JP2016135879A - Method for producing metallocene preliminary polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallocene preliminary polymerization catalyst that has a high polymerization activity and exhibits a good powder characteristic.SOLUTION: Provided is a metallocene preliminary polymerization catalyst obtained by bulk preliminary-polymerizing a supported metallocene catalyst containing the following (A), (B) and (C), in a liquified propylene at 0 to 70°C, to a preliminary polymerization magnification of 200 to 8,000. (A): different 2 kinds of binary complexes comprising group 4 metallocene represented by the formula below; (B) an aluminum oxy compound; and (C) a carrier.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a metallocene prepolymerization catalyst, and in particular, relates to a method for producing a metallocene prepolymerization catalyst characterized by polymerizing a polymer having excellent particle properties with high polymerization activity.

As a catalyst for producing a polypropylene-based polymer, a metallocene catalyst that has been heavily used in recent years has a molecular weight distribution of a propylene polymer or a propylene-α-olefin copolymer as compared with a conventionally used Ziegler-Natta catalyst. The composition distribution is narrow. In the case of a propylene homopolymer, a polymer with high regularity, low low molecular weight components and a narrow molecular weight distribution is obtained, and in the case of a propylene-α-olefin copolymer, there are few low crystalline components, A copolymer having a narrow composition distribution is obtained. Further, the metallocene catalyst has good reactivity with hydrogen as a chain transfer agent, and can polymerize a low molecular weight component without reducing the activity.
For these reasons, in metallocene catalysts, characteristics such as stereoregularity, catalytic activity (polymerization activity), molecular weight distribution and composition distribution are further enhanced, and further, the types of copolymers are expanded, and various molecular characteristics. Various research improvements, such as improving

  The polymerization method using the metallocene catalyst (for example, Patent Documents 1 and 2) has a very high polymerization activity per transition metal as compared with the conventional method using a Ziegler-Natta catalyst. However, in order to obtain sufficient polymerization activity using these catalysts, a large amount of expensive aluminoxane is required, so that the polymerization activity per aluminum is low and not uneconomical. It was necessary to remove the residue, which was not suitable for industrial use. Therefore, industrial metallocene catalysts are desired to have higher activity for the purpose of reducing the amount of organoaluminum compound used, reducing catalyst residues, and reducing catalyst costs.

Against this background, many techniques for improving the activity of metallocene catalysts and methods for producing propylene polymers using the same have been proposed.
As a technique for improving the activity of a metallocene catalyst, a method for polymerizing olefins using a catalyst in which one or both of a transition metal compound and an aluminoxane are supported on an inorganic oxide such as silica or alumina is proposed. (For example, patent documents 3 to 7). Similarly, a method of polymerizing olefins using a catalyst in which one or both of a transition metal compound and an organoaluminum compound is supported on an inorganic oxide or organic substance such as silica or alumina has been proposed (for example, Patent Documents 8 to 12). ).
However, even in the methods proposed in these methods, the polymerization activity per aluminum is still not sufficient.

Further, as a carrier improvement technique, production of an olefin polymer using a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a metallocene compound, a clay carrier, and, if necessary, a metallocene catalyst composed of an organoaluminum compound. A method (see, for example, Patent Document 13) is disclosed. According to this document, polymerization activity per unit amount of the metallocene-based transition metal compound superior to that of aluminoxane can be obtained without requiring the use of aluminoxane in the prior art. However, from the viewpoint of pursuing catalyst cost reduction, the polymerization activity was still not sufficient.
On the other hand, paying attention to the prepolymerization conditions, a method of changing the contact temperature between the supported metallocene catalyst and the olefin with time by raising and lowering the temperature during the prepolymerization step when preparing the clay-supported metallocene catalyst (for example, patents) Reference 14) and a method for controlling the rate of polymer formation during prepolymerization of a supported metallocene catalyst (for example, see Patent Document 15) are disclosed. However, in either case, the catalytic activity is still not sufficient.

Similarly, focusing on prepolymerization conditions from the viewpoint of improving powder properties, (A) a metallocene compound capable of producing stereoregular polypropylene, (B) a solid catalyst component formed from an aluminoxane and a particulate carrier, Disclosed is a method for producing stereoregular polypropylene, characterized in that (C) slurry prepolymerization with ethylene in the presence of a catalyst comprising an organoaluminum compound (C) in advance, followed by bulk polymerization of propylene. (For example, see Patent Document 16). However, in the said literature, although the improvement of powder property was confirmed, it has not confirmed about the improvement of catalyst activity.
Furthermore, when propylene and other olefins are copolymerized with the same ethylene prepolymerization catalyst, homopolymerization is performed in liquefied propylene at a polymerization temperature of 5 to 40 ° C. using a tubular reactor in the first step. A method of copolymerizing propylene and other olefins after producing 2 to 15% by weight of the homopolymer is disclosed (for example, see Patent Document 17). However, similarly, although the improvement of the powder properties was confirmed in this document, the improvement of the catalytic activity was not confirmed.
In addition, for the purpose of suppressing the formation of aggregates of the produced polymer and the decrease in incorporation efficiency of the comonomer, a method in which the supported metallocene catalyst is prepolymerized in the presence of a liquid whose amount is less than the total pore volume of the supported catalyst system (for example, patent Reference 18) is disclosed. The comparative example discloses a prepolymerization example in liquefied propylene, but it is not suitable as prepolymerization conditions because of high temperature and high pressure. On the contrary, deterioration of powder properties was observed, and improvement in catalyst activity could not be confirmed.
Furthermore, it comprises the step of continuously contacting propylene or propylene and up to 20 mol% of one or more α-olefins with a metallocene-based catalyst system in a loop reaction kettle to obtain a prepolymerization degree of 60-500. An olefin polymerization method is disclosed. In the examples, the improvement of the contamination of the reactor was confirmed by preparing the prepolymerization ratio of 78 to 145 in liquefied propylene at 30 to 50 ° C. However, the improvement of the catalytic activity was not confirmed (for example, patent Reference 19).

JP 58-019309 A JP-A-2-167307 JP-A-61-108610 JP-A-60-135408 JP-A 61-296008 Japanese Patent Laid-Open No. 3-074412 Japanese Patent Laid-Open No. 3-074415 JP-A-1-101303 JP-A-1-207303 JP-A-3-234709 JP-A-3-234710 Japanese National Patent Publication No. 3-501869 Japanese Patent Laid-Open No. 5-301917 JP 2001-026613 A JP 2002-275206 A JP-A-8-217816 Japanese Patent Laying-Open No. 2005-068261 Japanese National Patent Publication No. 11-508932 Japanese Patent No. 4709748

  The object of the present invention is to optimize the prepolymerization conditions in view of the problems of the prior art in the metallocene catalyst described above, thereby having high productivity (polymerization activity) and high powder density and the like. An object of the present invention is to provide a method for producing a metallocene prepolymerization catalyst exhibiting properties.

  As a result of examining the prepolymerization conditions from various viewpoints and seeking optimization of the prepolymerization conditions, the present inventors focused on the prepolymerization conditions in order to solve the above-mentioned problems. After pre-polymerization, a main polymerization was carried out to find a polymerization method in which powder properties such as bulk density and catalytic activity were improved at the same time, and the present invention was completed.

In the olefin polymerization of the supported metallocene catalyst, the carrier particles are disintegrated with the growth of the polymer particles. If the growth rate of the polymer particles and the disintegration rate of the support are not balanced, Generation of fine powder (decrease in activity) occurs. For this reason, in order to suppress non-uniform particle growth, it is necessary to proceed with prepolymerization commensurate with the carrier strength. In particular, when a catalyst component containing an ion-exchange layered silicate is used as the component (B), the balance between the growth rate of polymer particles and the rate of disintegration of the carrier has a great influence on the catalyst performance.
In the course of the development of the present invention, the present inventors made such a hypothesis based on experience and tried to solve the problem while attempting verification.

In general, the polymer produced in the supported catalyst is the so-called replica effect (Polypropylene Handbook, Edward P. Moore, Jr., Hanser Publishers, Munich, 1996, P86), that is, the replication effect (catalyst shape of the polymer produced). However, the polymer particles may break up and generate fine powder, which may deteriorate the powder properties. The present inventors believe that this is because of the high polymerization rate of the supported metallocene catalyst. As a result, due to the rapid and non-uniform growth of the powder particles, a phenomenon occurs in which the powder particles do not grow in a shape similar to that of the carrier and the particles themselves break finely. This is because when the polymerization rate is very high, the active rate in the particles does not polymerize at a uniform rate because the diffusion rate of the monomer cannot catch up with the polymerization. It is considered that the shape becomes uneven, and further, the particles are crushed with the polymerization of the particles themselves. Usually, in order to avoid these phenomena, the catalyst is generally polymerized in advance under mild conditions (so-called pre-polymerization).
On the other hand, there is a method of increasing the number of active sites on the support as one of the activity improvements of the metallocene catalyst. For example, as a technique for increasing the number of active sites on the carrier, there is a technique of increasing the number of active sites by increasing the surface area of the carrier by collapsing many carriers at the initial stage of polymerization by prepolymerization.
That is, in order to improve the powder properties and the catalytic activity, it is important to efficiently balance the growth rate of the polymer particles and the collapse rate of the carrier.

Thus, as a result of the examination and verification based on these two viewpoints, the present inventors have determined that specific and selective conditions as compared with the conventional prepolymerization in 0 to 70 ° C. liquefied propylene, It has been found that bulk prepolymerization at a polymerization ratio of 0.01 to 8,000 is effective in solving the problems of the present invention, and the present invention has been completed.
By selecting and setting such conditions, there is a remarkable effect that powder properties and catalytic activity can be improved at the same time, which could not be achieved in the past.

