JP2016141635A - Metallocene compound, olefin polymerization catalyst component and olefin polymerization catalyst containing the same, and method for producing olefin polymer by using olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallocene compound which improves copolymerizability of an α-olefin while keeping the capacity for forming a long-chain branch and makes higher the molecular weight (Mw) of a copolymer to be obtained, and to provide an olefin polymerization catalyst component containing the metallocene compound, an olefin polymerization catalyst containing the metallocene compound, and a method for producing an olefin polymer (particularly an ethylene-based polymer) by using the olefin polymerization catalyst.SOLUTION: The metallocene compound is expressed by a general formula (1).SELECTED DRAWING: None

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. More specifically, the present invention relates to a phenyl group at the 4-position of the indene ring. Metallocene compounds having a substituent and having a crosslinked Cp-Ind as a basic skeleton, olefin polymerization catalyst components and olefin polymerization catalysts containing the same, and olefin polymers using these olefin polymerization catalysts (especially ethylene-based polymers) The present invention relates to a method for producing a polymer.

  In general, methods for improving the moldability of metallocene-based polyethylene, which has poor moldability, include blending high-pressure low-density polyethylene with metallocene-based 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 it is applied to the polymerization.
Furthermore, 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 improve the processability of metallocene-based polyethylene while maintaining the long-chain branching ability equivalent to that of the prior art and the copolymerizability of α-olefin. Improved metallocene compound having a high molecular weight (Mw), an olefin polymerization catalyst component containing the same, an olefin polymerization catalyst, and an olefin polymer using the olefin polymerization catalyst It is in providing the manufacturing method of (especially ethylene polymer).
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 to achieve the above-mentioned problems, the present inventors have cross-linked a metallocene compound having a specific substituent, that is, a cyclopentadienyl ring and an indenyl ring, and further a phenyl group at the 4-position of the indene ring. When a metallocene compound having a substituent 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, a sufficient number and length It has been found that a metallocene polyethylene having a long chain branch can be produced, and the present invention has been completed based on these findings.

