JP5396773B2 - Olefin polymerization catalyst and process for producing olefin polymer - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same.

  Low density polyethylene (LDPE) produced by the high pressure radical method is a branched polyolefin, and its side chain has a non-linear dendritic structure. Such a structure is excellent in molding processability such as melt fluidity and melt tension, and is advantageous when melt-processing a polymer, but on the other hand it reduces the mechanical strength of the solid polymer and the stretchability of the melt polymer. There are drawbacks.

  For this reason, linear high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) obtained with Ziegler catalysts or metallocene catalysts are generally used in applications that require the mechanical strength of solid polymers and the stretchability of molten polymers. Has been used. However, these HDPE and LLDPE do not have good moldability, which is an advantage of LDPE.

  Examples of techniques for improving the molding processability of HDPE and LLDPE by a polyethylene production method include, for example, (a) a method of widening the molecular weight distribution by a multistage polymerization method using a conventional Ziegler catalyst (see, for example, Patent Documents 1 to 3) (B) a method for producing polyethylene having a long chain branch using a traditional Cr-based catalyst, and (c) a method for producing polyethylene having a long chain branch by polymerizing ethylene using a specific metallocene catalyst ( For example, see Patent Document 4), (d) a method of producing a polyethylene having a long chain branch by completely copolymerizing ethylene and a macromonomer using a specific metallocene catalyst (see, for example, Patent Document 5), ) A method of blending linear polyethylene with an ethylene / macromonomer copolymer (for example, see Patent Document 6) has been proposed. However, the moldability of polyethylene obtained by these methods is still not sufficient. Furthermore, the polyethylene obtained by the methods (a) and (b) has a problem that the mechanical strength is lowered due to the broadening of the molecular weight distribution.

  And (f) a method for producing a long-chain branched olefin polymer having a high flow activation energy (Ea) using a catalyst containing a specific metallocene compound (see, for example, Patent Document 7), A method for producing an olefin polymer having a high flow activation energy (Ea) using a specific metallocene catalyst has been proposed (see, for example, Patent Document 8). The resulting olefin polymer has a high melt tension only in a specific molding processing temperature range, and it is necessary to select a processing machine suitable for the olefin polymer to be processed in the molding process.

  As a method for producing an olefin polymer having excellent mechanical strength and excellent molding processability under a wide range of molding process conditions, a specific transition metal compound, a macromonomer, and a macromolecular monomer having a vinyl group at the terminal are used. A catalyst containing a specific transition metal compound that is copolymerized with an olefin to produce a high molecular weight component as a constituent component and a method for producing an olefin polymer using the catalyst are disclosed (for example, see Patent Documents 9 and 10).

  Generally, the strength of the olefin polymer is improved by increasing the ratio of the high molecular weight component. Therefore, development of a catalyst capable of efficiently producing a high molecular weight component is demanded. In addition, for the purpose of suppressing fouling in the reactor and improving continuous productivity, it is desired to improve the particle shape of the produced olefin polymer.

  Regarding the polymerization activity of the metallocene compound, it is disclosed that the polymerization activity is improved by introducing a substituent into the cyclopentadienyl group and its analog in the ligand (for example, Patent Document 11).

JP-A-2-53811 JP-A-2-132109 JP-A-10-182742 US Pat. No. 5,272,236 Japanese translation of PCT publication No. 8-502303 Special table 2001-511212 gazette JP 2002-105132 A Japanese Patent Laid-Open No. 2004-292772 JP 2006-321991 A JP 2007-169341 A Japanese Patent Laid-Open No. 10-226694

  An object of the present invention is to provide an olefin polymerization catalyst capable of efficiently producing a high molecular weight component and a method for producing an olefin polymer using the same, in order to solve the problems of the prior art as described above. There is.

As a result of intensive studies to solve the above problems, a transition metal compound (component (A)) having a specific structure as a transition metal compound for copolymerizing an olefin and a macromonomer to produce a high molecular weight component, a macromonomer, In the olefin polymerization catalyst comprising the specific transition metal compound (component (B)) and the activating cocatalyst (component (C)) for producing the low molecular weight component, the following general formula (1) )
It came to discover that a high molecular weight component can be efficiently manufactured by manufacturing an olefin polymer using the transition metal compound represented by these.

  That is, the present invention provides a component (A) represented by the following general formula (1)

（ここで、Ｍ^１はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｘ^１は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｒ^１からＲ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示し（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）、互いに同じでも異なっていてもよい。また、互いに連結し環を形成していても良い。ｆは０から４の整数を示す。Ｅ^１は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子である。）で表される遷移金属化合物、
成分（Ｂ）下記一般式（２）

(Wherein M ¹ is a titanium atom, a zirconium atom or a hafnium atom, X ¹ is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number ¹ to R ⁴ . 20 represents a silyl group, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein a hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms) Is a silyl group Which may be substituted by an amino group, an alkoxy group, an aryloxy group or a halogen atom), may be the same or different from each other, and may be linked to each other to form a ring. E ¹ is a carbon atom, a silicon atom, a germanium atom, or a tin atom.)
Component (B) The following general formula (2)

（ここで、Ｍ^２はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｘ^２は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｅ^２は酸素原子、硫黄原子または下記一般式（３）

(Here, M ² is a titanium atom, a zirconium atom or a hafnium atom, and X ² is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) E ² may be an oxygen atom, a sulfur atom, or the following general formula (3).

（ここでＲ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｅ^３はケイ素原子、ゲルマニウム原子または錫原子であり互いに同じでも異なっていても良い。）で表され、ｅは１から５の整数である。eが２以上の場合、Ｅ^２は互いに同じでも異なっていてもよい。
Ｃｐ^１は下記一般式（４）、（５）または（６）

(Wherein R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); E ³ is a silicon atom, a germanium atom, or a tin atom, and may be the same or different from each other), and e is an integer of 1 to 5. When e is 2 or more, E ² may be the same as or different from each other.
Cp ¹ represents the following general formula (4), (5) or (6)

（ここでＲ^５〜Ｒ^９は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。）で示され、互いに同じでも異なっていても良い。Ｃｐ^１はＭ^２とともにサンドイッチ構造を形成している。）で表される遷移金属化合物および
成分（Ｃ）活性化助触媒を構成成分とするオレフィン重合用触媒を提供するものである。

(Wherein R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or 1 carbon atom) Represents an alkoxy group having 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom) They may be substituted))) and may be the same or different. Cp ¹ forms a sandwich structure with M ² . The catalyst for olefin polymerization which uses a transition metal compound represented by (II) and a component (C) activation promoter as constituents is provided.

  Hereinafter, the present invention will be described in detail. Although a specific example is given, it is not limited to them.

  Component (A) of the present invention is a transition metal compound represented by the general formula (1).

（ここで、Ｍ^１はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｘ^１は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｒ^１からＲ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示し（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）、互いに同じでも異なっていてもよい。また、互いに連結し環を形成していても良い。ｆは０から４の整数を示す。Ｅ^１は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子である。）
ここで、一般式（１）において、Ｘ^１のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げることができる。炭素数１〜２０の炭化水素基としては、アルキル基、アリール等が挙げられ、具体的にはメチル基、エチル基、ビニル基、ノルマルプロピル基、イソプロピル基、アリル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、シクロへキシル基、フェニル基、ヘプチル基、ベンジル基、２−メチルフェニル基、４−メチルフェニル基、オクチル基、２，６−ジメチルフェニル基、２−エチルフェニル基、ノニル基、クミル基、２−イソプロピルフェニル基、２，４，６−トリメチルフェニル基、２−エチル−６−メチルフェニル基、デシル基、ナフチル基、アダマンチル基、２−ターシャリーブチルフェニル基、２，６−ジエチルフェニル基、２−メチル−６−イソプロピルフェニル基、ウンデシル基、２−エチル−６−イソプロピル基、２，６−ジエチル−４メチルフェニル基、ドデシル基、２，６−ジイソプロピルフェニル基、２−ビフェニル基、２−シクロへキシルフェニル基、トリデシル基、２,６−ジイソプロピル−４−メチルフェニル基、テトラデシル基、２,６−ジブチルフェニル基、１−アントラセニル基、ペンタデシル基、２，６−ジターシャリーブチル−４−メチルフェニル基、２−フェニル−６−イソプロピル基、ヘキサデシル基、２−ナフチルフェニル基、２−ターシャリーブチル−６−フェニルフェニル基、ヘプタデシル基、２−ターシャリーブチル−４−メチル−６−フェニルフェニル基、オクタデシル基、２,６−ジフェニルフェニル基、ノナデシル基、トリフェニルメチル基、４−メチル２,６−ジフェニルフェニル基、アラキジル基、２，６−ジパラトリルフェニル基等を挙げることができる。炭素数１〜２０のアルコキシ基としては、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、ターシャリーブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等を挙げることができる。炭素数６〜２０のアリールオキシ基としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基等を挙げることができる。炭素数１〜２０のシリル基としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。炭素数１〜２０のアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジノルマルプロピルアミノ基、ジイソプロピルアミノ基、ジノルマルブチルアミノ基、ジフェニルアミノ基等を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリフェニルシリルメチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、２−ジメチルアミノフェニル基、２−ジエチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数１〜２０の炭化水素基としては、２−メトキシフェニル基、２−エトキシフェニル基、２−イソプロポキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数１〜２０の置換炭化水素基としては、２−フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２,２,２−トリフルオロエチル基、ペンタフルオロフェニル基、２−クロロ−１−メチルエチル基等を挙げることができる。

(Wherein M ¹ is a titanium atom, a zirconium atom or a hafnium atom, X ¹ is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number ¹ to R ⁴ . 20 represents a silyl group, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein a hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms) Is a silyl group Which may be substituted by an amino group, an alkoxy group, an aryloxy group or a halogen atom), may be the same or different from each other, and may be linked to each other to form a ring. E ¹ is a carbon atom, a silicon atom, a germanium atom or a tin atom.)
Here, in the general formula (1), examples of the halogen atom for X ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, aryl, and the like. Specifically, a methyl group, an ethyl group, a vinyl group, a normal propyl group, an isopropyl group, an allyl group, a normal butyl group, and an isobutyl group. , Tertiary butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6 -Dimethylphenyl group, 2-ethylphenyl group, nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl Group, 2-tertiarybutylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropyl Pyrphenyl group, undecyl group, 2-ethyl-6-isopropyl group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, Tridecyl group, 2,6-diisopropyl-4-methylphenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-ditertiarybutyl-4-methylphenyl group, 2- Phenyl-6-isopropyl group, hexadecyl group, 2-naphthylphenyl group, 2-tertiarybutyl-6-phenylphenyl group, heptadecyl group, 2-tertiarybutyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl group, triphenylmethyl group, - include methyl 2,6-diphenyl phenyl group, arachidyl group, a 2,6-di-p-tolyl phenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a triphenylsilylmethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group etc. can be mentioned. Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a 2-phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, and 2-chloro-1-methylethyl. Groups and the like.

Here, examples of the halogen atom of R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, aryl, and the like. Specifically, a methyl group, an ethyl group, a vinyl group, a normal propyl group, an isopropyl group, an allyl group, a normal butyl group, and an isobutyl group. , Tertiary butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6 -Dimethylphenyl group, 2-ethylphenyl group, nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl Group, 2-tertiarybutylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropyl Pyrphenyl group, undecyl group, 2-ethyl-6-isopropyl group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, Tridecyl group, 2,6-diisopropyl-4-methylphenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-ditertiarybutyl-4-methylphenyl group, 2- Phenyl-6-isopropyl group, hexadecyl group, 2-naphthylphenyl group, 2-tertiarybutyl-6-phenylphenyl group, heptadecyl group, 2-tertiarybutyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl group, triphenylmethyl group, - include methyl 2,6-diphenyl phenyl group, arachidyl group, a 2,6-di-p-tolyl phenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a triphenylsilylmethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group etc. can be mentioned. Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a 2-phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, and 2-chloro-1-methylethyl. Groups and the like.

