ , R ¹⁵ , atoms and groups of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ shown in the description of the substituent R ³ represented by the general formula (1-a) described above A similar structure can be selected.
Preferred examples of R ¹³ , R ¹⁴ , and R ¹⁵ include a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. Among these, a hydrogen atom, a methyl group, a t-butyl group, and a trimethylsilyl group are more preferable.

  Although the specific example of the metallocene compound of this invention is shown by General formula (4) and Table 1-Table 3, it is not limited to these.

  Moreover, the compound etc. which replaced the zirconium of the said compound with titanium or hafnium are mentioned as a preferable thing.

Among the specific compounds exemplified above, those preferable as the metallocene compound of the present invention are shown below.
1 to 10, 16, 17, 64 to 66, 70 to 80, 86, 87, 96, 97, 105 and the like in Tables 1 to 3 are listed.
Moreover, the compound etc. which replaced the zirconium of the said compound with titanium or hafnium are mentioned as a preferable thing.
Among the specific compounds exemplified above, particularly preferred metallocene compounds of the present invention are shown below.
1-4 of Tables 1-3, 64-66, 70-74, 105 etc. are mentioned.
Moreover, the compound etc. which replaced the zirconium of the said compound with titanium or hafnium are mentioned as a preferable thing.

2. Method for Synthesizing Metallocene Compound The metallocene compound of the present invention can be synthesized by any method depending on the type of substituent or bond. An example of a typical synthesis route is shown below.

  In the above synthetic route, 2 is obtained by performing a coupling reaction of 1 and 4-trimethylsilylphenylboronic acid in the presence of a palladium catalyst. After anionizing 2 with 1 equivalent of n-butyllithium or the like, it is reacted with an excess amount of dimethyldichlorosilane, and 3 is obtained by distilling off the unreacted dimethyldichlorosilane. When 3 is obtained and sodium cyclopentadienylide is reacted, 4 is obtained. After 4 is dianionized with 2 equivalents of n-butyllithium or the like, the metallocene compound 5 is obtained by reaction with zirconium tetrachloride.

The synthesis of a metallocene compound having a substituent introduced therein can be synthesized by using a corresponding substitution raw material, and instead of 4-trimethylsilylphenylboronic acid, a corresponding boronic acid such as 4-chlorophenylboronic acid, 4- By using methoxyphenylboronic acid, 5-methylfuryl-2-boronic acid, 4,5-dimethylfuryl-2-boronic acid, 2-thienylboronic acid, etc., the substituents corresponding to the 4-position of the indenyl ring respectively Can be introduced.
Further, in place of 1 4-bromo-5-methyl-indene, a corresponding substituent, for example, 4-bromo-5-ethyl-indene is used, whereby a substituent corresponding to the 5-position of the indenyl ring is used. Can be introduced.
Further, instead of the cyclopentadienyl group (Cp), a corresponding substituted cyclopentadiene anion such as t-butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-methyl-3-t-butylcyclopentadiene, etc. By using it, the complex which introduce | transduced the substituent respectively corresponding to cyclopentadiene is compoundable.

3. Olefin Polymerization Catalyst (1) Each Component The metallocene compound of the present invention forms an olefin polymerization catalyst component, and the catalyst component can be used as an olefin polymerization catalyst.
The catalyst for olefin polymerization of the present invention can contain known components except that it contains the metallocene compound of the present invention described above, but preferably contains the following components (A), (B) and (C). .
Component (A): Metallocene compound of the present invention Component (B): Compound that reacts with component (A) to form a cationic metallocene compound Component (C): Fine particle carrier

(2) Component (A)
In the olefin polymerization catalyst of the present invention, the metallocene compound represented by the general formulas (1) to (3) described above is used as the essential component (A), and one or more of these can be used. It is.

(3) Component (B)
It is preferable that the catalyst for olefin polymerization of this invention contains the compound which reacts with the metallocene compound of a component (A) and forms a cationic metallocene compound other than the said component (A) as a component (B).

  The component (B) is not particularly limited as long as it is a compound that reacts with the component (A) to form a cationic metallocene compound, and known components can be used. For example, organoaluminum oxy compounds and borane compounds can be used. Examples thereof include a borate compound.

When an organoaluminum oxy compound is used as the component (B), the degree of strain hardening (λmax) of the resulting ethylene polymer increases, or Mz / Mw (where Mz is a measure of the high molecular weight component content). Z average molecular weight and Mw measured by GPC indicate the same weight average molecular weight), which is preferable because the moldability is further improved.
When a borane compound or a borate compound is used as the component (B), the polymerization activity and copolymerizability are increased, so that the productivity of an ethylene polymer having a long chain branch is improved.

As the component (B), a mixture of the organoaluminum oxy compound and the borane compound or borate compound can also be used. Furthermore, two or more of the above borane compounds and borate compounds can be used in combination.
Hereinafter, each of these compounds will be described in more detail.

(I) Organoaluminumoxy compound The organoaluminumoxy compound has an Al-O-Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.

Of the organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes and can be suitably used as the component (B). Among aluminoxanes, methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)) is particularly suitable as the organoaluminum oxy compound.
In addition, as the organoaluminum oxy compound, two or more of each organoaluminum oxy compound can be used in combination, or a solution in which the organoaluminum oxy compound is dissolved or dispersed in an inert hydrocarbon solvent described later. May be used.

  The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any compound represented by the following general formula (5) can be used, but trialkylaluminum is preferably used.
R ¹⁶ _t AlX ³ _3-t (5)
(In the formula (5), R ¹⁶ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ³ represents a hydrogen atom or a halogen atom. Represents an atom, and t represents an integer of 1 ≦ t ≦ 3.)

Examples of the alkyl group of the trialkylaluminum include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. Of these, a methyl group is particularly preferred.
The said organoaluminum compound can also be used 1 type or in mixture of 2 or more types.

  The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.

(Ii) Borane compound As the borane compound used for the component (B), for example, triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (O-fluorophenyl) borane, tris (p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris ( 4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane , Tris (perfluorobiphenyl), Tris (perfluoroa (Thryl) borane, tris (perfluorobinaphthyl) borane and the like.

  Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred borane compounds.