［式（１）中、Ｍは、Ｔｉ、ＺｒまたはＨｆのいずれかの遷移金属を示し；
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し；
Ｑは、炭素原子、ケイ素原子またはゲルマニウム原子を示し；
Ｒ^１およびＲ^２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とＲ^２は、結合しているＱと一緒に環を形成していてもよく；
ｍは、１、２または３であり；
Ｒ^３およびＲ^５〜Ｒ^１１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または炭素数１〜２０の炭化水素基置換シリル基を示し；
Ｒ^１２〜Ｒ^１６は、それぞれ独立して、水素原子、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、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、または炭素数１〜２０のハロゲン含有炭化水素基を示し、Ｒ^１２〜Ｒ^１６のうち少なくとも１つは水素原子ではない。］
で示されるメタロセン化合物。
［２］Ｒ^１２〜Ｒ^１６は、それぞれ独立して、水素原子、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、または炭素数１〜２０のハロゲン含有炭化水素基を示し、Ｒ^１２〜Ｒ^１６のうち少なくとも１つは水素原子ではないことを特徴とする［１］に記載のメタロセン化合物。
［３］Ｒ^１２〜Ｒ^１６は、それぞれ独立して、水素原子、炭素数１〜２０の炭化水素基を示し、Ｒ^１２〜Ｒ^１６のうち少なくとも１つは水素原子ではないことを特徴とする［２］に記載のメタロセン化合物。
［４］ｍが１であることを特徴とする［１］〜［３］のいずれか１項に記載のメタロセン化合物。
［５］Ｑが炭素原子またはケイ素原子であることを特徴とする［１］〜［４］のいずれか１項に記載のメタロセン化合物。
［６］ＭがＺｒまたはＨｆであることを特徴とする［１］〜［５］のいずれか１項に記載のメタロセン化合物。
［７］ＭがＺｒであることを特徴とする［６］に記載のメタロセン化合物。
［８］［１］〜［７］のいずれか１項に記載のメタロセン化合物を含むことを特徴とするオレフィン重合用触媒成分。
［９］［１］〜［７］のいずれか１項に記載のメタロセン化合物を含むことを特徴とするオレフィン重合用触媒。
［１０］以下の必須成分（Ａ）、（Ｂ）および（Ｃ）を含むことを特徴とするオレフィン重合用触媒。
成分（Ａ）：［１］〜［７］のいずれか１項に記載のメタロセン化合物
成分（Ｂ）：成分（Ａ）のメタロセン化合物と反応してカチオン性メタロセン化合物を生成させる化合物
成分（Ｃ）：微粒子担体
［１１］前記成分（Ｂ）がアルミノキサンであることを特徴とする［１０］に記載のオレフィン重合用触媒。
［１２］前記成分（Ｃ）がシリカであることを特徴とする［１０］または［１１］に記載のオレフィン重合用触媒。
［１３］更に、次の成分（Ｄ）を含むことを特徴とする［１０］〜［１２］のいずれか１項に記載のオレフィン重合用触媒。
成分（Ｄ）：有機アルミニウム化合物
［１４］［９］〜［１３］のいずれか１項に記載のオレフィン重合用触媒を用いてオレフィンを重合させることを特徴とするオレフィン系重合体の製造方法。
［１５］オレフィンが少なくともエチレンを含むことを特徴とする［１４］に記載のオレフィン系重合体の製造方法。
［１６］オレフィン系重合体がエチレン系重合体であることを特徴とする［１５］に記載のオレフィン系重合体の製造方法。 That is, the present invention
[1] 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;
Q represents a carbon atom, a silicon atom or a germanium atom;
R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² may form a ring together with Q bonded thereto ;
m is 1, 2 or 3;
R ³ and R ^{5 to} R ¹¹ 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 or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms;
R ^{12 to} R ¹⁶ are each independently a hydrogen atom, 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 group substitution having 1 to 20 carbon atoms. An amino group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, wherein at least one of R ^{12 to} R ¹⁶ is a hydrogen atom; is not. ]
A metallocene compound represented by
[2] R ^{12 to} R ¹⁶ are each independently a hydrogen atom, 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. 1 to 20 halogen-containing hydrocarbon groups, at least one of R ^{12 to} R ¹⁶ is not a hydrogen atom, The metallocene compound according to [1].
[3] R ^{12 to} R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{12 to} R ¹⁶ is not a hydrogen atom. The metallocene compound according to [2].
[4] The metallocene compound according to any one of [1] to [3], wherein m is 1.
[5] The metallocene compound according to any one of [1] to [4], wherein Q is a carbon atom or a silicon atom.
[6] The metallocene compound according to any one of [1] to [5], wherein M is Zr or Hf.
[7] The metallocene compound according to [6], wherein M is Zr.
[8] An olefin polymerization catalyst component comprising the metallocene compound according to any one of [1] to [7].
[9] An olefin polymerization catalyst comprising the metallocene compound according to any one of [1] to [7].
[10] An olefin polymerization catalyst comprising the following essential components (A), (B) and (C):
Component (A): Metallocene compound according to any one of [1] to [7] Component (B): Compound that reacts with the metallocene compound of component (A) to form a cationic metallocene compound Component (C) : Fine particle carrier [11] The catalyst for olefin polymerization as described in [10], wherein the component (B) is an aluminoxane.
[12] The olefin polymerization catalyst as described in [10] or [11], wherein the component (C) is silica.
[13] The catalyst for olefin polymerization according to any one of [10] to [12], further comprising the following component (D):
Component (D): Organoaluminum compound [14] A method for producing an olefin polymer, wherein an olefin is polymerized using the olefin polymerization catalyst described in any one of [9] to [13].
[15] The method for producing an olefin polymer according to [14], wherein the olefin contains at least ethylene.
[16] The method for producing an olefin polymer according to [15], wherein the olefin polymer is an ethylene polymer.