一般式（ａ１）
［一般式（ａ１）中、Ｅ^１１及びＥ^１２は、それぞれ独立して、シクロペンタジエニル基、インデニル基、フルオレニル基又はアズレニル基であり、それぞれ置換基を有していてもよい。Ｑ^１１は、炭素数１〜２０の二価の炭化水素基、炭素数１〜２０の炭化水素基を有していてもよいシリレン基又はゲルミレン基を表し、Ｍ^１１は、ジルコニウム又はハフニウムを表し、Ｘ^１１及びＹ^１１は、それぞれ独立して、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の炭化水素基を有するシリル基、炭素数１〜２０のハロゲン化炭化水素基、アミノ基又は炭素数１〜２０のアルキルアミノ基を示す。］
成分（Ｂ）：アルミニウムオキシ化合物［Ｂ−１］、成分（Ａ）と反応してカチオンに変換することが可能なイオン性化合物又はルイス酸［Ｂ−２］、固体酸微粒子［Ｂ−３］、及びイオン交換性層状珪酸塩［Ｂ−４］からなる化合物群から選ばれる少なくとも一種
成分（Ｃ）：担体
成分（Ｄ）：有機アルミニウム化合物
なお、成分（Ｂ）が担体を兼ねる「Ｂ−３］と［Ｂ−４］の場合は、担体（Ｃ）はあってもなくてもよい。 Specifically describing the present invention, according to the first invention of the present invention, a supported metallocene catalyst comprising (A), (B), (C) and any (D) represented by the following general formula: In particular, using two different binary complexes , bulk prepolymerization is performed in liquefied propylene at 0 to 70 ° C. to a prepolymerization ratio of 0.01 to 8,000 , particularly 200 to 8,000. A process for producing a metallocene prepolymerized catalyst is provided.
Component (A): Group 4 transition metal compound represented by formula (a1)

Formula (a1)
[In General Formula (a1), E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. , X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. A hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component (B): Aluminum oxy compound [B-1], ionic compound or Lewis acid [B-2] that can be converted to a cation by reacting with component (A), solid acid fine particles [B-3] And at least one compound selected from the group consisting of ion-exchangeable layered silicates [B-4] Component (C): carrier Component (D): organoaluminum compound In addition, component (B) also serves as a carrier "B-3 ] And [B-4], the carrier (C) may or may not be present.

According to the second aspect of the present invention, there is provided the method for producing a metallocene prepolymerization catalyst according to the first aspect , wherein the prepolymerization ratio is 1,000 to 8,000 .

一般式（ａ２）
［一般式（ａ２）中、Ｒ^２１及びＲ^２２は、各々独立して、窒素、酸素又は硫黄を含有する炭素数４〜１６の複素環基を示す。また、Ｒ^２３及びＲ^２４は、各々独立して、ハロゲン、ケイ素、酸素、硫黄、窒素、ホウ素、リン若しくはこれらから選択される複数のヘテロ元素を含有してもよい、炭素数６〜１６のアリール基、又は窒素、酸素若しくは硫黄を含有する炭素数４〜１６の複素環基を表す。更に、Ｑ^２１は、炭素数１〜２０の二価の炭化水素基、炭素数１〜２０の炭化水素基を有していてもよいシリレン基又はゲルミレン基を表し、Ｍ^２１は、ジルコニウム又はハフニウムを表し、Ｘ^２１及びＹ^２１は、それぞれ独立して、上記一般式（ａ１）のＸ^１１及びＹ^１１と同様の置換基を示す。］ According to a third invention of the present invention, one of the components (A) comprises a complex represented by the following general formula (a2), and the metallocene prepolymerization catalyst according to the first or second invention A manufacturing method is provided. However, the complex represented by the following general formula (a2) has a ratio in the component (A) of 0.30 or more and 0.99 or less.

Formula (a2)
[In General Formula (a2), R ²¹ and R ²² each independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. R ²³ and R ²⁴ each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, having 6 to 16 carbon atoms It represents an aryl group or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent the same substituent as X ¹¹ and Y ^{11 in} the general formula (a1). ]

According to a fourth aspect of the present invention, the component (B) is an ion-exchange layered silicate [B-4], and the component (B) also serves as the component (C). In 3 invention, the manufacturing method of the metallocene prepolymerization catalyst is provided.

  According to the fifth aspect of the present invention, there is provided a method for producing a metallocene prepolymerization catalyst according to the first to fourth aspects, wherein hydrogen is allowed to coexist in liquefied propylene in bulk prepolymerization.

  According to the sixth aspect of the present invention, there is provided the method for producing a prepolymerization catalyst in the first to fifth aspects, wherein the prepolymerization time is 30 minutes or more in bulk prepolymerization.

  According to the seventh aspect of the present invention, the first to sixth aspects of the invention are characterized in that ethylene is added in the range of 0.01 to 5.0 wt% with respect to propylene in addition to liquefied propylene in bulk prepolymerization. A method for producing a prepolymerized catalyst is provided.

According to the eighth aspect of the present invention, at least one of the components (A), wherein the Oh Rukoto racemic general group 4 of the periodic table represented by the formula (a1) a transition metal compound, In the first to seventh inventions, a method for producing a metallocene prepolymerized catalyst is provided.

  According to the ninth aspect of the present invention, the bulk prepolymerization catalyst concentration at the end of prepolymerization in bulk prepolymerization is in the range of 10 to 300 g / L with respect to the amount of liquefied propylene charged initially. A method for producing a metallocene prepolymerized catalyst in the first to eighth inventions is provided.

  According to a tenth invention of the present invention, a bulk main polymerization is carried out using a prepolymerized catalyst produced by the method for producing a metallocene prepolymerized catalyst in the first to ninth inventions. A method for producing a polymer is provided.

  According to the present invention, in the polymerization using a metallocene catalyst, the powder properties and the catalytic activity are improved at the same time, whereby a powder having a high bulk density is obtained, and the stable operation and the catalyst cost are greatly reduced. However, it becomes possible to obtain a high-quality product.

The present invention uses a supported metallocene catalyst consisting of (A), (B), (C) and any (D), particularly two different binary complexes, in a liquefied propylene at 0 to 70 ° C. The present invention also relates to a method for producing a metallocene prepolymerization catalyst, characterized in that bulk prepolymerization is performed at a prepolymerization ratio of 0.01 to 8,000, particularly 200 to 8,000 . Below, the manufacturing method of the metallocene prepolymerization catalyst of this invention is demonstrated in detail.
And the catalyst used by this invention is a metallocene catalyst which carry | supported the metallocene complex which is an active point precursor on the support | carrier. If it is not supported, particle properties deteriorate and adhesion and blockage in the polymerization system occur, which is not preferable. The supported metallocene catalyst used in the polymerization of the present invention will be described in detail below.

1. Metallocene Catalyst The supported metallocene catalyst according to the present invention comprises (A), (B), (C) and an optional component (D).

一般式（ａ１） (1) Component (A)
Component (A) is a metallocene compound represented by the following general formula (a1).

Formula (a1)

[In General Formula (a1), E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. , X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. A hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent.
Of these, a substituted cyclopentadienyl group, a substituted indenyl group, and a substituted azulenyl group are preferable.

一般式（ａ２） Here, when E ¹¹ and E ¹² are substituted indenyl groups, the following structures can be exemplified.

Formula (a2)

[In General Formula (a2), R ²¹ and R ²² each independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. R ²³ and R ²⁴ each independently represent halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a C 6-16 aryl that may contain a plurality of hetero elements selected from these. Or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Further, M ²¹ represents zirconium or hafnium, and X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. A silyl group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. ]

R ²¹ and R ²² are each independently a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur, preferably a 2-furyl group, a substituted 2-furyl group, or a substituted group. The substituted 2-thienyl group or substituted 2-furfuryl group, more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ²¹ and R ²² are particularly preferably a 2- (5-methyl) -furyl group. R ²¹ and R ²² are preferably the same as each other.

R ²³ and R ²⁴ are halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or an aryl group having 6 to 16 carbon atoms that may contain a plurality of hetero elements selected from these. In addition, as the aryl group, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms and trialkylsilyl groups having 1 to 6 carbon atoms on the aryl cyclic skeleton The halogen-containing hydrocarbon group having 1 to 6 carbon atoms may be substituted.
^{Also, R 23} and ^{R 24,} the nitrogen may be a heterocyclic group having a carbon number of 4-16 which contains oxygen or sulfur. Such a heterocyclic group is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group. Furyl group. These substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl groups, halogen atoms such as fluorine and chlorine atoms, alkoxy having 1 to 6 carbon atoms such as methoxy and ethoxy groups. Group and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
At least one of R ²³ and R ²⁴ is preferably a phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5 -Di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t -A butylphenyl group and a 4-chlorophenyl group. R ²³ and R ²⁴ are preferably the same as each other.

Furthermore, X ²¹ and Y ²¹ are auxiliary ligands, which react with the cocatalyst of component (B) to produce an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, or triarylsilyl group having 1 to 20 carbon atoms.

Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ligands via carbon having 1 or 2 carbons, which bonds two five-membered rings, carbon It shows either a silylene group or a germylene group which may have a hydrocarbon group of 1 to 20. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ^21, methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, alkylene groups such as, arylalkylene group such as diphenylmethylene also, silylene group, methylsilylene, dimethylsilylene, diethyl silylene Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylenes such as diphenylsilylene Group, an alkyl oligosilylene group such as tetramethyldisilylene, a germylene group, an alkylgermylene group in which the silicon of the silylene group having a hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium, (alkyl) (aryl ) Germylene group, Examples thereof include an arylgermylene group.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Among the compounds represented by the general formula (a2), specific examples of preferable compounds are given below.
(1) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl-indenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(4) dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(5) Dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(6) dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(11) Dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] hafnium,
(12) dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium,
(15) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium,
(16) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium,
(17) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium,
(18) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium

(19) Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(20) Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(21) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium,
(23) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(24) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(25) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(26) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium,
(27) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(28) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(29) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(30) Dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel are more preferable. Mylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl}] hafnium, dichloro [1,1′- Methylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl- 2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-biphenylyl-indenyl}] hafnium It is.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl }] Hafnium.