(Iii) Borate compound When the borate compound used in component (B) is specifically represented, the first example is a compound represented by the following general formula (6).
[L ¹ −H] ⁺ [BR ¹⁷ R ¹⁸ X ⁴ X ⁵ ] ⁻ (6)

In Formula (6), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium or the like. Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

  Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium. Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In the formula (6), R ¹⁷ and R ¹⁸ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable. Further, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula (6) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) Borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyla Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

  Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

Moreover, the 2nd example of a borate compound is represented by following General formula (7).
[L ² ] ⁺ [BR ¹⁷ R ¹⁸ X ⁴ X ⁵ ] ⁻ (7)

In the formula (7), L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ¹⁷ , R ¹⁸ , X ⁴ and X ⁵ are the same as defined in the general formula (6).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (o-F-Ph)} 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) _{4, NaB (2,6- (CF 3} ) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, HBPh 4 · 2 diethyl ether, _{HB (3,5-F 2 -Ph)} 4 · 2 diethyl _{ether, HB (C 6 F 5)} 4 · 2 diethyl _{ether, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl ether, HB (3,5- (CF ₃ ) ₂ -Ph) ₄ · 2 diethyl ether and HB (C ₁₀ H ₇ ) ₄ · 2 diethyl ether can be exemplified.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,
5- (CF ₃ ) ₂ -Ph) ₄ , NaB (C ₁₀ F ₇ ) ₄ , HB (C ₆ F ₅ ) ₄ · 2 diethyl ether, HB (2,6- (CF ₃ ) ₂ -Ph) ₄ · 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 diethyl ether.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , HB (C ₆ F ₅ ) ₄ · 2 diethyl ether, HB (2,6- ( _{CF 3) 2 -Ph) 4 ·} 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7) 4} · 2 diethyl ether.

(4) Component (C)
In the catalyst for olefin polymerization of the present invention, an inorganic carrier, a particulate polymer carrier, or a mixture thereof is preferably used as the fine particle carrier as the component (C). As the inorganic carrier, metals, metal oxides, metal chlorides, metal carbonates, carbonaceous materials, or a mixture thereof can be used.

Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.
Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Table 1-14 Group elements include, for _{example, SiO 2, Al 2 O 3} , MgO, CaO, B 2 O 3, TiO 2, Zr
O ₂ , Fe ₂ O ₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , Al Examples include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.
As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.

  Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides, silica, alumina and the like is particularly preferable.

These inorganic carriers are usually calcined in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl groups is 0.8 to 1.5 mmol / g. It is preferable to adjust to use. The properties of these inorganic carriers are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1000 mm, preferably 50 to 500 mm, and the specific surface area is 150 to 1000 m. ² / g, preferably 200-700 m ² / g, pore volume 0.3-2.5 cm ³ / g, preferably 0.5-2.0 cm ³ / g, apparent specific gravity 0.20-0 It is preferable to use an inorganic carrier having a density of .50 g / cm ³ , preferably 0.25 to 0.45 g / cm ³ .

  The above-mentioned inorganic carriers can be used as they are, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, diisobutyl. It can be used after being brought into contact with an organoaluminum compound such as aluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

(5) Preparation Method of Olefin Polymerization Catalyst Component (A), which is a metallocene compound that is an essential component of the method for producing an ethylene polymer of the present invention, reacts with component (A) to produce a cationic metallocene compound. The contact method of each component when obtaining the catalyst for olefin polymerization which consists of a component (B) and the component (C) which is a fine particle support is not specifically limited, For example, the following methods are arbitrarily employable.

(I) The component (A) and the component (B) are contacted, and then the component (C) is contacted.
(II) The component (A) and the component (C) are contacted, and then the component (B) is contacted.
(III) The component (B) and the component (C) are contacted, and then the component (A) is contacted.

  Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed. This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, as described above, the solvent used when contacting the component (A), the component (B), and the component (C) includes an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble, and a certain type of solvent. Any aliphatic or alicyclic hydrocarbon solvent in which the components are insoluble or hardly soluble can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

  In the present invention, the use ratio of the component (A), the component (B) and the component (C) is not particularly limited, but the following ranges are preferable.

When an organoaluminum oxy compound is used as the component (B), the atomic ratio (Al / M) of aluminum of the organoaluminum oxy compound to the transition metal (M) in the component (A) that is the metallocene compound of the present invention is usually 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200.
When a borane compound or a borate compound is used as the component (B), the atomic ratio (B / M) of boron to the transition metal (M) in the component (A) that is the metallocene compound of the present invention is usually It is desirable that the range be 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound and a borane compound and / or a borate compound is used as the component (B), the component (A) which is the metallocene compound of the present invention for each compound in the mixture. It is desirable to use the same proportions of Al and B as described above with respect to the transition metal (M).

  The amount of component (C) used as the fine particle carrier is 1 g per 0.0001 to 5 mmol of transition metal (M) in component (A), preferably 1 g per 0.001 to 0.5 mmol, more preferably 0. 1 g per .01-0.1 mmol.

  The component (A), the component (B), and the component (C) are brought into contact with each other by any one of the contact methods (I) to (III), and then the solvent is removed, whereby olefin polymerization is performed. The catalyst can be obtained as a solid catalyst. The removal of the solvent is desirably performed under normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The olefin polymerization catalyst of the present invention can also be obtained by the following method.
(IV) The component (A) and the component (C) are brought into contact with each other to remove the solvent, and this is used as a solid catalyst component, which is an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Contact with (B).
(V) The component (B) and the component (C) which are an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof are brought into contact with each other to remove the solvent, and this is used as a solid catalyst component. Contact with (A).
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

  Moreover, a layered silicate can also be used as a component which serves as both the component (B) and the component (C). The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

In general, natural products are often non-ion-exchangeable (non-swellable). In that case, in order to have preferable ion-exchange (or swellable), ion exchange (or swellable) is provided. It is preferable to perform the process for providing. Among such treatments, particularly preferred are the following chemical treatments. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment performed using NaOH, KOH, NH _3, etc., (c) selected from Groups 2 to 14 of the periodic table Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one atom and a halogen atom or an anion derived from an inorganic acid, (d) alcohol, hydrocarbon Examples thereof include organic compounds such as compounds, formamide and aniline. These processes may be performed independently or two or more processes may be combined.

  The layered silicate can be controlled in particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after all the steps. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method and submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

  Of course, the above-mentioned layered silicate can be used as it is, but these layered silicates are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It can be used in combination with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

In order to carry the component (A), which is an essential component of the method for producing an ethylene polymer of the present invention, on the layered silicate, the component (A) and the layered silicate are brought into contact with each other, or the component (A), An organoaluminum compound and a layered silicate may be brought into contact with each other.
The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
(VI) The component (A) and the organoaluminum compound are brought into contact with each other and then brought into contact with the layered silicate carrier.
(VII) The component (A) and the layered silicate support are contacted and then contacted with the organoaluminum compound.
(VIII) The organoaluminum compound and the layered silicate support are contacted and then contacted with the component (A).

  Of these contact methods, (VI) and (VIII) are preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.

  Although the usage-amount of a component (A), an organoaluminum compound, and a layered silicate support | carrier is not specifically limited, The following ranges are preferable. The supported amount of component (A) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support. In the case of using an organoaluminum compound, the amount of Al supported is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.

  For the method of supporting and removing the solvent, the same conditions as those for the inorganic carrier can be used. When a layered silicate is used as a component serving as both the component (B) and the component (C), the resulting ethylene polymer has a narrow molecular weight distribution. Furthermore, the productivity of an ethylene polymer having a high polymerization activity and having a long chain branch is improved. The olefin polymerization catalyst thus obtained may be used after the prepolymerization of the monomer if necessary.