Specific examples of the transition metal compound of component (A) include diphenylmethylene (3-vinyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (2-methylvinyl) -1- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (2,2-dimethylvinyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-allyl-1) -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-methylallyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-phenyl- Allyl) -1-cyclopent Dienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3,3-dimethylallyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-butenyl)- 1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (4-methyl-3-butenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (4,4-Dimethyl-3-butenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (4-pentenyl) -1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, dipheni Methylene (3- (5-methyl-4-pentenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (5,5-dimethyl-4-pentenyl) -1-cyclopenta Dienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (5-hexenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (6-methyl-5-hexenyl) ) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (6,6-dimethyl-5-hexenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Methylene (3-benzyl-1-cyclope Ntadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (2-phenyl-ethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-phenyl-propyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-butyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-vinyl-1- Cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (2-methylvinyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9 -Fluorenyl) di Conium dichloride, diphenylmethylene (3- (2,2-dimethylvinyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-allyl-1- Cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-methylallyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-phenyl-allyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3,3 -Dimethylallyl) -1-cyclopentadie ) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3-butenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (3- (4-methyl-3-butenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (4,4- Dimethyl-3-butenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (4-pentenyl) -1-cyclopentadienyl) (2 , 7-tertiarybutyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3- (5-methyl-4-pentenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (5,5-dimethyl). -4-pentenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (5-hexenyl) -1-cyclopentadienyl) (2, 7-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (6-methyl-5-hexenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3- (6,6-dimethyl-5-hexe) L) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-benzyl-1-cyclopentadienyl) (2,7-tertiarybutyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (3- (2-phenyl-ethyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3- (3- Phenyl-propyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-butyl) -1-cyclopentadienyl) (2,7- Tertiary butyl-9-fluorenyl) zirconium Chloride, isopropylidene (3-vinyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (2-methylvinyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride Isopropylidene (3- (2,2-dimethylvinyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-allyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, isopropylidene (3- (3-methylallyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (3-phenyl-allyl) -1-cyclopentadienyl) (9 -Fluorenyl) zirconium di Chloride, isopropylidene (3- (3,3-dimethylallyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (3-butenyl) -1-cyclopentadienyl) ( 9-fluorenyl) zirconium dichloride, isopropylidene (3- (4-methyl-3-butenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (4,4-dimethyl-3) -Butenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (4-pentenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (5-methyl-4-pentenyl) -1-cyclo Ntadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (5,5-dimethyl-4-pentenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (5- Hexenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (6-methyl-5-hexenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (6,6-Dimethyl-5-hexenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-benzyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, isopro Riden (3- (2-phenyl-ethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3- (3-phenyl-propyl) -1-cyclopentadienyl) (9- Fluorenyl) zirconium dichloride, isopropylidene (4-phenyl-butyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-vinyl-1-cyclopentadienyl) (2,7-tarsha Libutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (2-methylvinyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (2,2-dimethylvinyl) -1-si Clopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3-allyl-1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride Isopropylidene (3- (3-methylallyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (3-phenyl-allyl) -1- Cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (3,3-dimethylallyl) -1-cyclopentadienyl) (2,7-tertiarybutyl) -9-fluorenyl) zirconium dichloride, isopropyl Den (3- (3-butenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (4-methyl-3-butenyl) -1- Cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (4,4-dimethyl-3-butenyl) -1-cyclopentadienyl) (2,7- Tertiary butyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (4-pentenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (5-Methyl-4-pentenyl) -1-cyclopentadienyl) (2,7-ta Shalybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (5,5-dimethyl-4-pentenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, Isopropylidene (3- (5-hexenyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (6-methyl-5-hexenyl) -1 -Cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (6,6-dimethyl-5-hexenyl) -1-cyclopentadienyl) (2,7 -Tertiarybutyl-9-fluorenyl) zirconium dichloride, Isopropylidene (3-benzyl-1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (2-phenyl-ethyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, isopropylidene (3- (3-phenyl-propyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium Dichloride, isopropylidene (4-phenyl-butyl) -1-cyclopentadienyl) (2,7-tertiarybutyl-9-fluorenyl) zirconium dichloride, dimethylsilyl (3-allyl-1-cyclopentadienyl) ( 2,7-tertiary butyl) zirconium dichrome Dimethylgermyl (3-allyl-1-cyclopentadienyl) (2,7-tertiarybutyl) zirconium dichloride, dimethylstannyl (3-allyl-1-cyclopentadienyl) (2,7-tersia) Libutyl) zirconium dichloride and the like. Moreover, the compound which substituted the chlorine atom of the said transition metal compound by the fluorine atom, the bromine atom, the iodine atom, the methyl group, the ethyl group, the hydroxy group, the phenyl group, the benzyl group, and the trimethylsilylmethyl group can be illustrated. Furthermore, the compound which substituted the zirconium atom of the said transition metal compound with the titanium atom or the hafnium atom can also be illustrated.

  The component (B) of the present invention is a transition metal compound represented by the general formula (2).

（ここで、Ｍ^２はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｘ^２は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｅ^２は酸素原子、硫黄原子または下記一般式（３）

(Here, M ² is a titanium atom, a zirconium atom or a hafnium atom, and X ² is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) E ² may be an oxygen atom, a sulfur atom, or the following general formula (3).

（ここでＲ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。Ｅ^３はケイ素原子、ゲルマニウム原子または錫原子であり互いに同じでも異なっていても良い。）で表され、ｅは１から５の整数である。eが２以上の場合、Ｅ^２は互いに同じでも異なっていてもよい。
Ｃｐ^１は下記一般式（４）、（５）または（６）

(Wherein R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); E ³ is a silicon atom, a germanium atom, or a tin atom, and may be the same or different from each other), and e is an integer of 1 to 5. When e is 2 or more, E ² may be the same as or different from each other.
Cp ¹ represents the following general formula (4), (5) or (6)

（ここでＲ^５〜Ｒ^９は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。）で示され、互いに同じでも異なっていても良い。Ｃｐ^１はＭ^２とともにサンドイッチ構造を形成している。）
ここで、Ｘ^２のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等を挙げることができる。炭素数１〜２０の炭化水素基としては、アルキル基、アリール等が挙げられ、具体的にはメチル基、エチル基、ビニル基、ノルマルプロピル基、イソプロピル基、アリル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、シクロへキシル基、フェニル基、ヘプチル基、ベンジル基、２−メチルフェニル基、４−メチルフェニル基、オクチル基、２，６−ジメチルフェニル基、２−エチルフェニル基、ノニル基、クミル基、２−イソプロピルフェニル基、２，４，６−トリメチルフェニル基、２−エチル−６−メチルフェニル基、デシル基、ナフチル基、アダマンチル基、２−ターシャリーブチルフェニル基、２，６−ジエチルフェニル基、２−メチル−６−イソプロピルフェニル基、ウンデシル基、２−エチル−６−イソプロピル基、２，６−ジエチル−４メチルフェニル基、ドデシル基、２，６−ジイソプロピルフェニル基、２−ビフェニル基、２−シクロへキシルフェニル基、トリデシル基、２,６−ジイソプロピル−４−メチルフェニル基、テトラデシル基、２,６−ジブチルフェニル基、１−アントラセニル基、ペンタデシル基、２，６−ジターシャリーブチル−４−メチルフェニル基、２−フェニル−６−イソプロピル基、ヘキサデシル基、２−ナフチルフェニル基、２−ターシャリーブチル−６−フェニルフェニル基、ヘプタデシル基、２−ターシャリーブチル−４−メチル−６−フェニルフェニル基、オクタデシル基、２,６−ジフェニルフェニル基、ノナデシル基、トリフェニルメチル基、４−メチル２,６−ジフェニルフェニル基、アラキジル基、２，６−ジパラトリルフェニル基等を挙げることができる。炭素数１〜２０のアルコキシ基としては、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、ターシャリーブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等を挙げることができる。炭素数６〜２０のアリールオキシ基としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基等を挙げることができる。炭素数１〜２０のシリル基としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。炭素数１〜２０のアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジノルマルプロピルアミノ基、ジイソプロピルアミノ基、ジノルマルブチルアミノ基、ジフェニルアミノ基等を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリフェニルシリルメチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、２−ジメチルアミノフェニル基、２−ジエチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数１〜２０の炭化水素基としては、２−メトキシフェニル基、２−エトキシフェニル基、２−イソプロポキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数１〜２０の置換炭化水素基としては、２−フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２,２,２−トリフルオロエチル基、ペンタフルオロフェニル基、２−クロロ−１−メチルエチル基等を挙げることができる。

(Wherein R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or 1 carbon atom) Represents an alkoxy group having 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom) They may be substituted))) and may be the same or different. Cp ¹ forms a sandwich structure with M ² . )
Here, examples of the halogen atom for X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, aryl, and the like. Specifically, a methyl group, an ethyl group, a vinyl group, a normal propyl group, an isopropyl group, an allyl group, a normal butyl group, and an isobutyl group. , Tertiary butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6 -Dimethylphenyl group, 2-ethylphenyl group, nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl Group, 2-tertiarybutylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropyl Pyrphenyl group, undecyl group, 2-ethyl-6-isopropyl group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, Tridecyl group, 2,6-diisopropyl-4-methylphenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-ditertiarybutyl-4-methylphenyl group, 2- Phenyl-6-isopropyl group, hexadecyl group, 2-naphthylphenyl group, 2-tertiarybutyl-6-phenylphenyl group, heptadecyl group, 2-tertiarybutyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl group, triphenylmethyl group, - include methyl 2,6-diphenyl phenyl group, arachidyl group, a 2,6-di-p-tolyl phenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a triphenylsilylmethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group etc. can be mentioned. Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a 2-phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, and 2-chloro-1-methylethyl. Groups and the like.

Examples of the halogen atom for R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, aryl, and the like. Specifically, a methyl group, an ethyl group, a vinyl group, a normal propyl group, an isopropyl group, an allyl group, a normal butyl group, and an isobutyl group. , Tertiary butyl group, pentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6 -Dimethylphenyl group, 2-ethylphenyl group, nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl Group, 2-tertiarybutylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropyl Pyrphenyl group, undecyl group, 2-ethyl-6-isopropyl group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, Tridecyl group, 2,6-diisopropyl-4-methylphenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-ditertiarybutyl-4-methylphenyl group, 2- Phenyl-6-isopropyl group, hexadecyl group, 2-naphthylphenyl group, 2-tertiarybutyl-6-phenylphenyl group, heptadecyl group, 2-tertiarybutyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl group, triphenylmethyl group, - include methyl 2,6-diphenyl phenyl group, arachidyl group, a 2,6-di-p-tolyl phenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a triphenylsilylmethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group etc. can be mentioned. Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a 2-phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, and 2-chloro-1-methylethyl. Groups and the like. E ³ is a silicon atom, a germanium atom, or a tin atom, and may be the same as or different from each other. e is an integer of 1 to 5. When e is 2 or more, E ² may be the same as or different from each other.