  The metallocene compound of the present invention has an excellent feature that the copolymerization property of α-olefin is improved while having a long chain branching ability equivalent to that of the prior art by having a substituent in the phenyl group at the 4-position of the indene ring. Have Further, by using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a long-chain branched olefin polymer (particularly an ethylene polymer) having a higher molecular weight (Mw) than that of a conventional metallocene compound is obtained. Can do.

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

1. Metallocene Compound The metallocene compound of the present invention is characterized in that it has a cyclopentadinyl ring represented by the following general formula (1) and an indenyl ring, and further has a substituent in the phenyl group at the 4-position of the indene ring.

  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 C1-C20 hydrocarbon group-substituted amino group represented by X ¹ and X ² include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-propylamino group, and di-n-butyl. Examples thereof include an amino group, a di i-butylamino group, a di-t-butylamino group, and a diphenylamino group.
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.

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 represents 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), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² are a ring together with Q bonded thereto. May be formed. M is 1, 2 or 3, preferably 1.

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

Preferable R ¹ and R ² include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an ethylene group, and a cyclobutylidene group when Q is a carbon atom, and a methyl group when Q is a silicon atom. , Ethyl group, phenyl group, and silacyclobutyl group.

In General Formula (1), R ³ and R ^{5 to} R ¹¹ are each independently a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a C 1 to 18 carbon atom containing 1 to 6 silicon atoms. A silicon-containing hydrocarbon 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 ³ and R ^{5 to} R ¹¹ 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, and 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- Examples thereof include a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-t-butylphenyl group, and a 3,5-di-t-butylphenyl group.
Examples of the silicon-containing hydrocarbon group having 1 to 18 carbon atoms and having 1 to 6 silicon atoms represented by R ³ and R ^{5 to} R ¹¹ include bis (trimethylsilyl) methyl group and bis (t-butyldimethylsilyl) methyl. 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, and 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 and the like.
Examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms represented by R ³ and R ^{5 to} R ¹¹ include trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, and t-butyldimethylsilyl group. Group, triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group and the like.

Preferred R ³ and R ^{5 to} R ¹¹ are a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms, Or it is a C1-C18 hydrocarbon group substituted silyl group. Preferred examples of the alkyl group having 1 to 6 carbon atoms include 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 can be mentioned. Preferred examples of the hydrocarbon group-substituted silyl group having 1 to 18 carbon atoms include trimethylsilyl group, ethyldimethylsilyl group, n-propyldimethylsilyl group, Triethylsilyl group, i-propyldimethylsilyl group, n-butyldimethylsilyl group, i-butyldimethylsilyl group, t-butyldimethylsilyl group, trii-propylsilyl group, t-butyldiethylsilyl group, dimethylphenylsilyl group Methyldiphenylsilyl group, t-butyldiphenylsilyl group, among these, Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group are more preferable, methyl group T-butyl group and trimethylsilyl group are more preferable.

In General Formula (1), R ^{12 to} R ¹⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or 1 carbon atom. Represents a hydrocarbon group-substituted amino group having -20 hydrocarbons, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and R ^{12 to} R ¹⁶ At least one of them is not a hydrogen atom.
In the metallocene compound of the present invention, when the phenyl group at the 4-position of the indene ring has a substituent of R ^{12 to} R ¹⁶ , the long chain branching ability equivalent to that of the prior art is exhibited as shown in the examples described later. As it is, the copolymerizability of α-olefin is improved, and a long-chain branched olefin polymer (especially ethylene polymer) having a high molecular weight (Mw) as compared with conventional metallocene compounds can be obtained. .

Specific examples other than a hydrogen atom represented by each of R ^{12 to} R ¹⁶ include a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, or 1 carbon atom. The hydrocarbon group-substituted amino group of ˜20 can include the same groups as those described in the description of X ¹ and X ² described above, and contains silicon having 1 to 18 carbon atoms including 1 to 6 silicon. Examples of the hydrocarbon group or the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described in the description of R ³ and R ^{5 to} R ¹¹ described above.
Preferable R ^{12 to} R ¹⁶ are a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. Preferred examples of the alkyl group having 1 to 6 carbon atoms include 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 are mentioned, and among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl A group is more preferable, and a methyl group, i-propyl group, n-butyl group, and t-butyl group are more preferable.