5. Method for Producing Ethylene Polymer The above-described catalyst for olefin polymerization can be used for olefin polymerization, in particular, homopolymerization of ethylene or copolymerization of ethylene and α-olefin.

  The α-olefins which are comonomers include those having 3 to 30 carbon atoms, preferably 3 to 8 carbon atoms, specifically, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl- Examples include 1-pentene and the like. As for the α-olefins, two or more types of α-olefins can be copolymerized with ethylene. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene and another α-olefin are copolymerized, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers, but generally 40 mol%. In the following, it is preferably selected in the range of 30 mol% or less, more preferably 10 mol% or less. Of course, a small amount of a comonomer other than ethylene or α-olefin can be used. In this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has polymerizable double bonds such as dienes such as hexadiene, 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate. A compound can be mentioned.

  In the present invention, the polymerization reaction can be carried out in the presence of the above-mentioned supported catalyst, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, with substantially no oxygen, water, etc., aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic rings such as cyclohexane and methylcyclohexane Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons and the like. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas flow of ethylene or comonomer is introduced, distributed, or circulated. In the present invention, more preferred polymerization is gas phase polymerization. The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and if the temperature is 60 to 90 ° C., more long chain branching tends to be introduced. is there. The pressure is in the range of normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa, and the polymerization time is 5 minutes to 10 hours, preferably 5 minutes to 5 hours. Is normal.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. Can do.
Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable. The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

6). Physical Properties of Ethylene Polymers Olefin polymers produced using the olefin polymerization catalyst of the present invention, particularly ethylene polymers, are long chains having a sufficient number and length compared to conventional metallocene polyethylene. A branch is introduced, and the moldability is further improved.

In general, polyethylene is processed into an industrial product by a molding method that passes through a molten state such as film molding, blow molding, foam molding, etc., but at this time, the elongational flow characteristics have a great influence on the ease of moldability. Giving is well known. That is, polyethylene having a narrow molecular weight distribution and no long-chain branching has poor melt strength because of its low melt strength, while polyethylene having an ultrahigh molecular weight component or a long-chain branching component is excellent in molding processability.
The ethylene polymer produced by the olefin polymerization catalyst of the present invention has a molecular weight of 100,000 measured by combining a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer) and a light scattering detector, and From the value of the branching index (g ′) at 1 million, it can be seen that a sufficient number and length of long-chain branches have been introduced, and the moldability is excellent.
In this specification, 'the value of each "g _a branching index _(g)' in the molecular weight of 100,000 and 100 of thousands" and "g _{b '".}

  Moreover, it is preferable that the ethylene-based polymer of the present invention further has the following characteristics from the viewpoint of excellent molding processability and mechanical properties.

(1) MFR
The MFR (melt flow rate, 190 ° C., 2.16 kg load) of the ethylene polymer in the present invention is preferably 0.001 to 1000 g / 10 min, more preferably 0.01 to 100 g / 10 min, and further Preferably it is 0.05-50 g / 10min, Most preferably, it is 0.1-50 g / 10min.
In addition, MFR of an ethylene-type polymer is a value when measured based on JISK6760 (190 degreeC, 2.16Kg load).

(2) Density The density of the ethylene polymer in the present invention is preferably 0.85 to 0.97 g / cm ³ , more preferably 0.88 to 0.95 g / cm ³ , and still more preferably 0.90. ˜0.94 g / cm ³ .
In addition, the density of an ethylene-type polymer is a value when measuring based on JISK7112.

(3) Mw / Mn
The molecular weight distribution (Mw / Mn) of the ethylene polymer in the present invention is preferably 2.0 to 10.0, more preferably 2.0 to 9.0, and further preferably 2.5 to 8.0. Particularly preferably, it is 2.5 to 7.5.
The molecular weight distribution (Mw / Mn) of the ethylene polymer is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is a gel permeation chromatography (GPC). According to the method, it means the value when measured under the following conditions.

Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for the viscosity formula [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733
PP: K = 1.03 × 10−4, α = 0.78

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour. The baseline and section of the obtained chromatogram are performed as illustrated in FIG.

(4) branching index _{(g a} 'and _{g b')}
The ethylene polymer in the present invention has a branching index (ga ′) at _a molecular weight of 100,000, preferably 0.50 to 0.99, more preferably 0.50 to 0.90, and still more preferably 0.55. 0.88. If branching index (g _a ') is in the above range, excellent ethylene polymer balance of melt flowability and elongation viscosity behavior is obtained.
In the ethylene polymer of the present invention, g _b ′ is 0.30 to 0.70, preferably 0.30 to 0.59, more preferably 0.35 to 0.55, and still more preferably 0.35. It is -0.50, Most preferably, it is 0.35-0.45. If the g _b ′ value is greater than 0.70, the ethylene-based polymer may be unsatisfactory due to insufficient molding processability or insufficient transparency. If the g _b ′ value is less than 0.30, the molding processability of the ethylene polymer is improved, but the impact strength of the molded body may be reduced or the transparency may be deteriorated, which may not be preferable.
Incidentally, the branching index (g a _'and g _b') is a value measured by the following method.

(I) Branch structure analysis by GPC-VIS Waters Alliance GPCV2000 was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors were connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. Two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. In order to obtain the absolute molecular weight (M) obtained from MALLS, the radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS was used. The calculation is performed with reference to the following documents.

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

(Ii) a branching index _{(g a} 'and _{g b')} calculating branching index (g ') is the intrinsic viscosity obtained sample was measured by the above Viscometer (ηbranch), separately obtained by measuring the linear polymer It is calculated as a ratio (η branch / η lin) to the intrinsic viscosity (η lin).
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity decreases as the radius of inertia decreases, the ratio of the intrinsic viscosity (ηbranch) of the branched polymer to the intrinsic viscosity (ηlin) of the linear polymer having the same molecular weight decreases as the long chain branching is introduced (ηbranch / ηlin). It will become. Therefore, when the branching index (g ′ = ηbranch / ηlin) is smaller than 1, it means that a branch is introduced, and the introduced long chain branching increases as the value decreases. Means that.
FIG. 2 shows an example of the analysis result by the GPC-VIS. FIG. 2 represents the branching index (g ′) in molecular weight (M). The g ′ value of logM = 5 was g _a ′, and the g ′ value of logM = 6 was g _b ′. Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) is used as the linear polymer.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in the examples are as follows, and the following catalyst synthesis step and polymerization step are all performed under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A. Was used.

1. Various evaluation (measurement) methods (1) MFR:
Based on JIS K6760, the measurement was performed at 190 ° C. and a load of 2.16 kg. The FR (flow rate ratio) was calculated from the ratio of MFR 10 kg and MFR (= MFR 10 kg / MFR), which was the same MFR measured at 190 ° C. and 10 kg load.

(2) Density:
The density was measured by a density gradient tube method after the strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 1 hour and further left at room temperature for 1 hour in accordance with JIS K7112.
(3) Melting point:
Using DSC (TA2000 model manufactured by DuPont or DSC6200 model manufactured by Seiko Instruments Inc.), the temperature is raised and lowered once from 20 to 170 ° C. at 10 ° C./min, and then the second time at 10 ° C./min. It was determined from the measured value at the time of temperature rise.