(E ² ) _{Examples of the e} group include an alkylene group, a silylene group, a disilane-1,2-diyl group, a disiloxane-1,3-diyl group, and specific examples include a methylene group, a methylmethylene group, Ethyl methylene group, vinyl methylene group, normal propyl methylene group, isopropyl methylene group, allyl methylene group, normal butyl methylene group, isobutyl methylene group, tertiary butyl methylene group, pentyl methylene group, neopentyl methylene group, cyclopentyl methylene group, hexyl Methylene, cyclohexylmethylene, phenylmethylene, heptylmethylene, benzylmethylene, octylmethylene, nonylmethylene, cumylmethylene, decylmethylene, naphthylmethylene, adamantylmethylene, dodecylmethylene, tri Silmethylene, tetradecylmethylene, pentadecylmethylene, hexadecylmethylene, heptadecylmethylene, octadecylmethylene, nonadecylmethylene, arachidylmethylene, dimethylmethylene, diethylmethylene, divinylmethylene, di Normal propylmethylene group, diisopropylmethylene group, diallylmethylene group, dinormalbutylmethylene group, diisobutylmethylene group, ditertiarybutylmethylene group, dipentylmethylene group, dineopentylmethylene group, dicyclopentylmethylene group, dihexylmethylene group, dicyclohexene Xylmethylene, diphenylmethylene, diheptylmethylene, dibenzylmethylene, dioctylmethylene, dinonylmethylene, dicumylmethylene, didecylmethylene Len group, dinaphthylmethylene group, diadamantylmethylene group, didodecylmethylene group, ditridecylmethylene group, ditetradecylmethylene group, dipentadecylmethylene group, dihexadecylmethylene group, diheptadecylmethylene group, dioctadecylmethylene group Group, dinonadecylmethylene group, diarachidylmethylene group, dimethylmethylene group, diethylmethylene group, divinylmethylene group, dinormalpropylmethylene group, diisopropylmethylene group, diallylmethylene group, dinormalbutylmethylene group, diisobutylmethylene group, diter Shaly butylmethylene group, dipentylmethylene group, dineopentylmethylene group, dicyclopentylmethylene group, dihexylmethylene group, dicyclohexylmethylene group, diphenylmethylene group, diheptylmethylene group Group, dibenzylmethylene group, dioctylmethylene group, dinonylmethylene group, dicumylmethylene group, didecylmethylene group, dinaphthylmethylene group, diadamantylmethylene group, didodecylmethylene group, ditridecylmethylene group, ditetradecylmethylene group Group, dipentadecylmethylene group, dihexadecylmethylene group, diheptadecylmethylene group, dioctadecylmethylene group, dinonadecylmethylene group, diarachidylmethylene group, ethylene group, tetramethylethylene group, phenylethylene group, methylsilylene Group, phenylsilylene group, dimethylsilylene group, methylphenylsilylene group, diethylsilylene group, divinylsilylene group, dinormalpropylsilylene group, diisopropylsilylene group, diallylsilylene group, dinormalbutylsilylene group, di Sobutylsilylene group, ditertiarybutylsilylene group, dipentylsilylene group, dineopentylsilylene group, dicyclopentylsilylene group, dihexylsilylene group, dicyclohexylsilylene group, diphenylsilylene group, diheptylsilylene group, dibenzylsilylene group, dioctyl Silylene group, dinonylsilylene group, dicumylsilylene group, didecylsilylene group, dinaphthylsilylene group, diadamantylsilylene group, didodecylsilylene group, ditridecylsilylene group, ditetradecylsilylene group, dipentadecylsilylene group, dihexadecylsilylene group, Diheptadecylsilylene group, dioctadecylsilylene group, dinonadecylsilylene group, diarachidylsilylene group, dimethylgermyl group, dimethylstannyl group, propane-1,3-diyl group 1,1,3,3-tetramethylpropane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, 2,2-diethylpropane-1,3-diyl group, 2,2 -Diphenylpropane-1,3-diyl group, 2-methoxypropane-1,3-diyl group, 2-dimethylamidopropane-1,3-diyl group, 2-trimethylsilylpropane-1,3-diyl group, 2- Pentafluorophenylpropane-1,3-diyl group, 2,2-dimethoxymethylpropane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, pentane-1,5 -Diyl group, pentane-1,5-diyl group, pentane-1,5-diyl group, pentane-1,5-diyl group, 1,1,2,2-tetramethyldisilane-1,2-diyl group, 1, 1, 2, 2 -Tetraphenyldisilane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1- Dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1 -Dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, , 1-Dimethyl-1-silaethane-1,2-diyl group 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group, 1,1-dimethyl-1-silaethane-1,2-diyl group 1,1-diisopropyltyl-1-silaethane-1,2-diyl group, 1,1-diphenyl-1-silaethane-1,2-diyl group, 1,1,3,3-tetramethyldisiloxane-1 , 3-diyl group, 1,1,3,3-tetramethyldisiloxane-1,3-diyl group, 1,1,3,3-tetramethyldisiloxane-1,3-diyl group, 1,1,3 3,3-tetraisopropyldisiloxane-1,3-diyl group, 1,1,3,3-tetraphenyldisiloxane-1,3-diyl group, cis-2-butene-1,4-diyl group, 2 , 3-Dibromo-cis-2-butene-1,4-dii Group, cis-5-decene-1,10-diyl - and bis cyclopentadienyl.

Examples of the halogen atom of R ^{5 to} R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, normal propyl group, isopropyl group, allyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, and cyclopentyl. Group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, nonyl group , Cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl group, 2-tertiarybutylphenyl group, 2,6 -Diethylphenyl group, 2-methyl-6-isopropylphenyl group, undecyl group, 2-ethyl- -Isopropyl group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, tridecyl group, 2,6-diisopropyl-4- Methylphenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-ditertiarybutyl-4-methylphenyl group, 2-phenyl-6-isopropyl group, hexadecyl group, 2 -Naphthylphenyl group, 2-tertiarybutyl-6-phenylphenyl group, heptadecyl group, 2-tertiarybutyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl group, Triphenylmethyl group, 4-methyl-2,6-diphenylphenyl group, arachi Group, can be exemplified 2,6-di-p-tolyl phenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a triphenylsilylmethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group etc. can be mentioned. Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a 2-phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, and 2-chloro-1-methylethyl. Groups and the like.

Specific compounds of Cp ¹ include cyclopentadienyl group, methylcyclopentadienyl group, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl. Group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, ethylcyclopentadienyl group , Vinylcyclopentadienyl group, normal propylcyclopentadienyl group, isopropylcyclopentadienyl group, 3-allylcyclopentadienyl group, normal butylcyclopentadienyl group, isobutylcyclopentadienyl group, tertiary butyl Cyclopentadienyl group, (3-butenyl) cyclopentadienyl group, no Normal pentylcyclopentadienyl group, normal hexyl cyclopentadienyl group, cyclohexyl cyclopentadienyl group, phenyl cyclopentadienyl group, normal heptyl cyclopentadienyl group, normal octyl cyclopentadienyl group, normal decyl cyclopenta Dienyl, dodecylcyclopentadienyl, tetradecylcyclopentadienyl, hexadecylcyclopentadienyl, octadecylcyclopentadienyl, arachidylcyclopentadienyl, trimethylsilylcyclopentadienyl, trimethylsilyl Cyclopentadienyl group, naphthylcyclopentadienyl group, indenyl group, 1-methylindenyl group, 2-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 1, -Dimethylindenyl group, 1,3-dimethylindenyl group, 1,4-dimethylindenyl group, 1,5-dimethylindenyl group, 1,6-dimethylindenyl group, 1,7-dimethylindenyl group 2,4-dimethylindenyl group, 2,5-dimethylindenyl group, 4,5-dimethylindenyl group, 4,6-dimethylindenyl group, 4,7-dimethylindenyl group, 1,2, 4-trimethylindenyl group, 1,2,5-trimethylindenyl group, 1,2,6-trimethylindenyl group, 1,2,7-trimethylindenyl group, 1,4,5-trimethylindenyl group 1,4,6-trimethylindenyl group, 1,4,7-trimethylindenyl group, 1,5,6-trimethylindenyl group, 1,5,7-trimethylindenyl group, 1,6,7 -Birds Tilindenyl group, 2,4,5-trimethylindenyl group, 2,4,6-trimethylindenyl group, 2,4,7-trimethylindenyl group, 2,5,6-trimethylindenyl group, 2,5 , 7-trimethylindenyl group, 1,2,4,5-tetramethylindenyl group, 1,2,4,6-tetramethylindenyl group, 1,2,4,7-tetramethylindenyl group, 1,2,5,6-tetramethylindenyl group, 1,2,5,7-tetramethylindenyl group, 1,2,6,7-tetramethylindenyl group, 2,4,5,6- Tetramethylindenyl group, 2,4,5,7-tetramethylindenyl group, 2,4,6,7-tetramethylindenyl group, 4,5,6,7-tetramethylindenyl group, 1, 4,5,6,7-pentamethylindenyl group, 2 , 4,5,6,7-pentamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, 2,4-dimethyl-7-ethylindenyl group, 2,4- Dimethyl-7-isopropylindenyl group, 2,4-dimethyl-7-tertiarybutylindenyl group, 2,4-dimethyl-7-phenylindenyl group, 2,4-dimethyl-6,7-benzoindenyl Group, 2-methyl-dibenzo [e, g] indenyl group, tetrahydroindenyl group, 2,4,7-trimethyltetrahydroindenyl group and the like.