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, R ¹ , R ² , and R ^{12 to} R ¹⁶ are the same as those of the metallocene compound represented by the general formula (1). A configuration similar to the atoms and groups shown in the description can be selected.

  Although the specific example of the metallocene compound of this invention is shown by General formula (2) and Table 1, 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.

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, 1 and 4-biphenylboronic acid are subjected to a coupling reaction in the presence of a palladium catalyst to give 2. 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.

A metallocene compound having a substituent introduced therein can be synthesized by using a corresponding substituted raw material. Instead of 4-biphenylboronic acid, a corresponding boronic acid such as 4-methylphenylboronic acid, 4- By using i-propylphenylboronic acid, 4-t-butylphenylboronic acid, 4-chlorophenylboronic acid, 4-methoxyphenylboronic acid, etc., it is possible to introduce a substituent corresponding to the 4-position of the indenyl ring. it can.
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 the metallocene compound of 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 (2) 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 the 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. Further, 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 of the compounds represented by the following general formula (3) can be used, but trialkylaluminum is preferably used.
R ¹⁷ _t AlX ³ _3-t (3)
(In the formula (3), R ¹⁷ 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 (4).
[L ¹ −H] ⁺ [BR ¹⁸ R ¹⁹ X ⁴ X ⁵ ] ⁻ (4)

In Formula (4), 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 formula (4), R ¹⁸ and R ¹⁹ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are linked 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 (4) 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 (5).
[L ² ] ⁺ [BR ¹⁸ R ¹⁹ X ⁴ X ⁵ ] ⁻ (5)

In the formula (5), L ² is carbo cation, 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 ¹⁸ , R ¹⁹ , X ⁴ and X ⁵ are the same as defined in the general formula (4).

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 is preferred.

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, _{ZrO 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, for 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 elongation flow characteristic has 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.
The MFR of the ethylene polymer is a value when measured according to JIS K6760 (190 ° C., 2.16 kg 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, still more 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 0.75, preferably 0.30 to 0.70, more preferably 0.35 to 0.65, and further preferably 0.35. ~ 0.61. If the g _b ′ value is greater than 0.75, the ethylene 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 inertia radius decreases, the ratio (ηbranch / ηlin) 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 long chain branching is introduced. 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) 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.

(3) 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-biphenyl) indenyl) (cyclopentadienyl) zirconium dichloride (1-1) Synthesis of 4- (4-biphenyl) indene