一般式（ａ３） In the case where E ¹¹ and E ¹² are substituted cyclopentadienyl groups, the following structures can be exemplified.

General formula (a3)

[In General Formula (a3), R ³¹ and R ³⁴ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ³² , R ³³ , R ³⁵ and R ³⁶ are each independently And a hydrocarbon group having 1 to 6 carbon atoms. X ³¹ and Y ³¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms, and Q ³¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. Represents a silylene group or a germylene group, and M ³¹ represents zirconium or hafnium. ]

R ³¹ and R ³⁴ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl and n-propyl, particularly preferably a methyl group.
R ³² , R ³³ , R ³⁵ and R ³⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. And particularly preferably a methyl group.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. Preferred are methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl.

In the general formula (a3), X ³¹ and Y ³¹ are auxiliary ligands, and react with the cocatalyst of the component (B) to generate an active metallocene having olefin polymerization ability. As this object is achieved, X ³¹ and Y ³¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms is represented.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, or triarylsilyl group having 1 to 20 carbon atoms.

In general formula (a3), Q ³¹ is a divalent valence having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. Or a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ³¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene. Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylenes such as diphenylsilylene Group: an alkyl oligosilylene group such as tetramethyldisilylene, a germylene group, an alkylgermylene group in which silicon in the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium, (alkyl) ( Aryl) germylene group, Examples thereof include an arylgermylene group.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Among the compounds represented by the general formula (a3),
(1) dichloro {dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(2) dichloro {diphenylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(3) dichloro {dimethylgermylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(4) dichloro {dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl)} hafnium,
(5) dichloro {dimethylsilylenebis (2-ethyl-3-phenyl-5-methylcyclopentadienyl)} hafnium,
(6) dichloro {dimethylsilylenebis (2,3,5-triethylcyclopentadienyl)} hafnium,
(7) dichloro {dimethylsilylenebis (2,5-dimethyl-3-ethylcyclopentadienyl)} hafnium,
(8) dichloro {dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl)} hafnium,
(9) dichloro {dimethylsilylenebis (2,5-dimethyl-3-i-propylcyclopentadienyl)} hafnium,
More preferably, dichloro {dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium, dichloro {diphenylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium, dichloro {dimethylgel Mylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium, dichloro {dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl)} hafnium.

一般式（ａ４）
［一般式（ａ４）中、Ｒ^５１及びＲ^５２は、それぞれ独立して、炭素数１〜６の炭化水素基である。Ｒ^５３及びＲ^５４は、それぞれ独立して、ハロゲン、ケイ素、或いは、これらから選択される複数のヘテロ元素を含有してもよい炭素数６〜３０のアリール基である。Ｑ^５１は、炭素数１〜２０の二価の炭化水素基、炭素数１〜２０の炭化水素基を有していてもよいシリレン基又はゲルミレン基を表し、Ｍ^５１は、ジルコニウム又はハフニウムを表し、Ｘ^５１及びＹ^５１は、それぞれ独立して、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の炭化水素基を有するシリル基、炭素数１〜２０のハロゲン化炭化水素基、アミノ基又は炭素数１〜２０のアルキルアミノ基を表す。］ In addition, when E ¹¹ and E ¹² are substituted azulenyl groups, the following structures can be exemplified.

General formula (a4)
[In General Formula (a4), R ⁵¹ and R ⁵² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ⁵³ and R ⁵⁴ each independently represent halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ⁵¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁵¹ represents zirconium or hafnium. , X ⁵¹ and Y ⁵¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

R ⁵¹ and R ⁵² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ⁵³ and R ⁵⁴ each independently contain halogen, silicon, or a plurality of heteroelements selected from these, having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms. Of the aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ⁵¹ and Y ⁵¹ are auxiliary ligands, and react with the co-catalyst of component (B) to generate active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ⁵¹ and Y ⁵¹ are not limited to the type of ligand, and are independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Show.

Q ⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, bonding two five-membered rings, It shows either a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene and diethylsilylene. Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylenes such as diphenylsilylene Group, alkyl oligosilylene group such as tetramethyldisilylene, germanium group, alkylgermylene group in which silicon of silylene group having divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium, (alkyl ) (Aryl) Germille And an arylgermylene group.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁵¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a4) include the following.
Although a compound in which the central metal is hafnium has been described, it is obvious that similar zirconium compounds can be used, and various ligands, crosslinking groups, or auxiliary ligands can be arbitrarily used.

(1) dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(5) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(6) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium,
(11) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(12) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium,
(15) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(16) dichloro [1,1′-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(17) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(18) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,

(19) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(20) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(21) Dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(23) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(24) dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, Etc.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

一般式（ａ５） In addition, when E ¹¹ and E ¹² are a cyclopentadienyl group and an azulenyl group, the following structures can be exemplified.

General formula (a5)

In the general formula (a5), R ⁶¹ is a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ⁶² is an aryl group having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.
R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, Examples include i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like, preferably methyl, ethyl, n-propyl, i- Propyl, t-butyl, phenyl. However, any two or more of R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are substituents other than hydrogen atoms, and any one or more of R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are hydrogen atoms. is there.

X ⁶¹ and Y ⁶¹ are auxiliary ligands that react with the cocatalyst of component (B) to produce an active metallocene having olefin polymerization ability. In order to achieve this object, X ⁶¹ and Y ⁶¹ are each independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkylamide group, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

Q ⁶¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ring ligands through carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, Either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms is shown. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁶¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene and diethylsilylene. Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylenes such as diphenylsilylene Group, alkyl oligosilylene group such as tetramethyldisilylene, germanium group, alkylgermylene group in which silicon of silylene group having divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium, (alkyl ) (Aryl) Germille And an arylgermylene group. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁶¹ is zirconium or hafnium, preferably hafnium.

Among the compounds represented by the general formula (a5),
(1) dichloro {1,1′-dimethylsilylene (2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(2) dichloro {1,1′-dimethylsilylene (3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(3) dichloro {1,1′-dimethylsilylene (2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(4) dichloro {1,1′-dimethylsilylene (2,3-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(5) dichloro {1,1′-dimethylsilylene (3,4-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(6) dichloro {1,1′-dimethylsilylene (2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(7) dichloro {1,1′-dimethylsilylene (2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(8) dichloro {1,1′-dimethylsilylene (3,4-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium, (9) dichloro {1,1′-dimethyl Silylene (2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(10) dichloro {1,1′-dimethylsilylene (2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(11) dichloro {1,1′-dimethylsilylene (2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(12) dichloro {1,1′-dimethylsilylene (2-methyl-4-tert-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(13) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(14) dichloro {1,1′-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(15) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(16) dichloro {1,1′-dimethylsilylene (2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(17) dichloro {1,1′-dimethylsilylene (2,3-dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} hafnium,
(19) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} hafnium,

(20) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (4-phenyl-2-i-propyl-4H-azurenyl)} hafnium,
(21) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-i-propyl-4-phenyl-4H-azurenyl)} hafnium,
(22) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)} hafnium,
(23) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)} hafnium,
(24) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azulenyl)} hafnium,
(25) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azurenyl)} hafnium,
(26) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-t-butylphenyl) -4H-azurenyl)} hafnium,
(27) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -4H-azurenyl)} hafnium,
(28) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azulenyl)} hafnium,
(29) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azulenyl)} hafnium,
(30) dichloro {1,1′-methylphenylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(31) dichloro {1,1′-silacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(32) dichloro {1,1′-silacyclopropenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(33) dichloro {1,1′-silafluorenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(34) dichloro {1,1′-methylphenylgermylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(35) dichloro {1,1′-germacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(36) Dichloro {1,1′-germacyclopropenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(37) dichloro {1,1′-germafluorenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,

(38) Dichloro [dimethylsilylene {2-methyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(39) Dichloro [dimethylsilylene {2-methyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(40) Dichloro [dimethylsilylene {3- (2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(41) Dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(42) Dichloro [dimethylsilylene {2-methyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(43) Dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(44) Dichloro [dimethylsilylene {3- (1-cyclopropylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(45) Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(46) Dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(47) Dichloro [dimethylsilylene {3- (1-cyclohexylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(48) Dichloro [dimethylsilylene {2-methyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(49) Dichloro [dimethylsilylene {2-methyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(50) dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(51) Dichloro [dimethylsilylene {2-methyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(52) Dichloro [dimethylsilylene {2-methyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(53) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(54) Dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(55) Dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(56) Dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azuler)] hafnium,
(57) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(58) Dichloro [dimethylsilylene {2-ethyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(59) Dichloro [dimethylsilylene {2-ethyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(60) Dichloro [dimethylsilylene {3- (2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(61) Dichloro [dimethylsilylene {2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(62) Dichloro [dimethylsilylene {2-ethyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(63) Dichloro [dimethylsilylene {2-ethyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(64) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(65) Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(66) Dichloro [dimethylsilylene {2-ethyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(67) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(68) Dichloro [dimethylsilylene {2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(69) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,

(70) dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(71) Dichloro [dimethylsilylene {2-ethyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(72) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(73) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(74) Dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(75) Dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(76) Dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(77) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(78) Dichloro [dimethylsilylene {2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(79) Dichloro [dimethylsilylene {3- (cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(80) Dichloro [dimethylsilylene {3- (2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(81) Dichloro [dimethylsilylene {2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(82) Dichloro [dimethylsilylene {3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(83) Dichloro [dimethylsilylene {2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(84) Dichloro [dimethylsilylene {3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(85) Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(86) Dichloro [dimethylsilylene {2-n-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(87) Dichloro [dimethylsilylene {3- (1-cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(88) Dichloro [dimethylsilylene {2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(89) Dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(90) Dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(91) Dichloro [dimethylsilylene {2-n-propyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(92) Dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(93) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(94) Dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(95) Dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(96) Dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(97) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium, and the like.