Specific compounds of component (B) include methylene bis (cyclopentadienyl) zirconium dichloride, dimethylmethylene bis (cyclopentadienyl) zirconium dichloride, diethylmethylene bis (cyclopentadienyl) zirconium dichloride, divinylmethylene bis ( Cyclopentadienyl) zirconium dichloride, dinormalpropylmethylenebis (cyclopentadienyl) zirconium dichloride, diisopropylmethylenebis (cyclopentadienyl) zirconium dichloride, diallylmethylenebis (cyclopentadienyl) zirconium dichloride, dinormalbutylmethylene Bis (cyclopentadienyl) zirconium dichloride, diisobutylmethylenebis (cyclopentadienyl) zirconium dichloride Ditertiary butylmethylenebis (cyclopentadienyl) zirconium dichloride, di (3-butenyl) methylenebis (cyclopentadienyl) zirconium dichloride, dinormalpentylmethylenebis (cyclopentadienyl) zirconium dichloride, dinormalhexylmethylenebis ( Cyclopentadienyl) zirconium dichloride, dicyclohexylmethylenebis (cyclopentadienyl) zirconium dichloride, di (5-hexenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, dinormal Heptylmethylenebis (cyclopentadienyl) zirconium dichloride, dibenzylmethylenebis (cyclopentadienyl) Luconium dichloride, dinormaloctylmethylenebis (cyclopentadienyl) zirconium dichloride, dinormalnonylmethylenebis (cyclopentadienyl) zirconium dichloride, dinormaldecylmethylenebis (cyclopentadienyl) zirconium dichloride, didodecylmethylenebis (Cyclopentadienyl) zirconium dichloride, ditetradecylmethylenebis (cyclopentadienyl) zirconium dichloride, dihexadecylmethylenebis (cyclopentadienyl) zirconium dichloride, dioctadecylmethylenebis (cyclopentadienyl) zirconium dichloride, Diarachidylmethylenebis (cyclopentadienyl) zirconium dichloride, dinaphthylmethylenebis (cyclopentadienyl) zyl Conium dichloride, bis (p-methoxyphenyl) methylenebis (cyclopentadienyl) zirconium dichloride, bis (p-dimethylaminophenyl) methylenebis (cyclopentadienyl) zirconium dichloride, bis (pentafluorophenyl) methylenebis (cyclopentadi) Enyl) zirconium dichloride, silylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, methylethylsilylenebis (cyclopentadienyl) zirconium dichloride, methylvinylsilylenebis (cyclopentadienyl) Zirconium dichloride, methylisopropylsilylenebis (cyclopentadienyl) zirconium dichloride, methylallylsilylenebis Cyclopentadienyl) zirconium dichloride, methyl tertiary butylsilylene bis (cyclopentadienyl) zirconium dichloride, methylphenylsilylene bis (cyclopentadienyl) zirconium dichloride, diethylsilylene bis (cyclopentadienyl) zirconium dichloride, divinylsilylene Bis (cyclopentadienyl) zirconium dichloride, dinormalpropylsilylene bis (cyclopentadienyl) zirconium dichloride, diisopropylsilylene bis (cyclopentadienyl) zirconium dichloride, diallylsilylene bis (cyclopentadienyl) zirconium dichloride, dinormal Butylsilylenebis (cyclopentadienyl) zirconium dichloride, diisobutylsilylenebis (Si Lopentadienyl) zirconium dichloride, ditertiary butylsilylenebis (cyclopentadienyl) zirconium dichloride, di (3-butenyl) silylenebis (cyclopentadienyl) zirconium dichloride, dinormalpentylsilylenebis (cyclopentadienyl) zirconium dichloride, di Normal hexylsilylene bis (cyclopentadienyl) zirconium dichloride, dicyclohexylsilylene bis (cyclopentadienyl) zirconium dichloride, di (5-hexenyl) silylene bis (cyclopentadienyl) zirconium dichloride, diphenylsilylene bis (cyclopentadienyl) Zirconium dichloride, dinormal heptylsilylene bis (cyclopentadienyl) zirconium dichloride, diben Dilsilylene bis (cyclopentadienyl) zirconium dichloride, dinormaloctylsilylene bis (cyclopentadienyl) zirconium dichloride, dinormalnonylsilylene bis (cyclopentadienyl) zirconium dichloride, dinormaldecylsilylene bis (cyclopentadienyl) ) Zirconium dichloride, didodecylsilylenebis (cyclopentadienyl) zirconium dichloride, ditetradecylsilylenebis (cyclopentadienyl) zirconium dichloride, dihexadecylsilylenebis (cyclopentadienyl) zirconium dichloride, dioctadecylsilylenebis ( Cyclopentadienyl) zirconium dichloride, diarachidylsilylene bis (cyclopentadienyl) zirconium dichloride, dinaphthy Silylene bis (cyclopentadienyl) zirconium dichloride, bis (p-methoxyphenyl) silylene bis (cyclopentadienyl) zirconium dichloride, bis (p-dimethylaminophenyl) silylene bis (cyclopentadienyl) zirconium dichloride, bis (pentafluorophenyl) ) Silylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (cyclopentadienyl) zirconium dichloride, methylethylene bis (cyclopentadienyl) zirconium dichloride, 1,2-dimethylethylenebis (cyclopentadienyl) zirconium dichloride, Tetramethylethylenebis (cyclopentadienyl) zirconium dichloride, ethylethylenebis (cyclopentadienyl) zirconium dichloride Lido, 1,2-diethylethylenebis (cyclopentadienyl) zirconium dichloride, tetraethylethylenebis (cyclopentadienyl) zirconium dichloride, normalpropylethylenebis (cyclopentadienyl) zirconium dichloride, 1,2-dinormalpropyl Ethylenebis (cyclopentadienyl) zirconium dichloride, tetranormalpropylethylenebis (cyclopentadienyl) zirconium dichloride, phenylethylenebis (cyclopentadienyl) zirconium dichloride, 1,2-diphenylethylenebis (cyclopentadienyl) Zirconium dichloride, 1,2-bis (p-tolyl) ethylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl) (3-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-normalpropyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-normalbutyl-cyclo Pentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-isobutyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-tertiarybutyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-normalpentyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-normalhexyl) -Cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-cyclohexyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-cyclopentadienyl) zirconium dichloride Dimethylsilylene (cyclopentadienyl) (3-normal octyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-trimethyl) Rusilyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-vinyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-allyl-cyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (3- (3-butenyl) -cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-benzyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (3-trimethylsilylmethyl-cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethyl Tylsilylene (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4-methylindenyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (5-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (6-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (7- Methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3-dimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4 Dimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) (5,6-dimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4-trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2, 4,5-trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4,6-trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4 , 7-tetramethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,5,6-tetramethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4) , 5,6,7-hexamethylindenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2- Methylindenyl) zirco Nium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (2,4,7-trimethylindene) Nyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (2-methylindenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylgermide (Cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylstannyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, (propane-1,3- Diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetramethylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (2,2-dimethylpropane-1,3) -Diyl-biscyclopentadienyl) zirconium dichloride, (2,2-dimethylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (2,2-diethylpropane-1,3-diyl-bis) Cyclopentadienyl) zirconium dichloride, (2 2-diphenylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (2-methoxypropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (2-dimethylamidopropane-1, 3-diyl-biscyclopentadienyl) zirconium dichloride, (2-trimethylsilylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (2-pentafluorophenylpropane-1,3-diyl-biscyclo) Pentadienyl) zirconium dichloride, (2,2-dimethoxymethylpropane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (butane-1,4-diyl-biscyclopentadienyl) zirconium dichloride (Pentane-1,5-diyl-biscyclopentadienyl) zirconium dichloride, (pentane-1,5-diyl-1- (1-indenyl) -5-cyclopentadienyl) zirconium dichloride, (pentane- 1,5-diyl-1- (9-fluorenyl) -5-cyclopentadienyl) zirconium dichloride, (pentane-1,5-diyl-1,5-bis (1-indenyl)) zirconium dichloride, (pentane- 1,5-diyl-1- (1-indenyl) -5- (9-fluorenyl)) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl-biscyclopentadienyl) Zirconium dichloride, (1,1,2,2-tetraphenyldisilane-1,2-diyl-biscyclopenta Enyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-Methylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (2,4-dimethylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (2,3,4,5-tetramethylcyclopentadienyl) -2-cyclo Pentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-ethylsilane) Lopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-n-butylcyclopentadienyl) -2-cyclopentadienyl ) Zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-allylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-) 1-silaethane-1,2-diyl-1- (3-phenylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1 -(3-trimethylsilylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, ( 1,1-dimethyl-1-silaethane-1,2-diyl-1- (3- (t-butyldimethylsilyl) cyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl -1-Silaethane-1,2-diyl-1- (3-methoxycyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl- 1- (3-dimethylamidocyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-methoxymethylcyclopentadi) Enyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-) -(3- (dimethylamidomethyl) -cyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl-1- (3-trifluoro) Methylcyclopentadienyl) -2-cyclopentadienyl) zirconium dichloride, (1,1-diisopropyltyl-1-silaethane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1-diphenyl) -1-silaethane-1,2-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetramethyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, 1,1,3,3-tetramethyldisiloxane-1,3-diyl-bis ( , 4-dimethylcyclopentadienyl)) zirconium dichloride, (1,1,3,3-tetramethyldisiloxane-1,3-diyl-bis (2,3,4,5-tetramethylcyclopentadienyl) ) Zirconium dichloride, (1,1,3,3-tetraisopropyldisiloxane-1,3-diyl-biscyclopentadienyl) zirconium dichloride, (1,1,3,3-tetraphenyldisiloxane-1,3 -Diyl-biscyclopentadienyl) zirconium dichloride, (cis-2-butene-1,4-diyl-biscyclopentadienyl) zirconium dichloride, (2,3-dibromo-cis-2-butene-1,4 -Diyl-biscyclopentadienyl) zirconium dichloride, (cis-5-decene-1,10-di) Il-biscyclopentadienyl) zirconium dichloride and the like can be exemplified. Moreover, the compound which substituted the chlorine atom of the said transition metal compound by the fluorine atom, the bromine atom, the iodine atom, the methyl group, the ethyl group, the hydroxy group, the phenyl group, and the benzyl group can be illustrated. Furthermore, the compound which substituted the zirconium atom of the said transition metal compound with the titanium atom or the hafnium atom can also be illustrated.

  The activation promoter of component (C) of the present invention forms a polymerization active species capable of polymerizing olefins by acting or reacting with transition metal compounds (component (A) and component (B)). The possible compounds are shown. An activation co-catalyst is a compound that provides a compound that, after forming a polymerization active species, coordinates weakly or interacts with the generated polymerization active species but does not react directly with the active species.

  Examples of the activation promoter for the component (C) used in the present invention include clay minerals, modified clay minerals treated with organic compounds, alkylaluminoxanes, ionized ionic compounds having non-coordinating anions, Lewis acids, sulfones And acid salts and carboxylic acid compounds. When the activation promoter (C) is a modified clay mineral treated with an organic compound, the resulting olefin polymer has a high bulk density and a good particle shape.

  When the component (C) used in the present invention is a clay mineral, the clay mineral is a fine particle mainly composed of a microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and it can be mentioned that the layers have negative charges of various sizes. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals are generally of a large layer charge, with pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is from about 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here includes various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Moreover, although these clay minerals exist naturally, a thing with few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and those not listed above but belonging to the definition of clay minerals can be used. it can. Furthermore, a mixture of a plurality of the above clay minerals can be used.

  The clay mineral may be used as it is, or may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. The clay mineral is preferably subjected to chemical treatment such as acid treatment, alkali treatment, salt treatment and the like. Acid treatment uses, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and other acids to remove impurities on the surface of clay minerals and to elute some or all of the cations such as Al, Fe, Mg in the crystal structure. To increase the surface area. In the alkali treatment, for example, an alkali such as sodium hydroxide is used to destroy the crystal structure of the clay mineral and cause a structural change. For example, lithium chloride, sodium phosphate, sodium sulfate, sodium acetate, sodium formate, sodium citrate, sodium nitrate, sodium oxalate, magnesium chloride, magnesium sulfate, magnesium phosphate, magnesium perchlorate, magnesium oxalate Swellability by replacing exchangeable ions between clay mineral layers with other ions using salts such as magnesium nitrate, magnesium acetate, magnesium succinate, aluminum sulfate, aluminum phosphate, aluminum oxalate, aluminum nitrate, etc. Increase interlayer distance.

  When the component (C) used in the present invention is a modified clay mineral treated with an organic compound, the clay mineral used is a fine particle mainly composed of the above-mentioned microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and it can be mentioned that the layers have negative charges of various sizes. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals generally have a large layer charge, and the pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is approximately 0.25 to 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here includes various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Moreover, although these clay minerals exist naturally, a thing with few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and those not exemplified above but belonging to the definition of clay minerals can be used. it can. Furthermore, a mixture of a plurality of the above clay minerals can be used.

  The organic compound treatment in the modified clay mineral treated with the organic compound of the present invention introduces organic ions between the clay mineral layers to form an ionic complex. Examples of the organic compound used in the organic compound treatment include a compound represented by the following general formula (8).

[R ¹¹ R ¹² _x-1 GH] _y [J] _z (8)
In the general formula (8), [R ¹¹ R ¹² _x-1 GH] is a cation, and G represents an atom of Group 15 or Group 16 of the periodic table. R ¹¹ represents a hydrocarbon group having 1 to 30 carbon atoms, and R ¹² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. When G is a Group 15 atom in the periodic table, x is 3, and when G is a Group 16 element, x is 2. [J] is an anion, such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetrafluoro ion. A borate ion or a hexafluorophosphate ion can be used, but is not limited thereto. Furthermore, y and z are integers chosen to balance the charges.

G in Formula (8) can illustrate a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms of R ¹¹ and R ¹² include an alkyl group and an aryl group, and specifically include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an allyl group, and a normal butyl group. , Isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tertiary pentyl group, cyclopentyl group, normal hexyl group , Isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2 -Butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, Cyclohexyl group, normal heptyl group, cycloheptyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, normal octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tertiary octyl group, 2,3-dimethylcyclohexyl group, 2- (1-cyclohexenyl) ethyl group, normal nonyl group, normal decyl group, isodecyl group, geranyl group, normal undecyl group, normal dodecyl group Group, cyclododecyl group, normal tridecyl group, normal tetradecyl group, normal pentadecyl group, normal hexadecyl group, normal heptadecyl group, normal octadecyl group, normal nonadecyl group, normal eicosyl group, normal eicosyl group Sil group, normal docosyl group, normal tricosyl group, lauryl group, myristyl group, stearyl group, oleyl group, behenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl Group, 3-ethylphenyl group, 4-ethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-tertiarybutylphenyl group, 4-normalbutylphenyl group, 4-secondary Butylphenyl group, 4-tertiarybutylphenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5 -Xylyl group, 2,6-diethylphenyl group, 2-isopropyl-6-methylphenyl group, 2-chlorophenyl group, 3-c Rophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2,3-dihydroindene-5 Examples include -yl group, 2-biphenyl group, 4-biphenyl group, and p-trimethylsilylphenyl group. R ¹¹ and R ¹² may be bonded to each other.