(4) Measurement of molecular weight distribution (Mw / Mn):
It was measured by the method described in “(3) Mw / Mn” of “6. Physical properties of ethylene polymer” described above.

(5) Measurement of branching index (g ′):
Aforementioned in "6. physical properties of the ethylene-based polymer," it was measured by the method described in the section "(4) branching index (g a _'and g _b')."

2. Materials used [Synthesis of metallocene compounds]
(1) Metallocene compound A: Synthesis of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride (1-1) 4- (4-trimethylsilyl-phenyl) Synthesis of -5-methyl-indene To a 200 ml flask, 4.82 g (24.8 mmol) of 4-trimethylsilylphenylboronic acid and 30 ml of dimethoxyethane were added to form a solution, and then 8.12 g (38.2 mmol) of potassium phosphate, water 30 ml, 4.00 g (19.1 mmol) of 4-bromo-5-methyl-indene, 0.250 g (0.956 mmol) of triphenylphosphine, and 0.330 g (0.478 mmol) of PdCl ₂ (PPh ₃ ) ₂ were sequentially added. The mixture was stirred and refluxed for 12 hours. After cooling to room temperature, 30 ml of water was added. After separating the organic phase, the aqueous phase was extracted twice with 30 ml of ethyl acetate, and the resulting organic phases were mixed and washed with brine, sodium sulfate was added to dry the organic phase. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 3.90 g (yield 73%) of 4- (4-trimethylsilyl-phenyl) -5-methyl-indene as a yellow liquid. .
(1-2) Synthesis of (4- (4-trimethylsilyl-phenyl) -5-methyl-indenyl) (cyclopentadienyl) dimethylsilane In a 200 ml flask, 4- (4-trimethylsilyl-phenyl) -5-methyl- After adding 4.60 g (16.5 mmol) of indene and 60 ml of THF to make a solution, the solution was cooled to −78 ° C., and 7.90 ml (19.8 mmol) of n-butyllithium / hexane solution (2.5 M) was added, and the mixture was brought to room temperature. The mixture was returned and stirred for 3 hours. To a 200 ml flask prepared separately, 4.26 g (33.0 mmol) of dimethyldichlorosilane and 20 ml of THF were added, cooled to −78 ° C., and the previous reaction solution was added. It returned to room temperature and stirred for 12 hours. The volatiles were removed by distillation under reduced pressure to obtain a yellow solution. To this yellow solution, 60 ml of THF was added to make a solution, and 8.67 ml (17.3 mmol) of CpNa / THF solution (2M) was added at −30 ° C. Return to room temperature and stir for 30 minutes. The yellow solution obtained by removing volatiles under reduced pressure was purified on a silica gel column, and a yellow liquid of (4- (4-trimethylsilyl-phenyl) -5-methyl-indenyl) (cyclopentadienyl) dimethylsilane was obtained. 3.00 g (45% yield) was obtained.
(1-3) Synthesis of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride In a 200 ml flask, (4- (4-trimethylsilylphenyl) -5- Methyl-indenyl) (cyclopentadienyl) dimethylsilane (2.00 g, 5.00 mmol) and diethyl ether (50 ml) were added, and the mixture was cooled to -78 ° C. Here, 4.2 ml (10.5 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution was dropped. After dropping, the temperature was returned to room temperature and stirred for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 70 ml of dichloromethane was added, and the solution was cooled to −78 ° C. in a dry ice-methanol bath. Thereto was added 1.30 g (5.50 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature. A yellow powder was obtained by distilling off the solvent from the filtrate obtained by filtering the reaction solution under reduced pressure. This powder was recrystallized with 10 ml of toluene to obtain 2.56 g (yield 91%) of dimethylsilylene (4- (4-trimethylsilylphenyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride as yellow crystals. It was.

¹ H-NMR value (C6D6): δ 0.20 (s, 3H), δ 0.23 (s, 9H), δ 0.45 (s, 3H), δ 2.31 (s, 3H), δ 5.49 (m , 1H), δ 5.53 (m, 1H), δ 5.73 (d, 1H), δ 6.62 (m, 1H), δ 6.70 (m, 1H), δ 6.96 (m, 2H), δ7 .12 (s, 1H), δ 7.27 (d, 1H), δ 7.58 (d, 2H), δ 8.27 (d, 1H).

(2) Metallocene compound B: Synthesis of dimethylsilylene (4- (2- (5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride (2-1) 4- (2- Synthesis of (5-methyl) -furyl) -5-methyl-indene To a 200 ml flask, 3.53 g (43.0 mol) of 2-methylfuran and 60 ml of THF were added to form a solution, which was then cooled to −78 ° C. and n- 18.9 ml (47.3 mmol) of a butyllithium / hexane solution (2.5 M) was added, and the mixture was returned to room temperature and stirred for 2 hours. To a 200 ml flask prepared separately, 5.86 g (43.0 mmol) of zinc chloride and 10 ml of THF were added to form a suspension, cooled to 0 ° C., and the previous reaction solution was added. It returned to room temperature and stirred for 1 hour. Furthermore, in a separately prepared 300 ml flask, 0.844 g (4.30 mmol) of copper (I) iodide, 1.62 g (2.15 mmol) of Pd (dppf) Cl _2, 4.50 g of 4-bromo-5-methyl-indene ( 21.5 mmol) and 1 ml of DMA were added to form a suspension, the previous reaction solution was added, and the mixture was stirred and refluxed for 15 hours. After cooling to room temperature, 100 ml of water was added. After separating the organic phase, the aqueous phase was extracted three times with 100 ml of ethyl acetate, and the resulting organic phases were mixed and washed twice with 100 ml of water and once with 100 ml of brine, and sodium sulfate was added to the organic phase. Was dried. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to give 2.70 g of 4- (2- (5-methyl) -furyl) -5-methyl-indene yellow liquid (yield 60%). )

Synthesis of (2-2) (4- (2- (5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) dimethylsilane 4- (4-trimethylsilyl-phenyl) -5-methyl- Using 4- (2- (5-methyl) -furyl) -5-methyl-indene instead of indene, the synthesis was performed in the same procedure as for metallocene compound A (1-2), and (4- (2- ( A pale yellow solid of 5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) dimethylsilane was obtained in 44% yield.

(2-3) Synthesis of dimethylsilylene (4- (2- (5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride (4- (4-trimethylsilylphenyl) -5- Metallocene compound A was prepared by using (4- (2- (5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) dimethylsilane instead of methyl-indenyl) (cyclopentadienyl) dimethylsilane. Synthesis was carried out in the same procedure as (1-3), and dimethylsilylene (4- (2- (5-methyl) -furyl) -5-methyl-indenyl) (cyclopentadienyl) zirconium dichloride was obtained as yellow crystals (yield). 60%).