一般式（ａ６）
一般式（ａ６）中、Ｒ^７２は、炭素数１〜２０の炭化水素基又は炭素数１〜２０のケイ素含有炭化水素基から選ばれ、Ｒ^７１、Ｒ^７３、Ｒ^７４、Ｒ^７５、Ｒ^７６、Ｒ^７７及びＲ^７８は、水素原子、炭素数１〜２０の炭化水素基又は炭素数１〜２０のケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ^７５〜Ｒ^７８までの隣接した置換基は、互いに結合して環を形成してもよい。
また、上記Ｘ^７１及びＹ^７１は、補助配位子であり、成分（Ｂ）の助触媒と反応してオレフィン重合能を有する活性なメタロセンを生成させる。この目的が達成するものとして、Ｘ^７１及びＹ^７１は、それぞれ独立して、水素原子、ハロゲン基、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルアミド基、トリフルオロメタンスルホン酸基、炭素数１〜２０のリン含有炭化水素基又は炭素数１〜２０のケイ素含有炭化水素基などを示す。 Also, E ¹¹ and E ¹² are, in the case of the cyclopentadienyl group and the fluorenyl group can be exemplified by the following structures.

General formula (a6)
In the general formula (a6), R ⁷² is selected from a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and R ⁷¹ , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ^76. , R ⁷⁷ and R ⁷⁸ are selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R ^{75 to} R ^78. Up to adjacent substituents may be bonded to each other to form a ring.
Moreover, said ^X71 and ^Y71 are auxiliary ligands, and react with the co-catalyst of the component (B) to generate an active metallocene having olefin polymerization ability. In order to achieve this object, X ⁷¹ and Y ⁷¹ are each independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkylamide group, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

In addition, Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. Or any one of a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the Q ^71, methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, alkylene groups such as; arylalkylene group such as diphenylmethylene also, silylene group, methylsilylene, dimethylsilylene, diethyl silylene, Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylene groups such as diphenylsilylene Alkylgermylene groups such as tetramethyldisilylene, germanium groups, alkylgermylene groups in which the silicon of the above divalent hydrocarbon group having 1 to 20 carbon atoms is substituted with germanium, (alkyl) (Aryl) germylene Group, arylgermylene group and the like.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁷¹ is zirconium or hafnium, preferably hafnium.

Among the compounds represented by the general formula (a6),
(1) dichloro {dimethylmethylene (3-i-propylcyclopentadienyl) fluorenyl} zirconium,
(2) dichlorodi {methylmethylene (3-tert-butylcyclopentadienyl) fluorenyl} zirconium,
(3) dichloro {dimethylmethylene (3-trimethylsilylcyclopentadienyl) fluorenyl} zirconium,
(4) dichloro {dimethylmethylene (3- (t-butyldimethylsilyl) cyclopentadienyl) fluorenyl} zirconium,
(5) dichloro {dimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) fluorenyl} zirconium,
(6) dichloro {dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenyl} zirconium,
(7) dichloro {dimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) fluorenyl} zirconium,
(8) dichloro {dimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) fluorenyl} zirconium,
(9) dichloro {dimethylmethylene (3-i-propyl-5-ethylcyclopentadienyl) fluorenyl} zirconium,
(10) dichloro {dimethylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) fluorenyl} zirconium,
(11) dichloro {dimethylmethylene (3-trimethylsilyl-5-ethylcyclopentadienyl) fluorenyl} zirconium,
(12) dichloro {dimethylmethylene (3- (t-butyldimethylsilyl) -5-ethylcyclopentadienyl) fluorenyl} zirconium,

(13) dichloro {dimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(14) dichloro {dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl)} zirconium,
(15) dichloro {dimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(16) dichloro {dimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(17) dichloro {dimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl)} zirconium,
(18) dichloro {dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-ditert-butylfluorenyl)} zirconium,
(19) dichloro {dimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl)} zirconium,
(20) dichloro {dimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl)} zirconium,
(21) dichloro {dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl)} zirconium,
(22) dichloro {dimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl)} zirconium,
(23) Dichloro {dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7 , 8,9,10-octahydrodibenzofluorenyl)} zirconium,
(24) Dichloro {dimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8 , 9,10-octahydrodibenzo [b, h] fluorenyl)} zirconium,
(25) dichloro {diphenylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(26) dichloro {diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl)} zirconium,
(27) dichloro {diphenylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(28) dichloro {diphenylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(29) dichloro {dimethylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(30) dichloro {dimethylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(31) dichloro {dimethylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(32) dichloro {dimethylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(33) dichloro {diphenylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(34) dichloro {diphenylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(35) dichloro {diphenylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl)} zirconium,
(36) Dichloro {diphenylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl)} zirconium.

一般式（ａ７）
上記一般式（ａ７）中、Ｒ^８１及びＲ^８２は、それぞれ独立して、炭素数１〜６の炭化水素基であり、好ましくはアルキル基であり、更に好ましくは炭素数１〜４のアルキル基である。具体的な例としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｎ−ペンチル、ｉ−ペンチル、ｎ−ヘキシルなどが挙げられ、好ましくはメチル、エチル、ｎ−プロピルである。 Also, E ¹¹ and E ¹² are, in the case of an indenyl group and azulenyl group, can be exemplified by the following structures.

General formula (a7)
In the general formula ^{(a7), R 81} and ^{R 82} are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms It is. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ⁸³ and R ⁸⁴ each independently contain halogen, silicon, or a plurality of heteroelements selected from these, having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms. Of the aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Moreover, said ^X81 and ^Y81 are auxiliary ligands, and react with the co-catalyst of the component (B) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ⁸¹ and Y ⁸¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Show.

Q ⁸¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings; Either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms is shown. When two hydrocarbon groups are present on the aforementioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁸¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene and diethylsilylene. Alkylsilylene groups such as di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, and arylsilylenes such as diphenylsilylene Group, alkyl oligosilylene group such as tetramethyldisilylene, germanium group, alkylgermylene group in which silicon of silylene group having divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium, (alkyl ) (Aryl) Germille And an arylgermylene group.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁸¹ is zirconium or hafnium, preferably hafnium.

Among the compounds represented by the general formula (a7),
(1) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(2) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(3) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(4) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(5) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] hafnium,
(6) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] hafnium,
(7) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-t-butylphenyl) -4H-1-azulenyl)] hafnium,
(8) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-t-butylphenyl) -4H-1-azurenyl)] hafnium,
(9) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] hafnium,
(10) Dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] hafnium,
(11) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] hafnium,
(12) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] hafnium,
(13) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] hafnium,
(14) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] hafnium,
(15) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium,
(16) Dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium,
(17) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(18) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,

(19) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(20) dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(21) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azulenyl)] hafnium,
(22) dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-t-butylphenyl) -4H-1-azulenyl)] hafnium,
(23) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] hafnium,
(24) dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azulenyl)] hafnium,
(25) dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azulenyl)] hafnium,
(26) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium,
(27) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azulenyl)] hafnium,
(28) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4- (4-fluorophenyl) -4H-1-azurenyl)] hafnium,
(29) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4- (4-t-butylphenyl) -4H-1-azulenyl)] hafnium,
(30) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4- (4-trimethylsilylphenyl) -4H-1-azulenyl)] hafnium,
(31) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-ethyl-4- (1-naphthyl) -4H-1-azulenyl)] hafnium,
(32) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] hafnium,
(33) Dichloro [dimethylsilylene (2-ethyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium.

(2) Component (B)
As the component (B), an aluminum oxy compound [B-1], an ionic compound that can be converted into a cation by reacting with the transition metal compounds (a1) and (a2), or a Lewis acid [B-2] , Solid acid fine particles [B-3], and at least one selected from the group of compounds consisting of ion-exchange layered silicate [B-4] are used.

・・・式（８）

・・・式（９）

・・・式（１０） (2-1) Component [B-1]
Specific examples of the aluminum oxy compound [B-1] include compounds represented by the following general formula (8), (9) or (10).

... Formula (8)

... Formula (9)

... Formula (10)

In each of the above general formulas, R ⁹¹ , R ¹⁰¹ and R ¹¹¹ represent a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. A plurality of R ⁹¹ , R ¹⁰¹ and R ¹¹¹ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (8) and (9) are also compounds called alumoxanes, and among these, methylalumoxane or methylisobutylalumoxane is preferable.
The above alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.

The compound represented by the general formula (10) is 10: 1 to 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (11). : 1 (molar ratio) reaction.
In general formulas (10) and (11), R ¹¹² and R ¹²¹ represent a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
R ¹²¹ ₂ B (OH) ₂ Formula (11)

(2-2) Component [B-2]
Component [B-2] is an ionic compound or a Lewis acid that can react with the transition metal compound (A) and can be converted to a cation.
Specifically, the ionic compound includes a cation such as a carbonium cation or an ammonium cation, and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron. And a complex with a cation.
Examples of Lewis acids that can convert the component (A) into cations include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a component (A) into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one.

(2-3) Component [B-3]
Examples of the solid acid fine particles [B-3] include solid acids such as silica, alumina, and silica-alumina.
In the present invention, the solid acid fine particles are not particularly limited in terms of their elemental composition and compound composition.

(2-4) Component [B-4]
Component [B-4] is an ion-exchange layered silicate. In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other and having exchangeable ions. Say. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can.
Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculite such as vermiculite, mica, mica, illite, sericite, sea green stone, attapulgite, sepiolite, palygorskite , Bentonite, pyrophyllite, talc, chlorite group.