  Among the compounds represented by formula (8), those in which G is a nitrogen atom include methylamine hydrochloride, ethylamine hydrochloride, normal propylamine hydrochloride, isopropylamine hydrochloride, normal butylamine hydrochloride, and isobutylamine hydrochloride. Salt, tertiary butylamine hydrochloride, normal pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tertiary pentylamine hydrochloride, normal hexylamine hydrochloride, isohexylamine hydrochloride Salt, normal heptylamine hydrochloride, normal octylamine hydrochloride, normal nonylamine hydrochloride, normal decylamine hydrochloride, normal undecylamine hydrochloride, normal dodecylamine hydrochloride, normal tetradecylamine hydrochloride, normal Xadecylamine hydrochloride, normal octadecylamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, laurylamine hydrochloride, myristylamine hydrochloride, palmitylamine hydrochloride, stearylamine hydrochloride, behenylamine hydrochloride, oleylamine hydrochloride, dimethyl Amine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-normal butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2-aminoheptane hydrochloride, 3-aminoheptane hydrochloride, normal heptylamine Hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, normal octylamine hydrochloride, tertiary octylamine hydrochloride, nonylamine hydrochloride, decylamine salt Salt, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, heptadecylamine hydrochloride, octadecylamine hydrochloride, nonadecylamine hydrochloride Salt, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride, cyclododecylamine Hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride, dideci Luamine hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tertiarybutylcyclohexylamine hydrochloride, N-allylcyclohexylamine hydrochloride, N-methyldioctyl Amine hydrochloride, N-methyldiundecylamine hydrochloride, N-methyldidodecylamine hydrochloride, N-methyldineral tetradecylamine hydrochloride, N-methyldineral hexadecylamine hydrochloride, N-methyldineral octadecyl Amine hydrochloride, N-methyldinormaleicosylamine hydrochloride, N-methyldilaurylamine hydrochloride, N-methyldimyristylamine hydrochloride, N-methyldipalmitylamine hydrochloride, N-methyldistearylamine hydrochloride Salt, N-me Rudibehenylamine hydrochloride, N-methyldioleylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyl Normal tetradecylamine hydrochloride, N, N-dimethyl-normal hexadecylamine hydrochloride, N, N-dimethyl-normal octadecylamine hydrochloride, N, N-dimethyl-normal eicosylamine hydrochloride, N, N- Dimethyl-normaldocosylamine hydrochloride, N, N-dimethyllaurylamine hydrochloride, N, N-dimethylmyristylamine hydrochloride, N, N-dimethylpalmitylamine hydrochloride, N, N-dimethylstearylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, N, N-dimethyloleylamine hydrochloride, Rehexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine hydrochloride, N-methyl-dioctadecylamine hydrochloride, N, N-dimethylcyclohexylamine hydrochloride Salt, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3-methyl Piperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2,2,6 , 6-Tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride Salt, aliphatic amine hydrochloride such as 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine hydrochloride, aniline hydrochloride N-methylaniline hydrochloride, N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N -Methyl-o-toluidine hydrochloride, N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-ethyl-m-toluidine hydrochloride, N -Ethyl-p-toluidine hydrochloride, N-allyl-o-toluidine hydrochloride, N-allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N-propyl Pill-o-toluidine hydrochloride, N-propyl-m-toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5- Dimethylaniline hydrochloride, 2,6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4-ethylaniline Hydrochloride, N, N-diethylaniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tertiary butylaniline hydrochloride, 4-normal butylaniline hydrochloride, 4-secondary butylaniline hydrochloride 4-tert-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl- -Methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o- Anisidine hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphthalene hydrochloride, 1- Aminofluorene hydrochloride, 2-aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoindan hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N, 2 , 3-Trimethylaniline hydrochloride, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethyl Aniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3,5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N- Methyl-3-ethylaniline hydrochloride, N-methyl-4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4 -Isopropylaniline hydrochloride, N-methyl-2-tertiary butylaniline hydrochloride, N-methyl-4-normal butylaniline hydrochloride, N-methyl-4-secondary butylaniline hydrochloride, N-methyl-4-tersia Libutylaniline hydrochloride, N-methyl-2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylaniline Acid salt, N-methyl-p-anisidine hydrochloride, N-ethyl-2,3-anisidine hydrochloride, N, N-dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N , N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-tetramethylaniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride, N, N, 2,5-tetramethylaniline Hydrochloride, N, N, 2,6-tetramethylaniline hydrochloride, N, N, 3,4-tetramethylaniline hydrochloride, N, N, 3,5-tetramethylaniline hydrochloride, N, N-dimethyl 2-ethylaniline hydrochloride, N, N-dimethyl-3-ethylaniline hydrochloride, N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride, N, N-dimethyl- -Isopropylaniline hydrochloride, N, N-dimethyl-4-isopropylaniline hydrochloride, N, N-dimethyl-2-tertiarybutylaniline hydrochloride, N, N-dimethyl-4-normalbutylaniline hydrochloride, N, N-dimethyl-4-secondary butylaniline hydrochloride, N, N-dimethyl-4-tertiarybutylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride, N, N-dimethyl-2- Isopropyl-6-methylaniline hydrochloride, N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N-dimethyl-2-bromoaniline hydrochloride, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoanily Hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N-dimethyl-m-anisidine hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride Salt, N, N-dimethyl-m-phenetidine hydrochloride, N, N-dimethyl-p-phenetidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride Salt, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-amino Fluorene hydrochloride, N, N-dimethyl-5-aminoindan hydrochloride, N, N-dimethyl-2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride Aromatic amine hydrochlorides such as N, N-dimethyl-p-trimethylsilylaniline hydrochloride and compounds in which the hydrochloride of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide or sulfate However, the present invention is not limited to these examples.

  Among the compounds represented by formula (8), those in which G is an oxygen atom include compounds such as methyl ether hydrochloride, ethyl ether hydrochloride, normal butyl ether hydrochloride, tetrahydrofuran hydrochloride, phenyl ether hydrochloride, and the like. A compound in which the hydrochloride of the compound is replaced with a hydrofluoric acid salt, a hydrobromide salt, a hydroiodide salt, or a sulfate salt can be exemplified, but is not limited thereto.

  Among the compounds represented by formula (8), those in which G is a sulfur atom include diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, dimethylsulfonium chloride, Examples thereof include, but are not limited to, dimethylsulfonium bromide and dimethylsulfonium iodide.

  Among the compounds represented by formula (8), those in which G is a phosphorus atom include triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, tri (p-tolyl) phosphine hydrochloride, and trimesityl. Examples include, but are not limited to, compounds such as phosphine hydrochloride, and compounds obtained by replacing hydrochloride of the above compound with hydrofluoride, hydrobromide, hydroiodide, or sulfate. It is not a thing.

  In the organic compound treatment, it is preferable to carry out the treatment by selecting the conditions of a clay mineral concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay mineral and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay mineral. Treatment solvents include aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or normal butyl ether, chloride Halogenated hydrocarbons such as methylene or chloroform, acetone, 1,4-dioxane, tetrahydrofuran, water or the like can be used, but alcohols or water are preferably used alone or as a component of a solvent.

  When component (C) is an alkylaluminoxane, the structure is preferably a compound represented by the following general formula (9) and / or (10).

ここで、Ｒ^１３は各々同一でも異なっていてもよく、水素原子、メチル基、エチル基、プロピル基、イソブチル基、ターシャリーブチル基などの炭素数１〜２０の炭化水素基である。また、ｑは２〜６０の整数である。なお、アルキルアルミノキサンには有機アルミニウム化合物の単量体、そのニ量体およびオリゴマー等の有機金属化合物が含まれていてもよい。

Here, R ¹³ may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isobutyl group, or a tertiary butyl group. Moreover, q is an integer of 2-60. The alkylaluminoxane may contain organometallic compounds such as organoaluminum compound monomers, dimers and oligomers thereof.

  When component (C) is an ionized ionic compound having a non-coordinating anion, the structure is a compound having any one of the structures represented by the following general formulas (11), (12), and (13). It is desirable to be.

_{^{[R 15 R 16 a-1}} M 4 H] [Q (R 14) 4] (11)
[M ⁵ L ¹ _b ] [Q (R ¹⁴ ) ₄ ] _c (12)
[D] [Q (R ¹⁴ ) ₄ ] _d (13)
Here, [Q (R ¹⁴ ) ₄ ] represents a non-coordinating anion, and Q represents a boron atom or an aluminum atom. R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-substituted aryl group having 6 to 20 carbon atoms. M ⁴ is an element selected from Group 15 or 16 of the periodic table, R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, and R ¹⁶ is independently a hydrogen atom or a carbon atom having 1 to 30 carbon atoms. Indicates a hydrogen group. If M ⁴ is of the periodic table Group 15 element a is 3, if M ⁴ is an element of the periodic table Group 16 a shows a 2.

M ⁵ is a metal cation selected from lithium, sodium, potassium, iron or silver, and c represents the valence of the cation. L ¹ is a Lewis base such as ethers, aliphatic amines, aromatic amines, phosphines, a cyclopentadienyl group, or a hydrocarbon group-substituted cyclopentadienyl group having 1 to 20 carbon atoms.

  D represents an organic cation such as carbonium cation or tropylium cation, and d represents the valence of the organic cation.

  Specific examples of the compound represented by the general formula (11) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, and tetramethyleneoxonium tetrakis (pentafluorophenyl) borate. Hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-N-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, Dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminum , Hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, trinormalbutylammonium tetrakis (pentafluorophenyl) aluminate, etc. It is not limited to.

  Specific examples of the compound represented by the general formula (12) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, or ether complexes thereof, sodium tetrakis (pentafluoro Phenyl) borate, sodium salt such as sodium tetrakis (pentafluorophenyl) aluminate, ferrocenium salt such as ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis (pentafluoro) Examples thereof include, but are not limited to, silver salts such as phenyl) borate and silver tetrakis (pentafluorophenyl) aluminate.

  Specific examples of the compound represented by the general formula (13) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis ( Pentafluorophenyl) aluminate and the like can be mentioned, but the invention is not limited to these.

When the component (C) is a Lewis acid, examples include compounds represented by the following general formula (14). Q (R ¹⁴ ) ₃ (14)
Here, Q represents a boron atom or an aluminum atom, and R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-substituted aryl group having 6 to 20 carbon atoms.

  Specific examples of the compound represented by the general formula (14) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5). -Tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum, and the like. It is not limited.

  Specific examples when component (C) is a sulfonate include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, bis (trifluoromethanesulfonate) calcium, bis (trifluoromethanesulfonate) Barium, tris (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) zirconium, tetrakis (trifluoromethanesulfonate) hafnium, pentakis (trifluoromethanesulfonate) niobium, pentakis (trifluoro) Lomethanesulfonate) tantalum, tris (trifluoromethanesulfonate) iron, trifluoromethanesulfone Silver, tris (trifluoromethanesulfonate) boron, tris (trifluoromethanesulfonate) aluminum, tris (trifluoromethanesulfonate) gallium, tetrakis (trifluoromethanesulfonate) tin, lithium pentafluorobenzenesulfonate, pentafluorobenzene Sodium sulfonate, potassium pentafluorobenzenesulfonate, bis (pentafluorobenzenesulfonate) magnesium, bis (pentafluorobenzenesulfonate) calcium, bis (pentafluorobenzenesulfonate) barium, tris (pentafluorobenzenesulfonate) titanium , Tetrakis (pentafluorobenzenesulfonate) zirconium, tetrakis (pentafluorobenzenesulfonate) G) Hafnium, pentakis (pentafluorobenzene sulfonate) niobium, pentakis (pentafluorobenzene sulfonate) tantalum, tris (pentafluorobenzene sulfonate) iron, pentafluorobenzene sulfonate silver, tris (pentafluorobenzene sulfonate) boron , Tris (pentafluorobenzenesulfonate) aluminum, tris (pentafluorobenzenesulfonate) gallium, tetrakis (pentafluorobenzenesulfonate) tin, bis (trifluoromethanesulfonate) magnesium, pentakis (trifluoromethanesulfonate) niobium, bis (Pentafluorobenzenesulfonate) magnesium, tetrakis (pentafluorobenzenesulfonate) titanium and pentakis (Pentafluorobenzenesulfonate) niobium and the like can be exemplified.

  Specific examples when component (C) is a carboxylic acid compound include trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluorobenzoic acid, tetrafluorotoluic acid, 2,4- (trifluoromethyl) benzoic acid, penta A fluorophenylacetic acid etc. can be illustrated.

  In the olefin polymerization catalyst of the present invention, the transition metal compound (component (A) and component (B)), the activation promoter (component (C)), and the component (D) are represented by the following general formula (7). The compound may be a constituent component.

Al (R ¹⁰ ) ₃ (7)
^{(Wherein, R 10} is hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or an amino group having 1 to 20 carbon atoms of 6 to 20 carbon atoms. )
Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ¹⁰ include an alkyl group and an aryl group, and specifically include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a secondary group. Butyl group, tertiary butyl group, normal pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tertiary pentyl group, normal hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2 -Butyl group, normal pentyl group, isopentyl group, normal octyl group, normal nonyl group, normal Examples of the alkoxy group having 1 to 20 carbon atoms such as syl group, normal dodecyl group, normal tetradecyl group, normal hexadecyl group, normal octadecyl group, phenyl group, cyclohexyl group, methoxy group, ethoxy group, phenoxy group, pentafluoro Examples of the aryloxy group having 6 to 20 carbon atoms such as a phenoxy group include a phenoxy group, a paramethylphenoxy group, a paramethoxyphenoxy group, a 2,6-dimethylphenoxy group, and a 1-naphthoxy group. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a dinormalpropylamino group, a diisopropylamino group, a dinormalbutylamino group, and a diphenylamino group.

  Specific examples of component (D) include trimethylaluminum, dimethylaluminum hydride, triethylaluminum, diethylaluminum hydride, trinormalpropylaluminum, dinormalpropylaluminum hydride, triisopropylaluminum, diisopropylaluminum hydride, trinormalbutylaluminum, dinormal Butyl aluminum hydride, triisobutyl aluminum, diisobutyl aluminum hydride, tritertiary butyl aluminum, ditertiary butyl aluminum hydride, trinormal hexyl aluminum, dinormal hexyl aluminum hydride, triisohexyl aluminum, diisohexyl aluminum hydride, trinormal octyl aluminum , Zinol Octyl aluminum hydride, tri-isooctyl aluminum can be exemplified by aluminum compounds such as di-isooctyl aluminum hydride. Among these, an aluminum compound is preferable because of high polymerization activity.

  In the catalyst for olefin polymerization of the present invention, a transition metal compound (component (A) and component (B)), an activation co-catalyst (component (C)), and component (D) are further composed of a component (E) solid support. It may be an ingredient.