¹ H-NMR value (C6D6): δ 0.21 (s, 3H), δ 0.42 (s, 3H), δ 2.07 (s, 3H), δ 2.56 (s, 3H), δ 5.50 (m , 1H), δ 5.53 (m, 1H), δ 5.88 (d, 1H), δ 5.95 (m, 1H), δ 6.60 (m, 1H), δ 6.63 (m, 1H), δ6 .87 (m, 2H), δ 7.05 (d, 1H), δ 7.55 (d, 1H).

(3) Metallocene compound C: Synthesis of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride (3-1) Synthesis of 4- (4-trimethylsilyl-phenyl) -indene To a 500 ml flask, 10.0 g (51.5 mmol) of 4-trimethylsilylphenylboronic acid and 200 ml of dimethoxyethane were added to form a solution, and then 27.3 g (128 mmol) of potassium phosphate, 100 ml of water, 8.37 g of 4-bromoindene ( 43.0 mmol), 0.22 g (0.86 mmol) of triphenylphosphine, and 0.300 g (0.430 mmol) of PdCl ₂ (PPh ₃ ) ₂ were sequentially added, and the mixture was stirred and refluxed for 12 hours. After cooling to room temperature, 100 ml of water was added. After separating the organic phase, the aqueous phase was extracted twice with 100 ml of ethyl acetate, the obtained organic phases were mixed and washed with brine, sodium sulfate was added to dry the organic phase. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 9.0 g (yield 79%) of 4- (4-trimethylsilyl-phenyl) -indene as a yellow liquid.

Synthesis of (3-2) (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) dimethylsilane In a 200 ml flask, 16.2 g (61.2 mmol) of 4- (4-trimethylsilyl-phenyl) -indene ) And 100 ml of THF to make a solution, cooled to −78 ° C., added with 29.4 ml (173.5 mmol) of n-butyllithium / hexane solution (2.5 M), returned to room temperature, and stirred for 4 hours. To a separately prepared 300 ml flask, 14.8 ml (122 mmol) of dimethyldichlorosilane and 20 ml of THF were added to form a solution, cooled to −78 ° C., and the previous reaction solution was added. It returned to room temperature and stirred for 12 hours. Volatiles were removed by evaporation under reduced pressure to obtain 21.8 g of a yellow solution. To this yellow solution, 80 ml of THF was added to obtain a solution, and 36.7 ml (73.5 mmol) of a CpNa / THF solution (2M) was added at −30 ° C. The mixture was returned to room temperature and stirred for 1 hour, and 100 ml of ice water was added. Extraction was performed twice with 100 ml of ethyl acetate, and the obtained organic phases were mixed and washed with brine, sodium sulfate was added to dry the organic phase. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give 12.0 g of a yellow liquid of (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) dimethylsilane (yield) 51%).

(3-3) Synthesis of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride ) 1.20 g (3.00 mmol) of dimethylsilane and 20 ml of diethyl ether were added and cooled to -70 ° C. To this was added dropwise 2.60 ml (6.60 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution. After dropping, the temperature was returned to room temperature and stirred for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 30 ml of dichloromethane was added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto, 0.770 g (3.30 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred overnight while gradually returning to room temperature. A yellow powder was obtained by distilling off the solvent from the filtrate obtained by filtering the reaction solution under reduced pressure. This powder was recrystallized with 10 ml of toluene to obtain 0.500 g (yield 31%) of dimethylsilylene (4- (4-trimethylsilylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride as yellow crystals.

¹ H-NMR value (CDCl 3): δ 0.21 (s, 3 H), δ 0.23 (s, 9 H), δ 0.43 (s, 3 H), δ 5.48 (m, 1 H), δ 5.51 (m , 1H), δ 5.81 (d, 1H), δ 6.60 (m, 1H), δ 6.66 (m, 1H), δ 6.95 (dd, 1H), δ 7.13 (s, 1H), δ7 .39 (dd, 2H), δ 7.57 (d, 2H), δ 7.95 (d, 2H).

(4) Metallocene compound D: Synthesis of dimethylsilylene (4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride (4-1) 4- (2- (5-methyl) Synthesis of) -furyl) -indene To a 200 ml flask, 2.52 g (30.7 mmol) of 2-methylfuran and 30 ml of THF were added to form a solution, which was then cooled to −78 ° C. and an n-butyllithium / hexane solution (2. 5M) 14.7 ml (36.9 mmol) was added, and the mixture was returned to room temperature and stirred for 4 hours. To a separately prepared 200 ml flask, 4.18 g (30.7 mmol) of zinc chloride and 10 ml of THF were added to form a suspension, cooled to 0 ° C., and the previous reaction solution was added. It returned to room temperature and stirred for 1 hour. Furthermore, 0.35 g (1.84 mmol) of copper iodide (I), 0.690 g (0.932 mmol) of Pd (dppf) Cl _2, and 3.00 g (15.3 mmol) of 4-bromoindene were prepared in a separately prepared ml flask. DMA (5 ml) was added to form a suspension, the previous reaction solution was added, and the mixture was stirred and refluxed for 15 hours. After cooling to room temperature, 50 ml of water was added. After separating the organic phase, the aqueous phase was extracted twice with 50 ml of ethyl acetate, and the resulting organic phases were mixed and washed twice with 50 ml of water and once with 50 ml of brine, and sodium sulfate was added to the organic phase. Was dried. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 2.10 g (yield 70%) of 4- (2- (5-methyl) -furyl) -indene as a yellow liquid. .

Synthesis of (4-2) (4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) dimethylsilane 4- (2 instead of 4- (4-trimethylsilyl-phenyl) -indene Using-(5-methyl) -furyl) -indene, synthesis was carried out in the same procedure as for metallocene compound A (1-2), and (4- (2- (5-methyl) -furyl) -indenyl) (cyclo A pale yellow solid of pentadienyl) dimethylsilane was obtained in 38% yield.

(4-3) Synthesis of dimethylsilylene (4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride (4- (4-trimethylsilylphenyl) indenyl) (cyclopentadienyl) ) (4- (2- (5-Methyl) -furyl) -indenyl) (cyclopentadienyl) dimethylsilane was used in place of dimethylsilane, and the synthesis was performed in the same procedure as for metallocene compound A (1-3). Dimethylsilylene (4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride was obtained as yellow crystals (25% yield).

¹ H-NMR value (CDCl 3): δ0.00 (s, 3H), δ0.18 (s, 3H), δ1.79 (s, 3H), δ5.22 (m, 1H), δ5.32 (m , 1H), δ 5.64 (m, 1H), δ 5.72 (d, 1H), δ 6.33 (m, 1H), δ 6.35 (m, 1H), δ 6.70 (m, 2H), δ6 .82 (d, 1H), δ 7.43 (d, 1H), δ 7.60 (d, 1H).