The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite.
The kind of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.
Although the silicate used by this invention can be used as it is, without performing a process especially, it is preferable to give a chemical process. Here, the chemical treatment may be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Specific examples of the chemical treatment in the present invention include (a) acid treatment, (b) salt treatment, (c) alkali treatment, and (d) organic matter treatment described below.

(A) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, and Mg having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid. Acid Ru used for the treatment, may be two or more. The treatment conditions with the acid are not particularly limited. Usually, the acid concentration is 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of exchangeable layered silicates is eluted. The acid is generally used as an aqueous solution.

(B) Salt treatment In the present invention, 40% or more, preferably 60% or more, of the exchangeable Group 1 metal cation contained in the ion-exchangeable layered silicate before treatment with salts is described below. It is preferable to exchange ions with cations dissociated from the salts shown.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), And at least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O _7. It is a compound.

_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O ₄ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , Z rF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , _{HF (SO 4) 2, HFOCl} 2, HFF 4, HFCl 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, and the like _{VCl 4, VBr 3, Cr (} CH 3 COCHCOCH 3) 3 Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI _{3 , Mn (OOCCH 3) 2,} Mn (CH 3 COCHCOCH 3) 2, MnCO 3, Mn (NO 3) 2, MnO, _{n (ClO 4) 2, MnF} 2, MnCl 2, Fe (OOCCH 3) 2, Fe (CH 3 COCHCOCH 3) 3, FeCO 3, Fe (NO 3) 3, Fe (ClO 4) 3, FePO 4, FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O ₇ , Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) _2, NiSO _4, NiCl _2, etc. and _{NiBr 2, Zn (OOCCH 3)} 2, Zn (CH 3 COCHCOCH 3) 2, ZnC _{3, Zn (NO 3) 2} , Zn (ClO 4) 2, Zn 3 (PO 4) 2, ZnSO 4, ZnF 2, ZnCl 2, AlF 3, AlCl 3, AlBr 3, AlI 3, Al 2 (SO 4 ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.
Two or more salts may be used for the treatment. The treatment conditions with salts are not particularly limited. Usually, the salt concentration is 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of exchangeable layered silicates is eluted. The salts are generally used in an aqueous solution.

(C) Alkali treatment Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) ₂ .

(D) Organic matter treatment Examples of the organic matter used for the organic matter treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, and triphenylphosphonium.
Furthermore, examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the component (B).
The heat treatment method of the adsorbed layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the component (B) after removal is 3% by weight or less, preferably 0% by weight when the water content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. Is preferably 1% by weight or less.

As described above, in the present invention, as the component (B), an ion-exchange layered silicate having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment is particularly preferable. It is.
The ion-exchange layered silicate can be preferably treated with the component (D) described later before being used as a catalyst or as a catalyst. Although there is no restriction | limiting in the usage-amount of the component (D) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

The component (B) is preferably a spherical particle having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, or sorting may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization step. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

Among the above components (B), [B-4] ion-exchange layered silicate is particularly preferable.
In the catalyst for propylene polymerization according to the present invention, [B-1] an aluminum oxy compound, [B-2] an ionic compound capable of reacting with component (A) to convert component (A) into a cation, or Lewis The acid, [B-3] solid acid fine particles, or [B-4] ion-exchange layered silicate fine particles are each used alone as the component (B), and these four components may be appropriately combined, Can be used.

(3) Component C
Component (C) may be any carrier of inorganic compounds and organic compounds. Examples of the inorganic compound carrier include magnesium chloride, activated carbon, the aforementioned [B-3] solid acid fine particles, and [B-4] ion-exchange layered silicate. Alternatively, a mixture thereof may be used. [B-4] is particularly preferably used as the component (C). That is, when the component (B) is [B-4], [B-4] also serves as the component (C). Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated carbonization such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer of hydrogen. Alternatively, a mixture thereof may be used.
These fine particle carriers usually have an average particle diameter of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.

(4) Component (D)
An organoaluminum compound is used as necessary (ie, the optional component (D)). In the present invention, the following general formula:
An organoaluminum compound represented by AlR _q Z _3-q is preferred.
In this invention, it cannot be overemphasized that the compound represented by this formula can be used individually or in mixture of multiple types or in combination. In this formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q is a number greater than 0 and up to 3. R is preferably an alkyl group, and Z is a chlorine atom when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and a carbon number 1 to 3 when it is an amino group. Eight amino groups are preferred.

Specific examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-npropylaluminum, tri-nbutylaluminum, tri-ibutylaluminum, tri-nhexylaluminum, tri-noctylaluminum, tri-ndecyl. Examples include aluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, trialkylaluminum and dialkylaluminum hydride having q = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(5) Production Method of Solid Metallocene Catalyst The catalyst according to the present invention can be formed by bringing the above component (A) and component (B) into contact with each other simultaneously or continuously, or once or multiple times. . In addition, although a component (D) is a component used as needed and it does not need to be contained in the said catalyst component, it is preferable to use a component (D).
Further, when the component (A) is contacted with the components (B) and (C), the component (C) and the component (D) may be contacted simultaneously or continuously, or at one time or a plurality of times. Particularly, in [a1] or [a2] of component (A), when X ¹¹ and Y ¹¹ , or X ²¹ and Y ²¹ are other than a hydrocarbon group having 1 to 20 carbon atoms, for example, a halogen group, the component It is preferable to use (D).
In the catalyst preparation, the contact order of the components (A) to (D) is not particularly limited. Arbitrary combinations are possible as the contact order. Particularly preferable ones for each component are as follows.
When component (D) is used, component (A), component (B), (C), or component (A) before contacting component (A) with component (B), (C) ) And components (B) and (C) are contacted with components (C) and (D), or components (A) and (B) are contacted simultaneously with components (C) and (D). Alternatively, it is possible to contact the components (C) and (D) after contacting the components (A) with the components (B) and (C), but preferably the components (A) and (B) ) And (C) are brought into contact with any one of the components (C) and (D).
The contacting of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. After contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components (A), (B), (C) and (D) used in the present invention is arbitrary. For example, the amount of component (A) used relative to components (B) and (C) is preferably 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of components (B) and (C). Range.
The amount of component (D) relative to component (A) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ . .

Regarding the component (A) used in the present invention, when the component (a1) and the component (a2) coexist, the ratio of the molar amount of (a2) to the total molar amount of each component (a1) and (a2) 0.30 or more and 0.99 or less. By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity.
That is, from the component (a2), a low molecular weight terminal vinyl macromer is produced, and from the component (a1), a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the proportion of the component (a2), the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branching (amount, length, distribution) The melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled. In order to efficiently produce a propylene-based polymer with higher catalytic activity, 0.30 or more is necessary, preferably 0.40 or more, and more preferably 0.5 or more. Further, the upper limit is 0.99 or less, and in order to efficiently obtain the polymer of the present invention with high catalytic activity, it is preferably 0.95 or less, and more preferably 0.90 or less. .
Further, by using the component (a2) within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the hydrogen amount.
In the prepolymerization method of the present invention, when both (a1) and (a2) are used, there are cases in which each is used alone, but each has two components, but the reason is not clear at this time, but (a2) was used. In some cases, the effect of the present invention in improving the activity and improving the bulk density is great. Therefore, it is preferable to use (a2) for the prepolymerization of the present invention.

2. Production of Bulk Prepolymerization Catalyst In the present invention, the prepolymerization means that a metallocene catalyst and a small amount of an olefin monomer are polymerized in advance before the main polymerization in order to further improve the catalyst activity and particle properties. In the present invention, the term “bulk” (also referred to as a lump) refers to a state in which the monomer itself acts as a reaction medium in a state where an organic solvent or a diluent is substantially absent.

(2-1) Prepolymerized monomer The catalyst used in the present invention needs to be subjected to bulk prepolymerization treatment in advance in a liquefied state in order to improve particle properties and catalytic activity.
In addition to propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. can be used in combination. Is possible. Further, it is possible to coexist hydrogen as necessary. It is also possible to carry out bulk prepolymerization in multiple stages under different reaction conditions.

Of these, ethylene is preferably combined with propylene. Ethylene has the effect of reactivating active sites deactivated by irregular insertion of propylene, and has the effect of increasing the number of active sites in the catalyst by adding ethylene during prepolymerization. Therefore, in the method for producing a prepolymerization catalyst of the present invention, it is preferable to add 0.01 to 5.0 wt% of ethylene with respect to propylene. More preferably, it is 0.5-3.0 wt%, More preferably, it is 1.0-2.5 wt%.
As another effect, when ethylene is added in the main polymerization, the melting point decreases, so that fusion on the polymer surface is likely to occur, the powder properties deteriorate, and the bulk density (BD) decreases. It becomes a problem to do. By adding ethylene during the prepolymerization of the present invention, the powder properties can be improved without affecting the crystallinity of the product of the main polymerization.

(2-2) Pre-polymerization reactor The reactor for bulk pre-polymerization is not particularly limited in shape and structure, and a generally used tank with a stirrer, a tubular (loop) reactor, and the like can be mentioned.

(2-3) Prepolymerization temperature and pressure The bulk prepolymerization temperature is 0 to 70 ° C, preferably 20 to 70 ° C, and more preferably 30 to 70 ° C. Below this range, a special cooling facility may be required in production, or the reaction rate may be lowered and the activation reaction may not proceed. On the other hand, if it exceeds, the prepolymerization rate is too high, and the prepolymerized polymer melts or the particle properties deteriorate. Further, there may be a negative effect that the active site is deactivated due to a side reaction.
Note that the prepolymerization temperature may be changed over time during the prepolymerization step. The temperature change with time here may be either temperature rise or temperature drop. Moreover, you may perform temperature increase or temperature decrease in multiple times in the same prepolymerization process. Furthermore, you may combine temperature rising and temperature falling in the same prepolymerization process.