Metallocene compound A

In a 100 ml flask, 2.00 g (10.3 mmol) of 4-bromoindene, 2.44 g (12.3 mmol) of 4-biphenylboronic acid, 0.054 g (0.21 mmol) of triphenylphosphine, 0.072 g of dichlorobistriphenylphosphine palladium (0.10 mmol), tripotassium phosphate 4.37 g (20.6 mmol), 1,2-dimethoxyethane 20 ml, and water 20 ml were added, and the mixture was stirred and refluxed for 16 hours under an argon atmosphere. The reaction mixture was cooled to room temperature, 20 ml of water was added, and the organic layer was separated. The aqueous phase was extracted twice with 20 ml of ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was distilled off with a rotary evaporator. The solid obtained was recrystallized with 5 ml of ethyl acetate to give 1.70 g of 4- (4-biphenyl) indene as a light green solid (yield) 62%).
(1-2) Synthesis of dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) silane Into a 200 ml flask was added 1.60 g (6.0 mmol) of 4- (4-biphenyl) indene and 20 ml of dehydrated THF. Cool to −78 ° C. under an argon atmosphere. 2.9 ml (7.3 mmol) of n-butyllithium / hexane solution (2.5 M) was added dropwise and reacted at 25 ° C. for 4 hours to obtain a suspension. A separately prepared solution of 1.6 ml (13.3 mmol) of dimethyldichlorosilane and 20 ml of THF was cooled to −78 ° C., and the suspension prepared above was added dropwise and stirred at 25 ° C. for 12 hours. Volatiles were removed under reduced pressure, and 25 ml of THF was added to the residue and cooled to -30 ° C. 3.1 ml (6.2 mmol) of cyclopentadienyl sodium / THF solution (2.0 M) was added dropwise, and the mixture was stirred at 25 ° C. for 1 hour. 30 ml of water was added to the reaction mixture, the organic layer was separated, and the aqueous phase was extracted twice with 30 ml of ethyl acetate. The organic layers were combined, dehydrated over anhydrous sodium sulfate, and the solution obtained by filtering out sodium sulfate was concentrated on a rotary evaporator. The resulting crude product was purified by column chromatography (silica gel, heptane), and dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) silane was obtained as a yellow solid in 1.40 g (yield 60%). Obtained.
(1-3) Synthesis of dimethylsilylene (4- (4-biphenyl) indenyl) (cyclopentadienyl) zirconium dichloride dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) silane in a 200 ml flask 00 g (7.7 mmol) and 40 ml of diethyl ether were added and stirred under an argon atmosphere. 6.5 mL (16.3 mmol) of n-butyllithium / hexane solution (2.5 M) was added dropwise, and the mixture was stirred at 20 ° C. for 4 hours. The solvent was distilled off under reduced pressure, and 70 ml of dichloromethane was added to the resulting solid and cooled to -78 ° C. 1.88 g (8.1 mmol) of zirconium tetrachloride was added, the temperature was raised to 20 ° C. over 3 hours, and the mixture was further stirred for 12 hours. Insoluble matter was removed by filtration, and the solid obtained by concentrating the recovered solution under reduced pressure was washed with a toluene / hexane mixed solution (volume ratio 2/1, 15 ml), and dimethylsilylene (4- (4-biphenyl) indenyl). (Cyclopentadienyl) zirconium dichloride was obtained as a yellow powdery solid in 3.50 g (yield 83%).
¹ H-NMR value (400 MHz, CDCl ₃ ): δ 0.88 (s, 3H), δ 1.09 (s, 3H), δ 5.92-5.95 (m, 1H), δ 5.94-5.96 (M, 1H), δ 6.27 (d, 1H), δ 6.79-6.82 (m, 1H), δ 6.87-6.89 (m, 1H), δ 7.17-7.25 (m , 2H), δ 7.38 (t, J = 8.0 Hz, 1H), δ 7.45-7.53 (m, 4H), δ 7.67 (d, J = 7.6 Hz, 2H), δ 7.73. (D, J = 8.4 Hz, 2H), δ 7.78 (d, J = 8.4 Hz, 2H).

(2) Metallocene compound B: Synthesis of dimethylsilylene (4- (3,5-dimethylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride

Metallocene compound B

(2-1) Synthesis of 4- (3,5-dimethylphenyl) indene 5.31 g (27.2 mmol) of 4-bromoindene and 7.06 g (47.0 mmol) of 3,5-dimethylphenylboronic acid in a 500 ml flask , 0.14 g (0.53 mmol) of triphenylphosphine, 0.19 g (0.27 mmol) of dichlorobistriphenylphosphine palladium, 11.50 g (54.2 mmol) of tripotassium phosphate, 200 ml of 1,2-dimethoxyethane, 50 ml of water Was stirred and refluxed for 16 hours under an argon atmosphere. The reaction mixture was cooled to room temperature, 100 ml of water was added, and the organic layer was separated. The aqueous phase was extracted twice with 100 ml of ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was distilled off with a rotary evaporator. The resulting crude product was purified by column chromatography (silica gel, petroleum ether) to give 4- (3,5-dimethylphenyl) indene as a colorless oil. As 5.00 g (yield 83%).

(2-2) Synthesis of dimethyl (4- (3,5-dimethylphenyl) indenyl) (cyclopentadienyl) silane 4- (3,5-dimethylphenyl) indene instead of 4- (4-biphenyl) indene Was synthesized in the same procedure as for metallocene compound A (1-2), and 3.30 g of a light yellow oily product of dimethyl (4- (3,5-dimethylphenyl) indenyl) (cyclopentadienyl) silane ( Yield 42%).