(5) Metallocene compound E: Synthesis of dimethylsilylene (3,5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride (5-1) 3,5 Synthesis of -dimethyl-4- (2- (5-methyl) -furyl) -indene To a 200 ml flask, 2.20 g (26.8 mol) of 2-methylfuran and 60 ml of THF were added to form a solution, and then cooled to -78 ° C. Then, 11.8 ml (29.5 mmol) of n-butyllithium / hexane solution (2.5 M) was added, and the mixture was returned to room temperature and stirred for 3 hours. To a separately prepared 200 ml flask, 3.65 g (26.8 mmol) of zinc chloride and 10 ml of THF were added to form a suspension, cooled to 0 ° C., and the previous reaction solution was added. It returned to room temperature and stirred for 1 hour. Furthermore, in a separately prepared 300 ml flask, 0.260 g (1.34 mmol) of copper (I) iodide, 0.386 g (0.672 mmol) of Pd (dba) _2, 0.640 g (1.34 mmol) of x-Phos, 3, 5 -3.00 g (13.4 mmol) of dimethyl-4-bromo-indene was added to form a suspension, the previous reaction solution was added, and the mixture was stirred and refluxed for 15 hours. Cool to 15 ° C. and add 100 ml of water. After separating the organic phase, the aqueous phase was extracted twice with 100 ml of ethyl acetate, and the resulting organic phases were mixed and washed twice with 50 ml of water and once with 50 ml of brine, and sodium sulfate was added to the organic phase. Was dried. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to give 2.46 g (yield) of 3,5-dimethyl-4- (2- (5-methyl) -furyl) -indene. 82%).

Synthesis of (5-2) (3,5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) dimethylsilane 4- (4-trimethylsilyl-phenyl) -5- Using 3,5-dimethyl-4- (2- (5-methyl) -furyl) -indene instead of methyl-indene, the synthesis was carried out in the same procedure as metallocene compound A (1-2), (3, A pale yellow solid of 5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) dimethylsilane was obtained in a yield of 62%.

(5-3) Synthesis of dimethylsilylene (3,5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride (4- (4-trimethylsilylphenyl)- Instead of 5-methyl-indenyl) (cyclopentadienyl) dimethylsilane, (3,5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) dimethylsilane was used. , Synthesized in the same procedure as metallocene compound A (1-3), dimethylsilylene (3,5-dimethyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium Dichloride was obtained as yellow crystals (44% yield).

¹ H-NMR value (C6D6): δ 0.00 (s, 3H), δ 0.24 (s, 3H), δ 1.88 (s, 3H), δ 2.02 (s, 3H), δ 2.15 (s , 3H), δ 5.15 (m, 1H), δ 5.22 (s, 1H), δ 5.31 (m, 1H), δ 5.69 (m, 1H), δ 6.33 (m, 1H), δ6 .43 (m, 1H), δ 6.45 (m, 1H), δ 6.60 (d, 1H), δ 6.89 (d, 1H).

(6) Metallocene compound F: Synthesis of dimethylsilylene (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) (cyclopentadienyl) zirconium dichloride (6-1) 2-bromophenyl- Synthesis of 2-chloroethyl ketone 2-bromobenzoic acid (5.30 g, 26.4 mmol) and 25 ml of thionyl chloride were added to a 100 ml flask and refluxed for 2 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and 5.50 g of the acid chloride obtained was used for the next reaction without purification.
An acid chloride (5.00 g, 22.7 mmol) and 50 ml of dichloromethane were added to a 100 ml flask to make a solution, and then aluminum chloride (3.02 g, 22.7 mmol) was further added, and ethylene was blown at 20 ° C. for 4 hours. The reaction was quenched with 4N hydrochloric acid, the organic phase and the aqueous phase were separated, and the aqueous phase was washed 3 times with 50 ml of methyl-t-butyl ether. The organic phase was collected 3 times with 50 ml of water and 100 ml of saturated aqueous sodium hydrogen carbonate solution Subsequently, it was washed with 100 ml of saturated saline. After drying with sodium sulfate, the solvent was distilled off under reduced pressure to obtain 4.80 g (yield 85%) of Compound 3. Used for the next reaction without further purification.

(6-2) Synthesis of 7-bromo-1-indanone Aluminum chloride (7.40 g, 55.6 mmol) and sodium chloride (2.15 g, 37.1 mmol) were added to a 100 ml flask and heated to 130 ° C. 2-Bromophenyl-2-chloroethyl ketone (4.60 g, 18.5 mmol) was added slowly and the mixture was stirred at 160 ° C. for 1 hour. After the reaction, it was cooled to 30 ° C. and quenched with ice water. After adjusting the pH to 5 with concentrated hydrochloric acid, the organic phase and the aqueous phase are separated, the aqueous phase is washed 3 times with 100 ml of dichloromethane, the organic phase is collected, washed with 100 ml of water and 100 ml of saturated brine, and dried over sodium sulfate. And the crude product was obtained by depressurizingly distilling a solvent. Further purification was performed with a silica gel column (petroleum ether / ethyl acetate = 30/1) to obtain 1.60 g (yield 33%) of 7-bromo-1-indanone.

(6-3) Synthesis of 7- (2- (5-methyl) -furyl) -1-indanone After adding 2-methylfuran (0.933 g, 11.4 mmol) and 10 ml of THF to a 100 ml flask, An n-butyllithium / hexane solution (2.5 M, 4.70 ml, 11.4 mmol) was added at 30 ° C., and the mixture was stirred at room temperature for 2 hours. To a 100 ml flask prepared separately, zinc chloride (1.55 g, 11.4 mmol) and 10 ml of THF were added, and then the above reaction solution was added at 0 ° C., followed by stirring at room temperature for 1 hour. Furthermore, copper (I) iodide (90 mg, 0.473 mmol), Pd (dppf) Cl ₂ (177 mg, 0.236 mmol), 7-bromo-1-indanone (2.00 g, 9.45 mmol) was added to a separately prepared 100 ml flask. ) And 10 ml of DMA were added to the above suspension and refluxed for 15 hours. After cooling to room temperature, 50 ml of water was added, and extraction was performed twice with 50 ml of ethyl acetate. The organic phase was collected, washed twice with 50 ml of water and 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Furthermore, it refine | purified with the silica gel column (petroleum ether / ethyl acetate = 20/1), and 0.70 g (yield 35%) of 7- (2- (5-methyl) -furyl) -1-indanone was obtained.

Synthesis of (6-4) 1-methyl-7- (2- (5-methyl) -furyl) -indene 7- (2- (5-methyl) -furyl) -1-indanone (1.40 g) in a 100 ml flask , 6.59 mmol) and 20 ml of THF to make a solution, methyl lithium / diethyl ether solution (1.6 M, 7.5 ml, 11.9 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 10 hours. The reaction was quenched with 20 ml of saturated aqueous ammonium chloride solution and the volatile components were removed in vacuo. The remaining solution was extracted twice with 50 ml of ethyl acetate, the organic phase was collected, washed with 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. Used for the next reaction without further purification.
The crude product and 30 ml of toluene were added to a 100 ml flask to prepare a solution, p-toluenesulfonic acid (62.0 mg, 0.330 mmol) was added, and the mixture was stirred at 130 ° C. for 2 hours. During the stirring, water generated using a Dean-Stark trap was removed. After cooling to room temperature, 30 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the organic phase was separated. After the aqueous phase was extracted three times with 50 ml of ethyl acetate, the organic phases were collected, washed with 50 ml of saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The product was further purified with a silica gel column (petroleum ether) to obtain 0.850 g (yield 61%) of 1-methyl-7- (2- (5-methyl) -furyl) -indene.