Examples of the solid support of component (E) include inorganic oxides of typical elements such as SiO ₂ , Al ₂ O ₃ , MgO, inorganic oxides of transition metal elements such as TiO ₂ and ZrO ₂ , and mixtures thereof, and MgCl ₂ Inorganic halides can be exemplified.

Inorganic oxides preferably have an average particle size of 1 to 300 μm, and particularly fine porous particles in the range of 3 to 200 μm are suitable because they are easy to handle during catalyst preparation and polymerization processes. is there. These inorganic oxides usually contain alkali metal or alkaline earth metal salts such as Na ₂ O, K ₂ CO ₃ and BaSO ₄ as impurities. The fine particle inorganic oxide may be used in a state containing these impurities, but it is preferable to use an inorganic oxide that has been previously subjected to an operation for removing these impurities. Such porous fine-particle inorganic oxides have different properties depending on the kind and production method. In the present invention, the specific surface area is 10 to 1000 m ² / g, particularly 50 to 800 m ² / g, pores. The one having a volume of 0.1 to 3 mL / g is preferable because a large amount of a transition metal compound-supporting component can be supported. These inorganic oxides are used after being calcined at 100 to 1000 ° C. under reduced pressure or in a gas stream as necessary.

Moreover, the hydroxyl group of these inorganic oxides can be substituted with halogen. As a method of replacing the hydroxyl group of the inorganic oxide with a halogen, a method of reacting with a reactive agent having a halogen exchangeable with a surface hydroxyl group is preferable. Examples of the reactant include halogens such as fluorine, chlorine, bromine and iodine; hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide: phosgene, thionyl chloride, ammonium fluoride, ammonium chloride, And halogen-containing compounds such as ammonium iodide, carbon tetrachloride, chloroform, and chlorofluorocarbon. These inorganic compounds may be subjected to heat treatment under reduced pressure or gas flow at 100 to 1000 ° C. for the purpose of removing H ₂ O, which is a by-product, after replacing some or all of the hydroxyl groups with halogen. Good.

  The inorganic oxide may be contacted with a metal compound in advance for the purpose of post-treatment of the —OH residue prior to contact with other catalyst components. The metal compound used here is not particularly limited, and component (D) is preferably used. The method for bringing the inorganic oxide into contact with the above metal compound is not particularly limited. For example, the method in which the oxide is insoluble in the organic solvent in which the metal compound is soluble, and the organic compound in which both are soluble. Examples include a method of contacting in a solvent and a method of contacting with a ball mill or the like in a substantially solvent-free condition.

  As the olefin polymerization catalyst of the present invention, a catalyst comprising component (A), component (B) and component (C), catalyst comprising component (A), component (B), component (C) and component (D). The catalyst which consists of a component (A), a component (B), a component (C), a component (D), and a component (E) can be illustrated.

  The amount of each component used in the olefin polymerization catalyst of the present invention will be described.

  There is no restriction | limiting in particular in the quantity of the component (B) with respect to a component (A), It is preferable that it is 0.0001-100 times mole, Most preferably, it is 0.001-10 times mole.

  When the component (C) is a clay mineral or a modified clay mineral treated with an organic compound, the component (A) per 1 g of the component (C) is preferably 0.0001 to 100 mmol, particularly preferably 0.001 to 10 mmol. is there. In addition, the component (B) is preferably 0.0001 to 100 mmol, particularly preferably 0.001 to 10 mmol, per 1 g of the component (C).

  When the component (C) is an alkylaluminoxane, the amount of the component (C) is preferably 0.1 to 10,000 mol, particularly preferably 1 to 1 mol per mol of the sum of the number of moles of the component (A) and the component (B). 1000 moles.

  When component (C) is an ionized ionic compound, the amount of component (C) is preferably 0.1 to 1000 mol, particularly preferably, per mol of the sum of the number of moles of component (A) and component (B). 0.3 to 100 mol.

  When component (C) is a Lewis acid, a sulfonate, or a carboxylic acid compound, the amount is preferably 0.1 to 1000 mol, particularly preferably 0, per mol of the sum of the number of moles of component (a) and component (b). 3 to 100 moles.

  The amount of component (D) used in the present invention is preferably 0.1 to 10,000 mol, particularly preferably 1 to 1000 mol, per mol of the sum of the number of moles of component (A) and component (B).

  When component (E) is used in the present invention, the sum of the number of moles of component (A) and component (B) is preferably 0.005 to 1 mmol, particularly preferably 0.05 to 1 g, relative to 1 g of component (E). 0.5 mmol.

  A method for preparing the olefin polymerization catalyst of the present invention will be described.

  Examples of the catalyst preparation method comprising component (A), component (B) and component (C) include a method of adding component (B) to the contact product of component (A) and component (C), and component (B). The method of adding the component (A) to the contact product of the component (C), the method of adding the component (C) to the contact product of the component (A) and the component (B), the component (A) ) And the contact product of component (B), a method of contacting component (A), component (B), and component (C) simultaneously, and the like.

  As a method for preparing a catalyst comprising component (A), component (B), component (C), and component (D), for example, component (A), component (B), component (C), and component in an organic solvent. Method of contacting (D), Method of adding component (B) to component (C) after adding contact products of component (A) and component (D), Component (A) to component (C) After the addition, the method of adding the contact product of component (B) and component (D), after adding the contact product of component (A) and component (D) to component (C), Method of adding contact product of component (D), Method of adding contact product of component (A), component (B) and component (D) to component (C), Component (C) and component (D) After adding component (A) to the contact product of, the method of adding component (B), contact of component (A) and component (D) with the contact product of component (C) and component (D) Method of adding component (B) after adding product, contact of component (C) and component (D), after adding component (A) to the contact product of component (C) and component (D), contact of component (B) and component (D) Method of adding the product, contact of the component (B) and the component (D) after adding the contact product of the component (A) and the component (D) to the contact product of the component (C) and the component (D) Method of adding product, method of adding contact product of component (A), component (B) and component (D) to contact product of component (C) and component (D), component (A) and component After adding the component (B) to the contact product of (D), the method of adding the component (C), after adding the contact products of the component (B) and the component (D) to the component (A), Method of adding (C), after adding the contact product of component (B) and component (D) to the contact product of component (A) and component (D), then adding component (C) After adding the component (B) to the component (A), the method of adding the contact product of the component (C) and the component (D), the component (A) to the contact product of the component (A) and the component (D) After adding B), the method of adding the contact product of component (C) and component (D), after adding the contact product of component (B) and component (D) to component (A), C) a method of adding the contact product of component (D), after adding the contact product of component (B) and component (D) to the contact product of component (A) and component (D), A method of adding the contact product of C) and component (D), a method of adding component (D) after adding component (B) to the contact product of component (A) and component (C), component ( A method of adding component (D) after adding component (A) to the contact product of B) and component (C), and adding component (C) to the contact product of component (A) and component (B). After adding the component (D), after adding the contact product of the component (A) and the component (B) to the component (C), and then adding the component (D) to the component (B) After adding the contact product of component (A) and component (C), after adding the contact product of component (B) and component (C) to component (A), the method of adding component (D), A method of adding the component (D), a method of adding the component (D) after adding the contact product of the component (B) and the component (C) to the contact product of the component (A) and the component (C) It can be illustrated.

  As a method for adjusting the catalyst comprising the component (A), the component (B), the component (C), the component (D), and the component (E), for example, the component (A), the component (B), and the component in an organic solvent. Method of contacting (C), component (D) and component (E), contacting component (A), component (B) and component (D) with the contact product of component (C) and component (E) A method of adding the product, a method of adding the component (A) and the component (B) to the contacting organism of the component (C), the component (D) and the component (E), and the component (A) and the component (B). The method of adding the contact product of a component (C) and a component (D) to a component (E) can be illustrated.

  Examples of the solvent used for contact include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethyl ether Or, ethers such as normal butyl ether; halogenated hydrocarbons such as methylene chloride or chloroform; 1,4-dioxane; acetonitrile or tetrahydrofuran can be exemplified.

  It is preferable that the temperature at the time of contact is selected between -20 to 200 ° C. for the treatment.

  The prepared catalyst for olefin polymerization may be used without washing, or may be used after washing.

  As the method for producing an olefin polymer in the present invention, an olefin is polymerized by single-stage polymerization or multi-stage polymerization of olefin using an olefin polymerization catalyst having component (A) and component (B) as constituent components. A method for producing a polymer (Method 1). As another method, (Step I) after producing an olefin polymer by polymerizing olefin using a catalyst component containing component (B) as a main component, (Step II) component ( Exemplifying a method (Method 2) for producing an olefin polymer by adding a catalyst component containing A) as a main component and polymerizing the olefin in the presence of the olefin polymer obtained in (Step I). Can do.

  Examples of the olefin used in the production method of the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Α-olefins such as eicosene, 4-methyl-1-pentene, 3-methyl-1-butene or vinylcycloalkane; cyclic olefins such as norbornene or norbornadiene; dienes such as butadiene or 1,4-hexadiene or styrene It can be illustrated. Two or more of these olefins can be mixed and used.

  An embodiment of Method 1 used in the production method of the present invention is shown below.

  There are no particular limitations on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in Method 1, and the polymerization temperature is preferably −100 to 120 ° C., particularly considering productivity, 20 to 120 ° C., more preferably 60 to It is preferable to carry out in the range of 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The olefin polymer can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after completion of the polymerization and drying.

  The polymerization in Method 1 can be carried out in a solution state, a suspension state or a gas phase state. In particular, when the polymerization is carried out in a suspension state, an olefin polymer having a uniform particle shape can be produced efficiently and stably. can do. The solvent to be used may be any organic solvent that is generally used. Specific examples include benzene, toluene, xylene, propane, isobutane, pentane, hexane, heptane, cyclohexane, gasoline, and the like. Olefin itself such as butene, 1-hexene and 1-octene can be used as a solvent.

  An embodiment of Method 2 used in the production method of the present invention is shown below.

  Examples of the catalyst containing component (B) as a main component include a catalyst comprising alkylaluminoxane as component (B) and component (C), a catalyst comprising component (D), and component (B) and component (C). As a catalyst comprising an ionized ionic compound, a catalyst comprising further component (D), a catalyst comprising a Lewis acid as component (B) and component (C), a catalyst further comprising component (D), and component (B ), A component (C) and a component (E), and further a catalyst comprising a component (D), preferably treated with an organic compound as component (B) and component (C). A catalyst comprising a modified clay mineral and a catalyst comprising the component (D) can be used.

  The catalyst comprising the modified clay mineral treated with the organic compound as the component (B) and the component (C) is obtained by contacting the component (B) with the modified clay mineral treated with the organic compound in an organic solvent. However, both the method of adding the modified clay mineral treated with the organic compound to the component (B) and the method of adding the component (B) to the modified clay mineral treated with the organic compound can be used.

  As the contact solvent, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane or cyclohexane, aromatic hydrocarbons such as benzene, toluene or xylene, ethyl ether or normal butyl ether, etc. And ethers, halogenated hydrocarbons such as methylene chloride or chloroform, 1,4-dioxane, acetonitrile or tetrahydrofuran.

  About a contact temperature, it is preferable to select between 0-200 degreeC and to process.

  The amount of each component used is 0.0001 to 100 mmol, preferably 0.001 to 10 mmol of component (B) per 1 g of the modified clay mineral treated with an organic compound.

  The contact product of the component (B) thus prepared and the modified clay mineral treated with the organic compound may be used without washing, or may be used after washing. Further, when the component (B) is a dichloro compound, it is preferable to further add the component (D). Moreover, a component (D) can be added for the purpose of removing the impurities in the modified clay mineral processed with the organic compound, the polymerization solvent, and the olefin.

  A catalyst comprising a modified clay mineral treated with an organic compound as component (B) and component (C) and component (D) brings component (B), component (C) and component (D) into contact in an organic solvent. The component (D) is added to the contact product of the component (B) and the component (C), and the contact product of the component (B) and the component (C) is added to the component (D). Method, Method of Adding Component (C) to Contact Product of Component (B) and Component (D), Method of Adding Contact Product of Component (B) and Component (D) to Component (C), Component ( Method of adding the contact product of component (C) and component (D) to the contact product of B) and component (D), and adding component (B) to the contact product of component (C) and component (D) Exemplifying a method of adding a contact product of component (B) and component (D) to a contact product of component (C) and component (D) It can be.