(2-3) Synthesis of dimethylsilylene (4- (3,5-dimethylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride Instead of dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) silane Dimethyl (4- (3,5-dimethylphenyl) indenyl) (cyclopentadienyl) silane was synthesized in the same procedure as for metallocene compound A (1-3), and dimethylsilylene (4- (3, Obtained as 3.50 g (69% yield) of a yellow powdery solid of 5-dimethylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride.

¹ H-NMR value (400 MHz, CDCl ₃ ): δ 0.87 (s, 3H), δ 1.07 (s, 3H), δ 2.38 (s, 6H), δ 5.87-5.90 (m, 1H) ), Δ 5.91-5.94 (m, 1H), δ 6.23 (d, J = 3.2 Hz, 1H), δ 6.76-6.80 (m, 1H), δ 6.84-6.86. (M, 1H), δ 7.03 (s, 1H), δ 7.16-7.23 (m, 2H), δ 7.30 (s, 2H), δ 7.41 (d, J = 7.6 Hz, 2H) ).

(3) Metallocene compound C: Synthesis of dimethylsilylene (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride

Metallocene compound C

(3-1) Synthesis of 4- (3,5-di-t-butylphenyl) indene In a 300 ml flask, 7.00 g (35.9 mmol) of 4-bromoindene and 9,5-di-t-butylphenylboronic acid 9. 05 g (38.7 mmol), 0.94 g (3.6 mmol) of triphenylphosphine, 1.26 g (1.8 mmol) of dichlorobistriphenylphosphine palladium, 15.20 g (71.6 mmol) of tripotassium phosphate, 1,2- Dimethoxyethane (100 ml) and water (100 ml) were added, and the mixture was stirred and refluxed for 16 hours under an argon atmosphere. The reaction mixture was cooled to room temperature, 100 ml of water was added, and the organic layer was separated. The aqueous phase was extracted twice with 100 ml of ethyl acetate, and the organic layers were combined and dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the crude product obtained by distilling off the solvent with a rotary evaporator was purified by column chromatography (silica gel, petroleum ether) to give 4- (3,5-di-t-butylphenyl) indene. Obtained as an orange oil in 10.00 g (91% yield).
(3-2) Synthesis of dimethyl (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) silane 4- (3,5-di-sine instead of 4- (4-biphenyl) indene t-butylphenyl) indene was synthesized in the same procedure as metallocene compound A (1-2), and dimethyl (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) silane As an orange oil (yield 61%).
(3-3) Synthesis of dimethylsilylene (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride Dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) Using dimethyl (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) silane in place of silane, synthesis was performed in the same procedure as metallocene compound A (1-3), and dimethylsilylene Obtained as 2.20 g (53% yield) of a yellow powdered solid of (4- (3,5-di-t-butylphenyl) indenyl) (cyclopentadienyl) zirconium dichloride.

¹ H-NMR value (400 MHz, CDCl ₃ ): δ 0.88 (s, 3H), δ 1.09 (s, 3H), δ 1.38 (s, 18H), δ 5.89-5.93 (m, 1H) ), Δ 5.94-5.97 (m, 1H), δ 6.22 (d, J = 3.6 Hz, 1 H), δ 6.79-6.83 (m, 1 H), δ 6.86-6.92. (M, 1H), [delta] 7.17-7.24 (m, 2H), [delta] 7.43-7.51 (m, 1H) [delta] 7.57 (s, 2H).