(6-5) Synthesis of dimethyl (cyclopentadienyl) (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) silane In a 100 ml flask was added 1-methyl-7- (2- (5 -Methyl) -furyl) -indene (4.80 g, 22.8 mmol) and 60 ml of THF were added to form a solution, and then n-butyllithium / hexane solution (2.5 M, 11.0 ml, 27.4 mmol) at -78 ° C. And stirred at room temperature for 3 hours. To a separately prepared 200 ml flask, dimethyldichlorosilane (5.89 g, 45.8 mmol) and 10 ml of THF were added to form a solution, and then the reaction product was added dropwise at −78 ° C. and stirred at room temperature for 12 hours. Volatile components were distilled off under reduced pressure, and 20 ml of THF was added again to make a solution. Then, a solution of sodium cyclopentadienylide / THF (2M, 12.0 ml, 24.0 mmol) was slowly added dropwise at −20 ° C. at room temperature. For 1 hour. A volatile component was distilled off under reduced pressure to obtain a crude product. Further purification with a silica gel column (petroleum ether) gave 4.20 g (55% yield) of dimethyl (cyclopentadienyl) (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) silane. It was.

(6-6) Synthesis of dimethylsilylene (cyclopentadienyl) (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride dimethyl (cyclopentadienyl) (3 -Methyl-4- (2- (5-methyl) -furyl) -indenyl) silane (2.00 g, 6.00 mmol) and 40 ml of diethyl ether were added to form a solution, and then n-butyllithium / hexane at -78 ° C. The solution (2.5 M, 5.1 ml, 12.6 mmol) was added, and the mixture was stirred at room temperature for 2 hours and further at 50 ° C. for 1 hour. Volatile components were distilled off under reduced pressure, followed by addition of 160 ml of dichloromethane, and zirconium tetrachloride (1.53 g, 6.60 mmol) was added at −78 ° C., followed by stirring at room temperature for 12 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated to give 2.1 g of dimethylsilylene (cyclopentadienyl) (3-methyl-4- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride ( Yield 70%).

¹ H-NMR value (CDCl 3): δ 0.80 (s, 3H), δ 1.04 (s, 3H), δ 2.25 (s, 3H), δ 2.36 (s, 3H), δ 5.75 (m , 1H), δ 5.77 (s, 1H), δ 5.87 (m, 1H), δ 6.07 (m, 1H), δ 6.40 (d, 1H), δ 6.81 (m, 1H), δ6 .85 (m, 1H), δ 7.06 (dd, 1H), δ 7.40 (m, 2H).

3. Examples and Comparative Examples (Example 1)
(1) Preparation of solid catalyst Under a nitrogen atmosphere, 5 g of silica calcined at 600 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while heating in an oil bath at 150 ° C. A separately prepared 100 ml two-necked flask was charged with 70 mg of metallocene compound A under a nitrogen atmosphere and dissolved in 13.4 ml of dehydrated toluene. At room temperature, 8.6 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was added to a toluene solution of the metallocene compound A and stirred for 30 minutes. While heating and stirring the 200 ml two-necked flask containing the vacuum-dried silica in a 40 ° C. oil bath, the whole amount of the toluene solution of the reaction product of the metallocene compound A and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating to 40 ° C. to obtain a solid catalyst.

(2) Production of ethylene / 1-butene copolymer An ethylene / 1-butene copolymer was produced using the solid catalyst obtained in (1) Preparation of solid catalyst in Example 1 above.
That is, 80 g of polyethylene pellets sufficiently dehydrated and deoxygenated and 33 mg of triethylaluminum were introduced into a 1 liter stainless steel autoclave having a stirring and temperature control device, and the temperature was raised to 70 ° C. while stirring. Ethylene containing 10% by weight of 1-butene was introduced until the partial pressure reached 2.0 MPa, and then 101 mg of the solid catalyst was injected with argon gas, and polymerization was performed for 60 minutes while maintaining the ethylene partial pressure at 2.0 MPa and the temperature at 70 ° C. Continued.
As a result, 12.5 g of ethylene / 1-butene copolymer was produced. The copolymer obtained had an MFR of 0.02 g / 10 min and a density of 0.918 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

(Example 2)
Ethylene 1-butene was obtained in the same manner as in Example 1 except that 100 mg of the solid catalyst obtained in Example 1 was used and 34 ml of hydrogen was introduced at normal pressure before introducing ethylene containing 10% by weight of 1-butene. A copolymer was produced.
As a result, 10.4 g of ethylene / 1-butene copolymer was produced. The copolymer obtained had an MFR of 0.79 g / 10 min and a density of 0.924 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

(Example 3)
An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that 60 mg of the solid catalyst obtained in Example 1 was used and the polymerization temperature was 90 ° C.
As a result, 12.4 g of ethylene / 1-butene copolymer was produced. The obtained copolymer had an MFR of 0.13 g / 10 min and a density of 0.928 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

Example 4
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 62 mg of metallocene compound B was used instead of 70 mg of metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Ethylene / 1-butene copolymer was prepared in the same manner as in Example 1 except that 53 mg of the solid catalyst obtained in the preparation of the solid catalyst of Example 4 above (1) was used. A polymer was produced.
As a result, 16.3 g of ethylene / 1-butene copolymer was produced. The MFR of the obtained copolymer was 0.14 g / 10 minutes. The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.
(Example 5)
An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that 48 mg of the solid catalyst obtained in Example 4 was used and the polymerization temperature was 90 ° C.
As a result, 23.8 g of ethylene / 1-butene copolymer was produced. The MFR of the obtained copolymer was 0.67 g / 10 minutes. The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

(Example 6)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 63 mg of metallocene compound E was used instead of 70 mg of metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Ethylene / 1-butene copolymer was prepared in the same manner as in Example 1, except that 49 mg of the solid catalyst obtained in the preparation of the solid catalyst of Example 6 above (1) was used. A polymer was produced.
As a result, 12.4 g of ethylene / 1-butene copolymer was produced. The MFR of the obtained copolymer was 0.42 g / 10 minutes. The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