Preferably, a prepolymerization step of raising the temperature with time is taken. At this time, the initial temperature is preferably 50 ° C. or less, more preferably 40 ° C. or less, and more preferably 30 ° C. or less. Any temperature increase rate can be used in the temperature increasing step, but preferably a relatively slow temperature increasing rate is preferable for obtaining a higher bulk density, and a temperature increasing rate of 3.0 ° C./1 min or less is preferable. More preferably, the temperature is 2.0 ° C./min or less, and more preferably the temperature is increased at a rate of temperature increase of 1.0 ° C./min or less.
As shown in the examples, one preferred form includes a step of starting prepolymerization at 30 ° C., raising the temperature at 1.0 ° C./min, and prepolymerizing to 70 ° C. over 40 minutes.

  Regarding the pressure, the saturation vapor pressure at that temperature is uniquely determined by the limitation of the bulk prepolymerization temperature. In the case of a full liquid state such as a tube reactor, the saturated vapor pressure is 5 MPa, preferably the saturated vapor pressure is 4 MPa due to mechanical compression.

(2-4) Prepolymerization time The prepolymerization time is related to the speed at which the prepolymerized particles grow. When the prepolymerization is carried out quickly in a short time, the prepolymerized particles grow rapidly, resulting in nonuniform polymerization on the particle surface and inside, thereby deteriorating the powder properties. As a result, the powder properties in the case of the main polymerization are deteriorated, that is, the bulk density is lowered and the productivity of the polymer is deteriorated. Therefore, the prepolymerization of the present invention is preferably carried out slowly at a prepolymerization rate of 30 minutes or more. More preferably, it is 40 minutes or more, More preferably, it is 60 minutes or more. Regarding the upper limit, if the prepolymerization time is too long, the productivity itself is impaired, so 180 minutes or less is preferable, more preferably 150 minutes or less, and still more preferably 120 minutes or less. However, when no prepolymerization is performed, the prepolymerization time is defined as 0 minutes.

(2-5) Prepolymerization ratio In the present invention, the prepolymerization ratio is a polymer imparted by prepolymerization to 1 part by weight of a metallocene catalyst composed of (A), (B), (C) and any (D). It is the ratio of weight. That is, a value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst. In order to exhibit the effect of the present invention, the bulk prepolymerization ratio is preferably 0.01 or more, more preferably 0.1 or more, and further preferably 1 or more. Below this range, the catalytic activity and particle properties are not improved. Furthermore, when considering the catalytic activity, 50 or more is preferable, more preferably 200 or more, and still more preferably 1,000 or more.
In addition, the upper limit of the bulk prepolymerization ratio is preferably 8,000 or less, more preferably 4,000 or less, and still more preferably 2,000 or less, in order to exhibit the effects of the present invention. However, considering the productivity of the catalyst and the productivity of the main polymerization, the prepolymerization ratio is preferably 200 or less from the viewpoint of balance, more preferably 150 or less, and further preferably 100 or less. Good.
Here, from the viewpoint of improving the catalyst activity and particle properties, the bulk prepolymerization ratio is preferably 200 or more. From the viewpoint of improving the productivity of the catalyst and the productivity of the main polymerization, the bulk prepolymerization ratio is It is preferable that it is 200 or less. At first glance, the magnification requirements are contradictory, but the bulk prepolymerization magnification may be adjusted and set according to each viewpoint, that is, each purpose.

(2-6) Prepolymerization Catalyst Concentration The concentration of the charged solid catalyst during bulk prepolymerization is not particularly limited, but is preferably 0.001 to 50 g / L per unit volume of liquefied propylene.
As described above, when the bulk prepolymerization ratio is preferably 200 or more, or 200 or less is preferable, it can be considered according to each purpose, but when the prepolymerization ratio is 200 or less, The concentration of the charged solid catalyst during bulk prepolymerization is preferably 0.05 to 50 g / L, more preferably 0.1 to 25 g / L, and particularly preferably 1 to 10 g / L per unit volume of liquefied propylene. . When the concentration is below this range, the monomer conversion efficiency is lowered, leading to a decrease in productivity. On the other hand, even if the temperature exceeds the range, uniform stirring and temperature control become difficult, and stable operation is hindered.
When the prepolymerization ratio is 200 or more, the concentration of the charged solid catalyst during bulk prepolymerization is preferably 0.001 to 0.05 g / L, more preferably 0.003 to 0, per unit volume of liquefied propylene. 0.045 g / L, particularly preferably 0.005 to 0.040 g / L. The reason is the same as when the prepolymerization ratio is 200 or less, but the bulk prepolymerization ratio is different, so that the optimum bulk prepolymerization concentration is different.
Thereafter, in the bulk prepolymerization, the concentration of the bulk prepolymerization catalyst at the end of the prepolymerization (the amount of the bulk prepolymerization catalyst generated with respect to the amount of liquefied propylene initially charged) is 10 g / L to 300 g / L regardless of the prepolymerization ratio. It is preferable to set L. More preferably, it is 20 g / L to 270 g / L, and more preferably 30 g / L to 250 g / L. When the concentration is below this range, the monomer conversion efficiency is lowered, leading to a decrease in productivity. On the other hand, even if the temperature exceeds the range, uniform stirring and temperature control become difficult, and stable operation is hindered.

(2-7) Prepolymerization by any other method Before and after bulk prepolymerization treatment in liquefied propylene, prepolymerization by other methods can be arbitrarily performed. In that case, it is preferable to subject to slurry prepolymerization treatment before bulk prepolymerization.
As the polymerization solvent for the slurry prepolymerization, a hydrocarbon solvent such as hexane, heptane, pentane, and cyclohexane is used. The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use it, and it is particularly preferable to use propylene. At that time, hydrogen can be allowed to coexist as necessary, and two or more olefins can be allowed to coexist.

  The preliminary or additional prepolymerization may employ any method such as slurry or gas phase, but the prepolymerization temperature is not particularly limited when the slurry prepolymerization is performed in a liquid such as an organic solvent. Usually, it is 0-100 degreeC, Preferably it is 0-80 degreeC, More preferably, it is 0-60 degreeC. The slurry prepolymerization pressure is not particularly limited, but is in the range of normal pressure to 0.5 MPa. The slurry prepolymerization time is not particularly limited, but is in the range of 5 minutes to 5 hours, preferably 5 minutes to 4 hours, and more preferably 5 minutes to 3 hours. The concentration of the solid catalyst during slurry prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst. Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

  In addition, the prepolymerization ratio obtained in advance or by another method is summed with the bulk prepolymerization ratio, and is 0.01 to 8,000 parts by weight (prepolymerization ratio 0.01 to 8, 8 parts per 1 part by weight of the metallocene catalyst. 000, the same applies hereinafter), preferably 0.1 to 4,000 parts by weight, more preferably 1 to 2,000 parts by weight. Below this range, the catalyst is not activated and does not contribute to the improvement of the catalyst activity, but also causes problems such as generation of fine powder during the main polymerization. On the other hand, even if it exceeds the above, since the activation of the catalyst is already sufficient, further activity improvement cannot be expected. Rather, it leads to lower production efficiency.

The ratio of the bulk prepolymerization ratio and the prepolymerization ratio by other methods is such that the bulk prepolymerization ratio is 100 to 50% by weight, preferably 99.9 to 75% by weight, more preferably 99.8 to the total amount of the prepolymerized polymer. 90% by weight, and the prepolymerization ratio according to another method is in the range of 0 to 50% by weight, preferably 0.1 to 25% by weight, more preferably 0.2 to 10% by weight, based on the total amount of the prepolymerized polymer. If the bulk prepolymerization ratio is below this range, the catalyst cannot be fully activated.
After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.

3. Use of Preliminary Polymerization Catalyst As a method for producing a propylene-based polymer using the metallocene prepolymerization catalyst of the present invention, any method can be adopted as long as the catalyst component and the monomer come into efficient contact. As a specific polymerization form, it is applied to slurry polymerization using a hydrocarbon solvent, bulk polymerization in a liquefied monomer, or gas phase polymerization using substantially no solvent.
In the case of slurry polymerization, a hydrocarbon solvent such as hexane, heptane, pentane, or cyclohexane is used as the polymerization solvent.
The polymerization reaction is applied to continuous polymerization, semi-continuous polymerization, and batch polymerization. Furthermore, a multistage polymerization method in which the polymerization reaction is performed in two or more stages having different reaction conditions is also possible.
As conditions at the time of superposition | polymerization, superposition | polymerization temperature is 30-150 degreeC normally, Preferably it is 50-100 degreeC. The polymerization pressure is normal pressure to 5 MPa, preferably normal pressure to 4 MPa.
In the main polymerization of the present invention, hydrogen can be used for the purpose of adjusting the molecular weight of the polymer. Moreover, as a monomer to be used, not only propylene alone but also a monomer copolymerizable with propylene, such as ethylene, 1-butene, 1-hexene and the like can be used.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples, and the examples are not limited to the rationality, significance, usefulness, and prior art of the configuration of the present invention. It demonstrates the excellence of.

The physical properties of the polymer obtained by the present invention were measured by the following method.
(1) Melt flow rate (MFR): determined in accordance with JIS K7210 (230 ° C., 2.16 kg load).
(2) BD measuring method: The bulk density was measured according to JIS K-6721.
The catalyst production methods and propylene polymerization methods used in the Examples and Comparative Examples are as follows.