(4) Metallocene compound D: Synthesis of dimethylsilylene (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride

Metallocene compound D

(4-1) Synthesis of 4-phenyl-indene To a 1 L flask, 31.8 g (260 mmol) of 4-bromo-indene and 400 ml of dimethoxyethane were added to form a solution, and then 42.4 g (217 mmol) of phenylboronic acid and triphenyl were added. Phosphine 0.360 g (1.38 mmol), PdCl ₂ (PPh ₃ ) ₂ 0.510 g (0.387 mmol), tripotassium phosphate 138 g (652 mmol) and water 400 ml were added at room temperature, and the mixture was stirred and refluxed for 6 hours. Cool to room temperature and add 400 ml of water. After separating the organic phase, the aqueous phase was extracted twice with 400 ml of ethyl acetate, and the resulting organic phase was mixed and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 34.0 g of 4-phenyl-indene yellow liquid (yield 81%).
(4-2) Synthesis of (4-phenyl-indenyl) (cyclopentadienyl) dimethylsilane Using 4-phenyl-indene instead of 4- (4-biphenyl) indene, the metallocene compound A (1-2) and Synthesis was carried out in the same procedure to obtain 3.7 g (yield 45%) of (4-phenyl-indenyl) (cyclopentadienyl) dimethylsilane as a yellow liquid.
(4-3) Synthesis of dimethylsilylene (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride Instead of dimethyl (4- (4-biphenyl) indenyl) (cyclopentadienyl) silane, (4-phenyl- Indenyl) (cyclopentadienyl) dimethylsilane was synthesized in the same procedure as metallocene compound A (1-3), and yellow crystals of dimethylsilylene (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride. Obtained as 5.90 g (60% yield).

¹ H-NMR value (CDCl ₃ ): δ 0.87 (s, 3H), δ 1.08 (s, 3H), δ 5.91 (m, 1H), δ 5.94 (m, 1H), δ 6.24 ( d, 1H), δ 6.79 (m, 1H), δ 6.86 (m, 1H), δ 7.20 (m, 2H), δ 7.46 (m, 5H), δ 7.68 (d, 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 69 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-hexene copolymer An ethylene / 1-hexene copolymer was produced using the solid catalyst obtained in the preparation of the solid catalyst in Example 1 (1).
Specifically, 300 ml of n-hexane, 15 ml of 1-hexene (0.12 mol), 1.0 ml of triethylaluminum / toluene (0.5 M) (0.5 mmol as triethylaluminum) were placed in a dry 1 L autoclave with an induction stirrer, The inside of the system was replaced with ethylene, and the internal temperature was raised to 70 ° C. Here, 0.066 g of the solid catalyst obtained in (1) preparation of the solid catalyst of Example 1 was injected with ethylene, and polymerization was performed for 60 minutes while maintaining the internal temperature at 75 ° C. and the ethylene partial pressure at 1.4 MPa. After the reaction, ethanol was added to the autoclave to stop the reaction, and the resulting polymer was recovered. The polymer obtained by this reaction was 5.2 g, the catalytic activity was 79 [g-polymer / g-catalyst · time], and the MFR of the obtained copolymer was 0.12 g / 10 min. The polymerization conditions are summarized in Table 1, and the polymerization results are summarized in Table 2.

(Example 2)
(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 B was used instead of 69 mg of metallocene compound A.
(2) Production of ethylene / 1-hexene copolymer Ethylene / 1-hexene copolymer was prepared in the same manner as in Example 1 except that 0.074 g of the solid catalyst obtained in the preparation of the solid catalyst in Example 2 (1) above was used. A hexene copolymer was produced. The polymer obtained by this reaction was 6.4 g, the catalytic activity was 86 [g-polymer / g-catalyst · hour], and the MFR of the obtained copolymer was 0.68 g / 10 min. The polymerization conditions are summarized in Table 1, and the polymerization results are summarized in Table 2.

(Example 3)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 66 mg of metallocene compound C was used instead of 69 mg of metallocene compound A.
(2) Production of ethylene / 1-hexene copolymer Ethylene / 1-hexene copolymer was prepared in the same manner as in Example 1 except that 0.080 g of the solid catalyst obtained in the preparation of the solid catalyst in Example 3 (1) was used. A hexene copolymer was produced. The polymer obtained by this reaction was 8.8 g, the catalytic activity was 110 [g-polymer / g-catalyst · hour], and the MFR of the obtained copolymer was 0.36 g / 10 min. The polymerization conditions are summarized in Table 1, and the polymerization results are summarized in Table 2.