(Comparative Example 1)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 68 mg of metallocene compound C was used instead of 70 mg of metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Ethylene / 1-butene copolymer was prepared in the same manner as in Example 1 except that 53 mg of the solid catalyst obtained in the preparation of the solid catalyst of Comparative Example 1 was used. A polymer was produced.
As a result, 5.4 g of ethylene / 1-butene copolymer was produced. The obtained copolymer had an MFR of 0.10 g / 10 min and a density of 0.924 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.
(Comparative Example 2)
Ethylene 1-butene was obtained in the same manner as in Example 1 except that 54 mg of the solid catalyst obtained in Comparative Example 1 was used and 34 ml of hydrogen was introduced at normal pressure before introducing ethylene containing 10% by weight of 1-butene. A copolymer was produced.
As a result, 4.3 g of ethylene / 1-butene copolymer was produced. The obtained copolymer had an MFR of 10.4 g / 10 min and a density of 0.919 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.
(Comparative Example 3)
Example 54 was used except that 54 mg of the solid catalyst obtained in Comparative Example 1 was used and 102 ml of hydrogen was introduced at normal pressure before introducing ethylene containing 10% by weight of 1-butene and the polymerization temperature was 90 ° C. Similarly, an ethylene / 1-butene copolymer was produced.
As a result, 10.8 g of ethylene / 1-butene copolymer was produced. The copolymer obtained had an MFR of 1.7 g / 10 min and a density of 0.930 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.
(Comparative Example 4)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 60 mg of metallocene compound D was used instead of 70 mg of metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Ethylene / 1-butene copolymer was prepared in the same manner as in Example 1 except that 203 mg of the solid catalyst obtained in (1) Preparation of solid catalyst of Comparative Example 4 was used. A polymer was produced.
As a result, 24.2 g of ethylene / 1-butene copolymer was produced. The copolymer obtained had an MFR of 0.3 g / 10 min and a density of 0.920 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.
(Comparative Example 5)
An ethylene / 1-butene copolymer was produced in the same manner as in Example 1, except that 203 mg of the solid catalyst obtained in Comparative Example 4 was used, the polymerization temperature was 90 ° C., and the polymerization time was 47 minutes.
As a result, 29.5 g of ethylene / 1-butene copolymer was produced. The MFR of the obtained copolymer was 8.5 g / 10 minutes. The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

(Comparative Example 6)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1, except that 62 mg of metallocene compound F was used instead of 70 mg of metallocene compound A.
(2) Production of ethylene / 1-butene copolymer Ethylene / 1-butene copolymer was prepared in the same manner as in Example 1 except that 52 mg of the solid catalyst obtained in (1) Preparation of solid catalyst in Comparative Example 6 was used. A polymer was produced.
As a result, 16.1 g of ethylene / 1-butene copolymer was produced. The obtained copolymer had an MFR of 0.21 g / 10 min and a density of 0.929 g / cm ³ . The polymerization conditions are summarized in Table 4, and the polymerization results are summarized in Table 5.

4). Evaluation From the results shown in Table 5, the ethylene polymers of Examples 1 to 6 produced using the metallocene compound satisfying the requirements of the present invention, except for the substituent at the 5-position (R ⁴ ) of the indenyl ring, Compared with the ethylene polymers of Comparative Examples 1 to 6 prepared using a metallocene compound having a similar structure, g _a ′ and / or g _b ′ is low, and a larger number of long chain branches are introduced, and molding processing is performed. It has been shown that sex is improved.
In particular, in the ethylene polymers of Examples 1, 2, 4 and 6 produced at a polymerization temperature of 70 ° C., compared with the ethylene polymers of Comparative Examples 1, 2, 4 and 6 produced under the same conditions, The decrease in g _a ′ and / or g _b ′ is significant.

  By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a metallocene polyethylene having a long chain branch having a sufficient number and length can be obtained as compared with conventional metallocene compounds. And the moldability of metallocene polyethylene can be improved. Therefore, the metallocene compound of the present invention, an olefin polymerization catalyst component containing the same, an olefin polymerization catalyst, and a method for producing an olefin polymer (particularly an ethylene polymer) using the olefin polymerization catalyst, It is very useful in industry.

Claims (14)

A metallocene compound represented by the following general formula (1).

[In the formula (1), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ and Q ² represent a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ and Q ² to which R ¹ is bonded. m is 0 or 1, and when m is 0, Q ¹ is directly bonded to a conjugated 5-membered ring containing R ² . R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. R ³ represents a substituent represented by the following general formula (1-a).

(In formula (1-a), A represents an atom of Group 14, 15 or 16 of the periodic table. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. A chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, a substituted amino group having 1 to 20 carbon atoms, a carbon number 1 to 20 An alkoxy group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may form a ring together with the atoms bonded to them at adjacent R. n is 0 or 1, If is 0, .p there is no substituent ^{R 6} on a is 0 or 1, p If 0, the carbon atom to which R ⁹ is attached is absent, if .A carbon atoms carbon atoms and R ¹⁰ which R ⁸ is bonded is attached is directly bonded is a carbon atom, R ^6, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are not hydrogen atoms.)] A metallocene compound represented by the following general formula (2).

[In the formula (2), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ represents a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ to which R ¹ is bonded. R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. R ¹¹ each independently represents a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or a carbon atom having 1 to 20 carbon atoms. A hydrogen group-substituted amino group, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom Represents a hydrocarbon group-substituted silyl group of ˜20, and at least one of the five R ¹¹ is not a hydrogen atom. ] A metallocene compound represented by the following general formula (3).

[In the formula (3), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ¹ represents a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may form a ring together with Q ¹ to which R ¹ is bonded. R ² and R ⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 to 1 carbon atoms. 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing oxygen or a C1-C20 hydrocarbon group-substituted silyl group. R ⁴ includes halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and oxygen. A C1-C20 hydrocarbon group or a C1-C20 hydrocarbon group-substituted silyl group is shown. Z represents an oxygen atom or a sulfur atom. R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, carbon A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, wherein R ¹³ , R ¹⁴ and R ¹⁵ are adjacent to each other. A ring may be formed together with the carbon atom to which they are bonded with each other. ]   The metallocene compound according to any one of claims 1 to 3, wherein M is Zr or Hf in the general formula (1), (2) or (3).   The metallocene compound according to claim 4, wherein M is Zr.   A catalyst component for olefin polymerization comprising the metallocene compound according to any one of claims 1 to 5.   An olefin polymerization catalyst comprising the metallocene compound according to any one of claims 1 to 5. An olefin polymerization catalyst comprising the following essential components (A), (B) and (C):
Component (A): Metallocene compound according to any one of claims 1 to 5 Component (B): Compound that reacts with component (A) to form a cationic metallocene compound Component (C): Fine particle carrier   9. The olefin polymerization catalyst according to claim 8, wherein the component (B) is an aluminoxane.   Component (C) is a silica, The olefin polymerization catalyst of Claim 8 or 9 characterized by the above-mentioned. Furthermore, the following component (D) is included, The catalyst for olefin polymerization of any one of Claims 8-10 characterized by the above-mentioned.
Component (D): Organoaluminum compound   The manufacturing method of the olefin polymer characterized by polymerizing an olefin using the catalyst for olefin polymerization of any one of Claims 7-11.   The method for producing an olefin polymer according to claim 12, wherein the olefin contains at least ethylene.   The method for producing an olefin polymer according to claim 13, wherein the olefin polymer is an ethylene polymer.

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