[ Reference Example 1]
(1) Component (A)
Transition metal compound (a2): Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (1 -1) Synthesis of 4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, add 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME), add a solution of 90 g (0.28 mol) of cesium carbonate and 100 ml of water, and add 4-bromoindene. 13 g (67 mmol) and tetrakistriphenylphosphinopalladium 5 g (4 mmol) were sequentially added, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(1-2) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene, 7.2 ml of distilled water and 200 ml of DMSO were added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. . The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(1-3) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, 6.7 g (82 ml 1 mol) of 2-methylfuran and 100 ml of DME were added and cooled to -70 ° C in a dry ice-methanol bath. To this, 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
The reaction solution was hydrolyzed with 50 ml of distilled water, and then a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 g (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in that order at 80 ° C. The mixture was heated and reacted for 3 hours while removing low-boiling components. After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene as a colorless liquid ( Yield 99%).

(1-4) Synthesis of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane:
To a 500 ml glass reaction vessel, 9.1 g (29 mmol) of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene and 200 ml of THF are added, and -70 in a dry ice-methanol bath. Cooled to ° C. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column, and dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane was diluted lightly. 8.6 g (88% yield) of a yellow solid was obtained.

Synthesis of (1-5) dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride:
To a 500 ml glass reaction vessel, 8.6 g (13 mmol) of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane and 300 ml of diethyl ether were added and dried. It cooled to -70 degreeC with the ice-methanol bath. Thereto was added dropwise 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure and recrystallized from dichloromethane-hexane to obtain a racemic dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride. As a yellow crystal, 7.6 g (yield 65%) was obtained.
The identified value by ^{1 H-NMR} of the obtained racemates are described below. ¹ H-NMR (C ₆ D ₆ ) identification result Racemate: δ 0.95 (s, 6H), δ 1.10 (d, 12H), δ 2.08 (s, 6H), δ 2.67 (m, 2H) , Δ 5.80 (d, 2H), δ 6.37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 ( s, 2H), δ 7.30 (d, 2H), δ 7.83 (d, 4H)

(2) Preparation of Component [B-4]: Chemical Treatment of Ion Exchangeable Layered Silicate 96% Sulfuric Acid (1,044 g) was added to 3,456 g of distilled water in a separable flask and then montmorillonite ( 600 g of Benclay SL manufactured by Mizusawa Chemical Co., Ltd. (average particle size 19 μm) was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2,400 g of distilled water and filtered to obtain 1,230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1,800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the whole amount of the cake-like solid was added, and further 522 g of distilled water was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1,980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1,150 g of a cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].
Then, before using as a catalyst component, 200 degreeC vacuum drying was implemented for 5 hours, and it was used by the following catalyst preparation.

(3) Preparation of solid catalyst All the following operations were performed under inert gas. The solvent used was dehydrated and deoxygenated.
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite prepared in Example 1 was added, and 66 mL of heptane was added to form a slurry. After stirring for 1 hour, the mixture was washed with heptane (residual liquid ratio up to 1/100), and heptane was added so that the total volume became 100 mL.
In another flask (volume 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (2-methyl-5-furyl) -4- (4-i-propyl) was added to toluene (60 mL). Phenyl) indenyl}] hafnium (0.15 mmol) was added to form a slurry solution.
Triisobutylaluminum (0.6 mmol: 1.7 mL of 144 mg / mL heptane solution) is added to the 1 L flask containing the ion-exchange layered silicate, and then the above slurry solution is added and stirred for 60 minutes at room temperature. And reacted. Thereafter, 340 mL of heptane was added.

(4) Slurry prepolymerization After stabilizing the heptane slurry containing 10 g of the solid catalyst in an autoclave at 40 ° C, propylene was fed at a rate of 10 g / hr, and prepolymerization was performed for 2 hours while maintaining 40 ° C. Thereafter, propylene feed was stopped, and residual polymerization was carried out at 40 ° C. for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a heptane solution having a concentration of 144 mg / mL) was added to the portion remaining by the decantation, and the mixture was stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 12.7 g of a dry slurry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the prepolymerized polymer amount by the solid catalyst amount) was 0.27.

(5) Bulk prepolymerization Subsequently, heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 20 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, and after introducing 750 g of liquid propylene, the temperature was raised to 40 ° C. After the temperature was stabilized, 3 g of the prepared catalyst (excluding the amount of prepolymerized polymer) was injected with argon to start bulk prepolymerization. (Concentration of charged solid catalyst: 2 g / L) After 60 minutes, the remaining propylene monomer was purged to complete the reaction. The obtained solid was dried at 90 ° C. for 1 hour to recover 288 g of a dry bulk prepolymerized catalyst. By this operation, a bulk prepolymerized catalyst containing 96 g of polypropylene per gram of catalyst was obtained (that is, the prepolymerization ratio was 96). The results are shown in Table 1. (Bulk prepolymerization catalyst concentration at the end of prepolymerization 194 g / L)

(6) Propylene main polymerization using prepolymerization catalyst Further, heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and the temperature was raised to 70 ° C. After the temperature was stabilized, 200 mg (excluding the amount of prepolymerized polymer) of the prepared bulk prepolymerization catalyst was injected with argon, and bulk main polymerization was started. After 1 hour, 10 mL of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 177 g of a propylene polymer was recovered. The activity per solid catalyst was 885 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.51 g / mL and an MFR of 40 g / 10 min. The results are shown in Table 2.

[ Reference Example 2]
(1) Component (A)
Transition Metal Compound (a1): Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium rac-dichloro [1,1′-dimethyl Synthesis of silylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium was carried out in the same manner as in Example 7 of JP-A-11-240909.

(2) Component (A)
Transition metal compound (a2): synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium rac- Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium was carried out in the same manner as in Reference Example 1.

(3) Preparation of component [B-4]: Chemical treatment of ion-exchangeable layered silicate Manufactured by the same method as described in paragraph 0118.

(4) Preparation of solid catalyst All the following operations were performed under inert gas. The solvent used was dehydrated and deoxygenated.
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite prepared above was added, and 66 mL of heptane was added to form a slurry, to which triisobutylaluminum (25 mmol: 34 mL of a heptane solution having a concentration of 144 mg / mL) was added. After stirring for 1 hour, the mixture was washed with heptane (residual liquid ratio 1/100), and heptane was added so that the total volume became 100 mL.
Thereafter, triisobutylaluminum (0.6 mmol: 0.85 mL of a 140 mg / mL concentration heptane solution) was added, and rac-dichloro [1,1′-dimethyl, which had been adjusted to another flask (volume: 200 mL), was added. A toluene solution (29 mL) of silylenebis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (0.105 mmol) was added, and another flask ( Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (0.075 mmol) in toluene (12. 9 mL) solution was added to make a slurry, and the mixture was stirred at room temperature for 45 minutes to be reacted. Thereafter, 357 mL of heptane was added.

(5) Preliminary polymerization of slurry After stabilizing a heptane slurry containing 10 g of solid catalyst in an autoclave at 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed in heptane while maintaining 40 ° C. for 2 hours. . Thereafter, propylene feed was stopped, and residual polymerization was performed at 50 ° C. for 0.5 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a heptane solution having a concentration of 144 mg / mL) was added to the portion remaining by the decantation, and the mixture was stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 31.1 g of a dry slurry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.11.

(6) Bulk prepolymerization Subsequently, heated nitrogen was passed through a 3 L autoclave to sufficiently dry it, and after cooling, the inside of the tank was replaced with propylene. After cooling to 20 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) and 20 mL of hydrogen were added, 750 g of liquid propylene was introduced, and then the temperature was raised to 20 ° C. After the temperature was stabilized, 5 g (excluding the amount of prepolymerized polymer) of the prepared catalyst was injected with argon to start bulk prepolymerization. (Concentration of charged solid catalyst: 3.3 g / L) After 30 minutes, the remaining propylene monomer was purged to complete the reaction. The obtained solid was dried at 90 ° C. for 1 hour to recover 360 g of a dry bulk prepolymerized catalyst. By this operation, a bulk prepolymerized catalyst containing 72 g of polypropylene per 1 g of catalyst was obtained (that is, the prepolymerization ratio was 72). The results are shown in Table 1. (Bulk prepolymerization catalyst concentration at the end of 240 g / L)

(7) Propylene main polymerization using prepolymerization catalyst Further, heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) and 20 mL of hydrogen were added, 750 g of liquid propylene was introduced, and the temperature was raised to 70 ° C. After the temperature was stabilized, 50 mg (excluding the amount of prepolymerized polymer) of the prepared bulk prepolymerization catalyst was injected with argon, and bulk main polymerization was started. After 1 hour, 10 mL of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 300 g of the propylene polymer was recovered. The activity per solid catalyst was 6,000 g / g-solid catalyst, and the obtained polymer had a bulk density (BD) of 0.45 g / mL and an MFR of 1.0 g / 10 min. The results are shown in Table 2.

[Example 3]
In the preparation of the solid catalyst, rac-dichloro [1,1′-dimethylsilylenebis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium and rac-dichloro [ The catalyst was synthesized in the same procedure as in Reference Example 1 except that the amount of 1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium was changed. Furthermore, slurry prepolymerization was also carried out in the same procedure. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.82.

(1) Bulk prepolymerization Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 20 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and the temperature was raised to 30 ° C. After the temperature was stabilized, 12.0 × 10 ⁻² NL of hydrogen was charged, 50 mg (excluding the amount of prepolymerized polymer) of the prepared catalyst was injected with argon, and bulk prepolymerization was started. (Concentration of charged solid catalyst: 0.033 g / L) The polymerization time was 40 minutes, and the internal temperature was gradually raised to 70 ° C. over 40 minutes. By this operation, a bulk prepolymerized catalyst containing 2,400 g of polypropylene per gram of catalyst was obtained (that is, the prepolymerization ratio was 2,400). Table 1 shows the results.

(2) Propylene main polymerization using prepolymerization catalyst After the previous bulk prepolymerization, the temperature was kept at 70 ° C., and the main polymerization was started. After 2 hours of polymerization, 10 mL of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 375 g of propylene polymer was recovered. The activity per solid catalyst was 7,500 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.45 g / mL and an MFR of 1.3 g / 10 min. The results are shown in Table 2.