(Comparative Example 1)
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 51 mg of metallocene compound D was used instead of 69 mg of metallocene compound A.
(2) Production of ethylene / 1-hexene copolymer Ethylene / 1-hexene copolymer was prepared in the same manner as in Example 1 except that 0.070 g of the solid catalyst obtained in (1) Preparation of solid catalyst of Comparative Example 1 was used. A hexene copolymer was produced. The polymer obtained by this reaction was 8.2 g, the catalytic activity was 117 [g-polymer / g-catalyst · hour], and the MFR of the obtained copolymer was 0.33 g / 10 min. The polymerization conditions are summarized in Table 1, and the polymerization results are summarized in Table 2.

4). Evaluation From the results shown in Table 3, the ethylene polymers of Examples 1 to 4 produced using the metallocene compound satisfying the requirements of the present invention are the same except for the substituent of the phenyl group at the 4-position of the indene ring. Since g _a ′ and / or g _b ′ are equivalent as compared with the ethylene polymer of Comparative Example 1 prepared using the metallocene compound having a structure, the same number of ethylene polymers as in Comparative Example 1 are obtained. It has been shown that long chain branching is introduced and the moldability is improved. In addition, it is shown that the ethylene-based polymers of Examples 1 to 4 have a higher molecular weight (Mw) than the ethylene polymer of Comparative Example 1.

  By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, the copolymerization property of α-olefin is improved while maintaining the long-chain branching ability equivalent to that of the prior art, and compared to conventional metallocene compounds. Thus, a metallocene polyethylene having a high molecular weight (Mw) of the obtained copolymer is obtained. 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 (16)

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;
Q represents a carbon atom, a silicon atom or a germanium atom;
R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² may form a ring together with Q bonded thereto ;
m is 1, 2 or 3;
R ³ and R ^{5 to} R ¹¹ 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 or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms;
R ^{12 to} R ¹⁶ are each independently a hydrogen atom, 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 group substitution having 1 to 20 carbon atoms. An amino group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, wherein at least one of R ^{12 to} R ¹⁶ is a hydrogen atom; is not. ]
A metallocene compound represented by R ^{12 to} R ¹⁶ are each independently a hydrogen atom, 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 20 carbon atoms. 2. The metallocene compound according to claim 1, wherein at least one of R ^{12 to} R ¹⁶ is not a hydrogen atom. R ^{12 to} R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{12 to} R ¹⁶ is not a hydrogen atom. Metallocene compounds described in 1.   The metallocene compound according to claim 1, wherein m is 1.   Q is a carbon atom or a silicon atom, The metallocene compound of any one of Claims 1-4 characterized by the above-mentioned.   M is Zr or Hf, The metallocene compound of any one of Claims 1-5 characterized by the above-mentioned.   The metallocene compound according to claim 6, wherein M is Zr.   An olefin polymerization catalyst component comprising the metallocene compound according to any one of claims 1 to 7.   An olefin polymerization catalyst comprising the metallocene compound according to any one of claims 1 to 7. 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 7 Component (B): Compound that reacts with the metallocene compound of component (A) to form a cationic metallocene compound Component (C): Fine particles Carrier   The said component (B) is an aluminoxane, The catalyst for olefin polymerization of Claim 10 characterized by the above-mentioned.   The catalyst for olefin polymerization according to claim 10 or 11, wherein the component (C) is silica. Furthermore, the following component (D) is included, The catalyst for olefin polymerization of any one of Claims 10-12 characterized by the above-mentioned.
Component (D): Organoaluminum compound   An olefin polymer is produced by using the olefin polymerization catalyst according to any one of claims 9 to 13, wherein the olefin polymer is produced.   The method for producing an olefin polymer according to claim 14, wherein the olefin contains at least ethylene.   The method for producing an olefin polymer according to claim 15, wherein the olefin polymer is an ethylene polymer.