  In Step I of Method 2, the polymerization temperature is preferably −100 to 120 ° C., and particularly considering productivity, the polymerization temperature is preferably 20 to 120 ° C., more preferably 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. When copolymerizing ethylene and an olefin having 3 or more carbon atoms, ethylene / olefin having 3 or more olefins (molar ratio) is 0 to 200, preferably 3 as a supply ratio of ethylene and olefin having 3 or more carbon atoms. A feed rate of -100, more preferably 5-50 can be used. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions.

  In Step I of Method 2, the polymerization can be carried out in solution, suspension or gas phase, and in particular when the polymerization is carried out in suspension, a long chain branched olefin copolymer having a well-defined particle shape. The coalescence can be produced efficiently and stably. The solvent to be used may be any organic solvent that is generally used. Specific examples include benzene, toluene, xylene, propane, isobutane, pentane, hexane, heptane, cyclohexane, gasoline, and the like. Olefin itself such as butene, 1-hexene and 1-octene can be used as a solvent.

Examples of the catalyst containing component (A) as a main component include a catalyst comprising component (A) and component (D), a catalyst comprising water, and a catalyst comprising alkylaluminoxane as component (A) and component (C). Further, a catalyst further comprising component (D), a catalyst comprising an ionized ionic compound as component (A) and component (C), a catalyst further comprising component (D), component (A) and component (C) As a catalyst comprising a Lewis acid, a catalyst comprising a component (D), and as components (A) and (C), an alkylaluminoxane or an ionized ionic compound is immobilized on a solid support such as an inorganic oxide or clay mineral. A catalyst comprising the above components and a catalyst comprising the component (D) can be exemplified, but preferably a catalyst comprising the components (A) and (D) can be used.
In Method 2 that can be used in the production method of the present invention, after producing an olefin polymer in Step I, a catalyst comprising the combination described above containing Component (A) as a main component in Step II is added to the polymerization system. The method is not particularly limited. After the olefin polymer is produced, the residual pressure in the polymerization system is removed, the system is replaced with an inert gas, and then each component is added to the system. Polymerization is performed after the olefin polymer is produced. After removing the residual pressure in the system and replacing the system with an inert gas, the method of adding each component to the system after contacting in advance, removing the residual pressure in the polymerization system after the production of the olefin polymer, A method in which each component is added to the system without replacing the system with an inert gas, the residual pressure in the polymerization system is removed after the production of the olefin polymer, and each component is replaced without replacing the system with an inert gas. In the system after contacting The method of adding, after producing the olefin polymer, without removing the residual gas, adding each component to the system as it is, after the production of the olefin polymer, without removing the residual gas, Examples of the method include addition to the system after contact. The temperature at the time of addition is not particularly limited, and can be carried out in the range of -50 ° C to the boiling point of the solvent.

  In method 2, after the olefin polymer is produced in step I, there is no particular limitation on the time from the addition of the catalyst containing component (A) as the main component in step II to the polymerization system until the start of olefin polymerization. 1 second to 24 hours, a method of polymerizing an olefin immediately after adding a catalyst containing the component (A) as a main component into the polymerization system, and a catalyst containing the component (A) as a main component into the polymerization system A method of polymerizing an olefin after the addition of the above time can be exemplified. The temperature at that time is not particularly limited, and it can be carried out in the range of -50 ° C to the boiling point of the solvent.

  In Step II, the polymerization temperature is preferably −100 to 120 ° C., and considering productivity, it is preferably 20 to 120 ° C., more preferably 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. When copolymerizing ethylene and an olefin having 3 or more carbon atoms, ethylene / olefin having 3 or more olefins (molar ratio) is 0 to 200, preferably 0 as a supply ratio of ethylene and olefin having 3 or more carbon atoms. A feed rate of 0.05 to 100, more preferably 0.1 to 50 can be used. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The obtained olefin polymer can be separated and recovered from the polymerization solvent by a conventionally known method after the completion of the polymerization and dried.

  The component (B) used in the olefin polymerization catalyst and olefin polymer production method of the present invention is preferably capable of producing an olefin polymer having a terminal vinyl by polymerizing an olefin in the presence thereof. it can. The olefin polymer obtained from the component (B) is preferably a low molecular weight component that functions as a macromonomer in the production of the olefin polymer of the present invention.

  The number average molecular weight (Mn) of the olefin polymer obtained from the component (B) is 1,000 or more and 300,000 or less, preferably 5,000 or more and 200,000 or less, and more preferably 10,000 or more. 100,000 or less. Mw / Mn is 2 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 10 or less.

  Among the olefin polymers obtained by the olefin polymer production catalyst and production method of the present invention, preferably, the olefin polymer obtained by component (A) is a part of the macromonomer obtained by component (B). As a result, a part of the olefin polymer has a long chain branch.

The density (kg / m ³ ) of the olefin polymer obtained in the present invention is a value measured by a density gradient tube method in accordance with JIS K6760 (1995), and is 890 kg / m ³ or more and 980 kg / m ³ or less.

  The weight average molecular weight (Mw) of the olefin polymer obtained in the present invention is 30,000 to 10,000,000, preferably 40,000 to 8,000,000, more preferably 50,000. 000 to 5,000,000. Mw / Mn is 2 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 10 or less.

  The melt flow rate [MFR (g / 10 min)] of the olefin copolymer obtained in the present invention is a value measured at 190 ° C. under a load of 2.16 kg, preferably 0.1 or more and 50 or less.

The powder bulk density of the olefin copolymer obtained by the present invention measured by a method based on JISK6760 (1995) is preferably 0.15 g / cm ³ or more and 0.70 g / cm ³ or less, particularly preferably 0.17 g. / Cm ³ or more and 0.70 g / cm ³ or less, more preferably 0.20 g / cm ³ or more and 0.70 g / cm ³ or less.

  The olefin polymer produced in the present invention includes, for example, a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a pigment, carbon black, talc, glass powder, Known additives such as inorganic fillers or reinforcing agents such as glass fibers, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents can be blended.

  The olefin polymer produced in the present invention can be used by mixing with other thermoplastic resins, such as HDPE, LLDPE, LDPE, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, It can be mixed with an ethylene / vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, polystyrene, or a maleic anhydride graft product thereof.

  By using the catalyst for olefin polymerization of the present invention, an olefin polymer having a high ratio of high molecular weight components can be produced efficiently.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Preparation of the olefin polymerization catalyst, polymerization reaction and solvent purification were all carried out in an inert gas atmosphere. As the preparation of the olefin polymerization catalyst and the solvent used for the polymerization reaction, all the solvents that had been purified, dried, and deoxygenated by a known method in advance were used. Tosoh Finechem Co., Ltd. was used for the toluene solution (0.848M) of triisobutylaluminum.

  Furthermore, various physical properties of the olefin polymers in Examples and Comparative Examples were measured by the following methods.

  The melt flow rate (MFR) was measured by a method according to ASTM D1238 Condition E.

  The weight average molecular weight (Mw), the number average molecular weight (Mn) and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) were measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgelGMHhr-H (20) HT is used, the column temperature is set to 140 ° C., and 1 and 2 are used as eluents. , 4-trichlorobenzene was used for measurement. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of the molecular weight is calibrated using a polystyrene sample having a known molecular weight by the universal calibration method. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

  The high molecular weight component ratio was determined as follows. First, the molecular weight distribution curve obtained by GPC measurement is separated into two curves having different molecular weights. The ratio of the area of the high molecular weight curve to the area of the combined curve of the two separated curves was defined as the high molecular weight component ratio. The two curves to be separated were log-normal distributions, and the peak top molecular weight, standard deviation, and ratio of each curve were determined so that the synthesized curve and the actually measured molecular weight distribution curve coincided.

  The bulk density was measured according to JIS K-6721 (1977). The melting point Tm and heat of fusion ΔH of the obtained polymer were measured using DSC (Differential Scanning Calorimeter) SEIKO SC-5000.

Example 1
[Preparation of component (C)]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 6.6 g (0.022 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride solution was prepared. To this solution was added 20 g of hectorite. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of ions per gram of modified hectorite was 0.85 mmol.
[Preparation of Olefin Polymerization Catalyst]
Component (B): Dimethylsilylenebis (1-cyclopentadienyl) zirconium dichloride (complex B-1, 55.8 mg, 160 μmol) is suspended in hexane (22.4 mL), and component (D): triisobutylaluminum A hexane solution (D-1, 0.714M, 22.4 mL) was added to obtain a contact product of component (B) and component (D). This contact product was added to the modified hectorite (4.0 g) of the above component (C) and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, and a hexane solution of triisobutylaluminum (0.03M, 40 ml) is added thereto, followed by stirring and standing, and then the supernatant is removed to wash the solid component. Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst component containing components (B) and (C).

Subsequently, component (A): diphenylmethylene (3-allyl-1-cyclopentadienyl) (2,7-ditertiary butyl-9-fluorenyl) zirconium dichloride (complex A-1-1, 6.0 mg, 8 0.5 μmol) is suspended in hexane (7.2 mL), component D: triisobutylaluminum in hexane solution (0.714 M, 5.6 mL) is added, and the contact product of component (A) and component (D) Was added to the catalyst component containing the above components (B) and (C). The molar ratio of component (A) to component (B) is 5/95 (mol / mol). After stirring at room temperature for 6 hours, the solution was left to stand to remove the supernatant, washed with a hexane solution of triisobutylaluminum (0.03M), and further added with a hexane solution of triisobutylaluminum (0.15M) to obtain a slurry concentration. (100 g of solid catalyst component per liter) was obtained, and an olefin polymerization catalyst containing component (A), component (B), component (C), and component (D) was obtained.
[Production of olefin polymer]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, the olefin polymerization catalyst (0.15 mL) was added, and an ethylene / hydrogen mixed gas (containing 2000 ppm of hydrogen) was introduced to initiate polymerization. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., and the internal pressure of the autoclave was depressurized. Then, the contents were suction filtered and dried. The obtained olefin polymer was 67.3 g, Mn = 10,000, Mw = 100,000, Mw / Mn = 10.0, the high molecular weight component ratio was 44%, and MFR = 1.3 g / 10 min. . The bulk density was 342 kg / m ³ .

Comparative Example 1
[Preparation of Olefin Polymerization Catalyst]
Except that diphenylmethylene (1-cyclopentadienyl) (2,7-ditertiary butyl-9-fluorenyl) zirconium dichloride (A-1, 5.7 mg, 8.5 μmol) was used as component (A) An olefin polymerization catalyst was obtained in the same manner as in Example 1.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 1 except that the above olefin polymerization catalyst (0.15 ml) was used and an ethylene / hydrogen mixed gas (hydrogen: 2000 ppm included) was used. 58.1 g of olefin polymer was obtained, and the obtained olefin polymer had Mn = 8,500, Mw = 51,900, Mw / Mn = 6.1, a high molecular weight component ratio of 20%, and MFR = 50. It was 4 g / 10 minutes. The bulk density was 294 kg / m ³ .

  The GPC curve of the olefin polymer obtained in Example 1 and Comparative Example 1 is shown in FIG.

Example 2
[Preparation of Olefin Polymerization Catalyst]
Dimethylmethylene (1-cyclopentadienyl) (1-indenyl) zirconium dichloride (complex B-2, 63.8 mg, 160 μmol) was used as component (B), and diphenylmethylene (3-allyl-1) was used as component (A). -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-1, 18.9 mg, 40 μmol), the molar ratio of component (A) to component (B) was 20/80 (mol / mol ), An olefin polymerization catalyst was obtained in the same manner as in Example 1.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 1 except that the above olefin polymerization catalyst (0.35 ml) was used and 1-butene (18.8 g) and an ethylene / hydrogen mixed gas (containing 5400 ppm of hydrogen) were used. did. 52.1 g of olefin polymer was obtained, and the obtained olefin polymer had Mn = 10,000, Mw = 65,700, Mw / Mn = 6.6, a high molecular weight component ratio of 62%, and MFR = 5. .2 g / 10 min, melting point = 117.2 ° C. The bulk density was 241 kg / m ³ .

Example 3
[Preparation of Olefin Polymerization Catalyst]
Example 2 except that diphenylmethylene (3-benzyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-2, 20.9 mg, 40 μmol) was used as component (A). An olefin polymerization catalyst was obtained in the same manner.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 2 except that the above olefin polymerization catalyst (0.40 ml) was used and a hydrogen mixed gas (hydrogen: 3800 ppm included) was used. 45.1 g of olefin polymer was obtained, and the obtained olefin polymer had Mn = 9,100, Mw = 63,200, Mw / Mn = 6.9, the high molecular weight component ratio was 31%, and MFR = 5. 0.7 g / 10 min, melting point = 119.9 ° C. The bulk density was 300 kg / m ³ .