[Example 4]
(1) Bulk prepolymerization Bulk prepolymerization was performed using the same catalyst as in Example 3. Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 20 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and the temperature was raised to 30 ° C. After the temperature was stabilized, 13.0 × 10 ⁻² NL of hydrogen and 9.5 g of ethylene were charged, 25 mg of catalyst (excluding the amount of prepolymerized polymer) was injected with argon, and bulk prepolymerization was started. . (Concentration of charged solid catalyst: 0.017 g / L) The polymerization time was 40 minutes, and the internal temperature was gradually raised to 70 ° C. over 40 minutes. By this operation, a bulk prepolymerized catalyst containing 3,600 g of polypropylene per gram of catalyst was obtained (that is, the prepolymerization ratio was 3,600). The results are shown in Table 1. (Bulk prepolymerization catalyst concentration at end 60 g / L)

(2) Propylene main polymerization using prepolymerization catalyst After the previous bulk prepolymerization, the temperature was kept at 70 ° C., and the main polymerization was started. After 2 hours of polymerization, 10 mL of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 325 g of propylene polymer was recovered. The activity per solid catalyst was 13,000 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.45 g / mL, an MFR of 11.0 g / 10 min, and a C2 content = 1.0 wt%. The results are shown in Table 2.

[Example 5]
(1) Bulk prepolymerization Bulk prepolymerization was performed using the same catalyst as in Example 3. Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 20 ° C. or lower, 2.86 m (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and the temperature was raised to 30 ° C. After the temperature was stabilized, 10.0 × 10 ⁻² NL of hydrogen and 40 g of ethylene were charged, 10 mg of the catalyst (excluding the amount of prepolymerized polymer) was injected with argon, and bulk prepolymerization was started. (Concentration of charged solid catalyst: 0.007 g / L) The polymerization time was 40 minutes, and the internal temperature was gradually raised to 65 ° C. over 40 minutes. By this operation, a bulk prepolymerized catalyst containing 6,000 g of polypropylene per gram of catalyst was obtained (that is, the prepolymerization ratio was 6,000). The results are shown in Table 1. (Bulk prepolymerization catalyst concentration at the end of prepolymerization 40 g / L)

(2) Propylene main polymerization using prepolymerization catalyst After the previous bulk prepolymerization, the temperature was kept at 65 ° C. and the main polymerization was started. After 2 hours of polymerization, 10 mL of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 250 g of propylene polymer was recovered. The activity per solid catalyst was 25,000 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.45 g / mL, MFR of 7.0 g / 10 min, and C2 content = 3.0 wt%. The results are shown in Table 2.

[Comparative Example 1]
The same procedure as in Reference Example 1 was performed except that bulk prepolymerization was not performed. The above results are shown in Tables 1 and 2.
[Comparative Example 2]
The same procedure as in Reference Example 2 was performed except that bulk prepolymerization was not performed. The above results are shown in Tables 1 and 2.

[Comparative Example 3]
Bulk prepolymerization was not performed using the same catalyst as in Example 3, but only this propylene polymerization was performed.
(1) Propylene polymerization Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, and then hydrogen was charged at 2.0 × 10 ⁻² NL. . Thereafter, the temperature was raised to 70 ° C. and the temperature was stabilized, and then 100 mg (excluding the amount of the prepolymerized polymer) of the prepared prepolymerized catalyst was injected with argon and bulk main polymerization was started. After 2 hours, 10 mL of ethanol was added to stop the polymerization, purge the remaining propylene monomer, and collect 195 g of propylene polymer. The activity per solid catalyst was 3,900 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.44 g / mL and an MFR of 1.3 g / 10 min. The above results are shown in Tables 1 and 2.

[Comparative Example 4]
Bulk prepolymerization was not performed using the same catalyst as in Example 3, but only this propylene polymerization was performed.
(1) Propylene polymerization Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or less, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, 6.0 × 10 ⁻² NL of hydrogen, 14 g of ethylene Was loaded. Thereafter, the temperature was raised to 70 ° C. and the temperature was stabilized, and then 100 mg (excluding the amount of the prepolymerized polymer) of the prepared prepolymerized catalyst was injected with argon and bulk main polymerization was started. After 2 hours, 10 mL of ethanol was added to stop the polymerization, purge the remaining propylene monomer, and collect 195 g of propylene polymer. The activity per solid catalyst was 6,800 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.44 g / mL, an MFR of 11.0 g / 10 min, and a C2 content = 1.0 wt%. The above results are shown in Tables 1 and 2.

[Comparative Example 5]
Bulk prepolymerization was not performed using the same catalyst as in Example 3, but only this propylene polymerization was performed.
(1) Propylene polymerization Heated nitrogen was passed through a 3 L autoclave and dried sufficiently. After cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, 750 g of liquid propylene was introduced, hydrogen 4.0 × 10 ⁻² NL, ethylene 26 .5 g was charged. Thereafter, the temperature was raised to 65 ° C. and the temperature was stabilized, and then 20 mg (excluding the amount of the prepolymerized polymer) of the prepared prepolymerized catalyst was injected with argon to start bulk main polymerization. After 2 hours, 10 mL of ethanol was added to stop the polymerization, purge the remaining propylene monomer, and collect 200 g of the propylene polymer. The activity per solid catalyst was 10,000 g / g-solid catalyst. The obtained polymer had a bulk density (BD) of 0.43 g / mL, MFR of 7.0 g / 10 min, and C2 content = 3.0 wt%. The above results are shown in Tables 1 and 2.

As a result of the above, as apparent from Tables 1 and 2 above, in Examples 3 to 5 of the method for producing the metallocene prepolymerization catalyst of the present invention and the method for producing propylene-based polymer using the same, bulk prepolymerization of the present application was performed. Since the conditions are satisfied, the catalytic activity of the resulting metallocene catalyst is improved and the catalyst cost can be greatly reduced as compared with the corresponding comparative examples in Table 1. Furthermore, the polymer bulk density (BD) was also improved and the powder properties were improved.
On the other hand, in Comparative Examples 1 to 5 that did not satisfy the requirements of the present application, the activation of the polymerization catalyst was insufficient, resulting in a low catalytic activity, and the particle properties were somewhat poor and inferior to those of the present example.
From the above results, the rationality, significance and usefulness of the requirements (specific matters of the invention) of the configuration of the invention of the present application and the superiority over the prior art are clarified.

As described above, the method for producing a metallocene prepolymerization catalyst of the present invention has excellent catalytic activity in the polymerization of propylene using a metallocene catalyst, and particle properties such as bulk density are also improved. It is industrially suitable as a production method. Further, since the catalyst cost is reduced and a high-quality polypropylene polymer can be produced, the industrial applicability of the propylene polymer production method is very large.

Claims (10)

Represented by the following general formula (A), as the (B), (C) and any supported metallocene catalyst comprising (D), in liquefied propylene 0 to 70 ° C., the monomer itself reaction medium, characterized by bulk prepolymerization preliminary polymerization rate 200 8,000 the method of metallocene prepolymerized catalyst.
Component (A): Two different binary complexes composed of transition metal compounds of Group 4 of the periodic table represented by general formula (a1)

Formula (a1)
[In General Formula (a1), E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. , X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. A hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]
Component (B): Aluminum oxy compound [B-1], ionic compound or Lewis acid [B-2] that can be converted to a cation by reacting with component (A), solid acid fine particles [B-3] And at least one selected from the group consisting of ion-exchangeable layered silicates [B-4] Component (C): Support Component (D): Organoaluminum compound The method for producing a metallocene prepolymerization catalyst according to claim 1, wherein the prepolymerization ratio is 1,000 to 8,000. One of component (A) consists of a complex shown by the following general formula (a2), The manufacturing method of the metallocene prepolymerization catalyst of Claim 1 or 2 characterized by the above-mentioned.
However, the complex represented by the following general formula (a2) has a ratio in the component (A) of 0.30 or more and 0.99 or less.

Formula (a2)
[In General Formula (a2), R ²¹ and R ²² each independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. R ²³ and R ²⁴ each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, having 6 to 16 carbon atoms It represents an aryl group or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ²¹ represents zirconium or hafnium. X ²¹ and Y ²¹ each independently represent the same substituent as X ¹¹ and Y ^{11 in} the general formula (a1). ] The metallocene prepolymerization according to any one of claims 1 to 3, wherein the component (B) is an ion-exchange layered silicate [B-4], and the component (B) also serves as the component (C). A method for producing a catalyst. The method for producing a metallocene prepolymerization catalyst according to any one of claims 1 to 4, wherein hydrogen is allowed to coexist in liquefied propylene in bulk prepolymerization. The method for producing a prepolymerization catalyst according to any one of claims 1 to 5, wherein the prepolymerization time is 30 minutes or more in bulk prepolymerization. The method for producing a prepolymerized catalyst according to any one of claims 1 to 6, wherein ethylene is added in a range of 0.01 to 5.0 wt% with respect to propylene in addition to liquefied propylene in bulk prepolymerization. . The metallocene according to any one of claims 1 to 7, wherein at least one of the components (A) is a racemate of a transition metal compound of Group 4 of the periodic table represented by the general formula (a1). A method for producing a prepolymerized catalyst. In the bulk prepolymerization, the concentration of the bulk prepolymerization catalyst at the end of the prepolymerization is in the range of 10 to 300 g / L with respect to the amount of liquefied propylene charged in the initial stage. The manufacturing method of the metallocene prepolymerization catalyst as described in 1 above. A method for producing a propylene-based polymer, wherein bulk main polymerization is carried out using a prepolymerized catalyst produced by the method for producing a metallocene prepolymerized catalyst according to claim 1.