Comparative Example 2
[Preparation of Olefin Polymerization Catalyst]
Olefin polymerization in the same manner as in Example 2 except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2, 22.3 mg, 40 μmol) was used as component (A). A catalyst was obtained.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 2 except that the above olefin polymerization catalyst (0.50 ml) was used and a hydrogen mixed gas (hydrogen: 1500 ppm included) was used. 62.0 g of an olefin polymer was obtained, and the obtained olefin polymer had Mn = 9,800, Mw = 76,400, Mw / Mn = 7.8, a high molecular weight component ratio of 9%, and MFR = 7. 0.6 g / 10 min, melting point = 120.0 ° C. The bulk density was 264 kg / m ³ .

  The GPC curves of the olefin polymers obtained in Examples 2 to 3 and Comparative Example 2 are shown in FIG.

Example 4
[Preparation of Olefin Polymerization Catalyst]
Dimethylmethylene (1-cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride (complex B-3, 70.4 mg, 160 μmol) was used as component (B), and diphenylmethylene was used as component (A). (3-Allyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-1, 18.9 mg, 40 μmol) was used for olefin polymerization in the same manner as in Example 1. A catalyst was obtained.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 1 except that the above olefin polymerization catalyst (0.25 ml) was used and a hydrogen mixed gas (hydrogen: 2800 ppm included) was used. 46.8 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 9,900, Mw = 62,400, Mw / Mn = 6.3, a high molecular weight component ratio of 15%, and MFR = 6. The melting point was 117.5 ° C. The bulk density was 214 kg / m ³ .

Comparative Example 3
[Preparation of Olefin Polymerization Catalyst]
Olefin polymerization in the same manner as in Example 4 except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2, 22.3 mg, 40 μmol) was used as component (A). A catalyst was obtained.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 4 except that the above olefin polymerization catalyst (0.40 ml) was used and a hydrogen mixed gas (hydrogen: 1700 ppm included) was used. 50.3 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 10,500, Mw = 49,400, Mw / Mn = 4.9, a high molecular weight component ratio of 4%, and MFR = 31. 0.6 g / 10 min, melting point = 118.0 ° C. The bulk density was 204 kg / m ³ .

  The polymerization results of Example 4 and Comparative Example 3 are shown in FIG.

Example 5
[Preparation of Olefin Polymerization Catalyst]
Dimethylmethylene (1-cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride (complex B-4, 68.3 mg, 160 μmol) was used as component (B), and diphenylmethylene was used as component (A). Using (3-allyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-1, 18.9 mg, 40 μmol), the molar ratio of component (A) to component (B) was 20 An olefin polymerization catalyst was obtained in the same manner as in Example 1 except that the amount was / 80 (mol / mol).
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 1 except that the above olefin polymerization catalyst (0.40 ml) was used and a hydrogen mixed gas (hydrogen: containing 3250 ppm) was used. 43.6 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 9,200, Mw = 80,900, Mw / Mn = 8.8, a high molecular weight component ratio of 37%, and MFR = 2. 0.1 g / 10 min, melting point = 116.2 ° C. The bulk density was 2226 kg / m ³ .
Example 6
[Preparation of Olefin Polymerization Catalyst]
Example 5 except that diphenylmethylene (3-benzyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-2, 20.9 mg, 40 μmol) was used as component (A). An olefin polymerization catalyst was obtained in the same manner.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 5 except that the above olefin polymerization catalyst (0.40 ml) was used and a hydrogen mixed gas (hydrogen: 2700 ppm included) was used. 50.6 g of an olefin polymer was obtained, and the obtained olefin polymer had Mn = 8,600, Mw = 64,500, Mw / Mn = 7.5, a high molecular weight component ratio of 29%, and MFR = 4. 0.2 g / 10 min, melting point = 119.0 ° C. The bulk density was 281 kg / m ³ .

Comparative Example 4
[Preparation of Olefin Polymerization Catalyst]
Olefin polymerization in the same manner as in Example 5 except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2, 22.3 mg, 40 μmol) was used as component (A). A catalyst was obtained.
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 5 except that the above olefin polymerization catalyst (0.40 ml) was used and a hydrogen mixed gas (hydrogen: 1050 ppm included) was used. 36.7 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 11,000, Mw = 66,000, Mw / Mn = 6.0, a high molecular weight component ratio of 7%, and MFR = 9. 0.0 g / 10 min, melting point = 117.8 ° C. The bulk density was 175 kg / m ³ .

  The polymerization results of Examples 5 to 6 and Comparative Example 4 are shown in FIG.

Example 7
[Preparation of solid support]
Collect component (E): silica (5 g) in a Schlenk tube and suspend in 45 mL of toluene. After cooling to 0 ° C., component (C): methylaluminoxane (63.3 mmol) was added. After reacting at 0 ° C. for 30 minutes, the temperature was raised to 95 ° C. and reacted for 4 hours. After cooling to room temperature, stirring was stopped, the supernatant was removed, and the solid was washed twice with toluene (45 ml). Toluene was added to obtain a solid support slurry of 50 ml in total.
[Preparation of olefin polymerization catalyst]
Component (B): Dimethylsilylene (1-cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride (complex B-4, 16 mg, 38 μmol) is dissolved in toluene (2 mL), and the above solid It was added to a carrier slurry (equivalent to 1 g of silica). After stirring at room temperature for 1 hour and allowing to stand, the supernatant was removed, washed twice with hexane (20 ml), hexane was added to adjust the slurry concentration (50 g of component (C) per liter), and component (B) A catalyst component containing was obtained. Subsequently, component (A): diphenylmethylene (3-allyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-1, 1.2 mg, 2.0 μmol) was added to toluene (mL). And added to the catalyst component containing the component (B). The molar ratio of component (A) to component (B) is 5/95 (mol / mol). After stirring at room temperature for 6 hours, the mixture is left to stand to remove the supernatant, washed twice with hexane (20 ml), and then added with hexane to adjust the slurry concentration (component (C) per liter is 50 g). An olefin polymerization catalyst containing (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution (0.714M) of component (D): triisobutylaluminum were introduced, and the internal temperature of the autoclave was increased to 70 ° C. The catalyst slurry (0.25 mL) was added to the autoclave, and 1-butene (16 g) and an ethylene / hydrogen mixed gas (containing 5000 ppm of hydrogen) were introduced to initiate polymerization. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.8 MPa, and the internal temperature of the autoclave was controlled at 70 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the content was suction filtered. After drying, 45 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 18,000, Mw = 100,000, Mw / Mn = 5.8, a high molecular weight component ratio of 15%, and MFR = 7.9 g / 10 min.

Comparative Example 5
[Preparation of Olefin Polymerization Catalyst]
An olefin polymerization catalyst was obtained in the same manner as in Example 7, except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2, 2 μmol) was used as component (A). .
[Production of olefin polymer]
Polymerization was carried out in the same manner as in Example 7 except that the above catalyst (0.1 ml) was used and a hydrogen mixed gas (hydrogen: containing 2800 ppm) was used. 36 g of olefin polymer was obtained. The obtained olefin polymer had Mn = 9,700, Mw = 74,000, Mw / Mn = 7.6, the high molecular weight component ratio was 8%, and MFR = 23.5 g / 10 minutes.

Example 8
[Production of olefin polymer]
In a Schlenk tube, component (A) diphenylmethylene (3-allyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2-1, 6.0 mg, 10 μmol) and dimethylsilylene as component (B) (1-Cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride (complex B-3, 83 mg, 190 μmol) is collected, and toluene is added and dissolved so that the total amount becomes 200 ml. A complex solution was prepared.

After introducing toluene (1,190 mL) into a 2 L autoclave, the complex solution (0.1 ml, complex amount 0.25 μmol) was added. Next, a toluene solution of component (C) methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., PMAO-S, 2.85 mol / L, 0.18 ml, 0.5 mmol) was added and stirred for 30 minutes, and then the internal temperature of the autoclave was adjusted. The temperature was raised to 85 ° C. Ethylene was introduced into the autoclave to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure of ethylene was maintained at 1.2 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the content was suction filtered. After drying, 70 g of an olefin polymer was obtained. The obtained olefin polymer had Mn = 44,000, Mw = 203,300, Mw / Mn = 4.62, a high molecular weight component ratio of 6%, and HLMFR = 1.8 g / 10 min Comparative Example 6
[Production of olefin polymer]
In a Schlenk tube, component (A) diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (complex A-2, 5.6 mg, 10 μmol) and component (B) dimethylsilylene (1-cyclopentadiene) Enyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride (complex B-3, 83 mg, 190 μmol) was collected, and toluene was added and dissolved so that the total amount became 200 ml to prepare a complex solution. .

  After introducing toluene (1,190 mL) into a 2 L autoclave, the complex solution (0.25 ml, complex amount 0.25 μmol) was added. Next, a toluene solution of component (C) methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., PMAO-S, 2.85 mol / L, 0.44 ml, 1.25 mmol) was added and stirred for 30 minutes, and then the internal temperature of the autoclave was adjusted. The temperature was raised to 85 ° C. Ethylene was introduced into the autoclave to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure of ethylene was maintained at 1.2 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the content was suction filtered. After drying, 42 g of olefin polymer was obtained. The obtained olefin polymer had Mn = 31,000, Mw = 76,000, Mw / Mn = 2.45, a high molecular weight component ratio of 1%, and HLMFR = 65 g / 10 min.

2 is a GPC curve of the olefin polymer obtained in Example 1 and Comparative Example 1. It is a GPC curve of the olefin polymer obtained in Examples 2-3 and Comparative Example 2. 4 is a GPC curve of the olefin polymer obtained in Example 4 and Comparative Example 3. It is a GPC curve of the olefin polymer obtained in Examples 5-6 and Comparative Example 4.

Claims (8)

Component (A) The following general formula (1)

(Wherein M ¹ is a titanium atom, a zirconium atom or a hafnium atom, X ¹ is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number ¹ to R ⁴ . 20 represents a silyl group, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein a hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms) Is a silyl group , An amino group, an alkoxy group, may be substituted by an aryl group or a halogen atom), 4 to each other may be the same or different. Further, good .f also form a ring connected to each other from 1 E ¹ is a carbon atom, a silicon atom, a germanium atom, or a tin atom.)
Component (B) The following general formula (2)

(Here, M ² is a titanium atom, a zirconium atom or a hafnium atom, and X ² is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, An amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group) E ² may be an oxygen atom, a sulfur atom, or the following general formula (3).

(Wherein R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); E ³ is a silicon atom, a germanium atom, or a tin atom, and may be the same or different from each other), and e is an integer of 1 to 5. When e is 2 or more, E ² may be the same as or different from each other.
Cp ¹ represents the following general formula (4), (5) or (6)

(Wherein R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or 1 carbon atom) Represents an alkoxy group having 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom) They may be substituted))) and may be the same or different. Cp ¹ forms a sandwich structure with M ² . A catalyst for olefin polymerization comprising a transition metal compound represented by formula (II) and a component (C) activation promoter as constituents. Furthermore, component (D) the following general formula (7)
Al (R ¹⁰ ) ₃ (7)
^{(Wherein, R 10} is hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or an amino group having 1 to 20 carbon atoms of 6 to 20 carbon atoms. The catalyst for olefin polymerization of Claim 1 which uses the compound represented by this as a structural component. The olefin polymerization catalyst according to claim 2, wherein the component (E) is a solid support. The olefin polymerization catalyst according to any one of claims 1 to 3, wherein the component (C) is a clay mineral. The olefin polymerization catalyst according to any one of claims 1 to 3, wherein the component (C) is a modified clay mineral treated with an organic compound. The modified clay mineral treated with the organic compound of component (C) is represented by the following general formula (8)
[R ¹¹ R ¹² _x-1 GH] _y [J] _z (8)
(Wherein [R ¹¹ R ¹² _x-1 GH] is a cation, G is an element selected from Group 15 or Group 16 of the periodic table, and R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms. Each of R ¹² is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, x = 3 when G is a Group 15 element, and x = 2 when G is a Group 16 element. And [J] is an anion, and y and z are integers chosen to balance the charge.)
The olefin polymerization catalyst according to claim 5, which is a modified clay mineral treated with an organic compound represented by the formula: The catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the component (C) is an alkylaluminoxane. A method for producing an olefin polymer, wherein an olefin is polymerized using the olefin polymerization catalyst according to any one of claims 1 to 7.

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