JP2015042617A - Metallocene compound and olefin polymer production method with polymerization catalyst using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst capable of producing an ethylenic copolymer having a sufficiently high molecular mass with industrially advantageous polymerization temperature and polymerization conditions in polymerizing an olefin.SOLUTION: A metallocene compound is represented by the general formula in the figure. [In the formula, M is Hf or the like; Q is a carbon atom or the like; Xand Xare each a C1-10 alkyl group or the like; and at least one of Rand Ris not a hydrogen atom.]

Description

  The present invention relates to a novel metallocene compound and a method for producing an olefin polymer using a polymerization catalyst using the same, and more particularly, an olefin having excellent copolymerizability in olefin copolymerization and capable of producing a high molecular weight olefin polymer. The present invention relates to a polymerization catalyst and an olefin polymerization method using the same.

  Olefin copolymers represented by ethylene / α-olefin copolymers or propylene / α-olefin copolymers are excellent in moldability and mechanical properties, and have a wide range of physical properties from hard to soft. The coalescence is produced economically, and its uses range from industrial use to daily life materials such as films and sheets, fibers and nonwoven fabrics, various containers and molded products, and modifiers.

  In general, an olefin copolymer obtained by copolymerizing a comonomer such as 1-butene or 1-hexene is more flexible, low temperature impact resistance, and environmental stress crack resistance than ethylene homopolymer and propylene homopolymer. It is known that performance such as transparency is excellent. In order to further improve these performances, it is necessary to increase the comonomer content in the copolymer while maintaining the high molecular weight. In addition, it is known that when a complex catalyst typified by a metallocene catalyst is used, the distribution of the comonomer introduced into the copolymer becomes uniform, and the above-mentioned performances are further improved.

Therefore, when producing ethylene and propylene copolymers having these performances, a high molecular weight olefin copolymer can be produced in a temperature range of 50 to 300 ° C. which is efficient in an industrial process, and in terms of process load. Therefore, a complex catalyst excellent in copolymerizability, which can produce a copolymer having a high comonomer content even at a low comonomer concentration, is desired.
However, when olefin copolymerization is carried out using a complex catalyst typified by a metallocene catalyst, the molecular weight of the resulting polymer generally increases as the polymerization temperature increases or the comonomer content in the resulting copolymer increases. There has been a report of a drawback that it decreases (see, for example, Non-Patent Document 1).

  Therefore, when producing an olefin polymer having these performances, a metallocene catalyst that is excellent in copolymerization in a temperature range of 50 to 300 ° C. that is efficient in an industrial process and that can produce a high molecular weight olefin copolymer is provided. It is desired.

By the way, a crosslinked bisindenyl complex having a phenyl group at the 4-position of an indenyl ring is known as a metallocene having excellent copolymerizability and capable of producing a high molecular weight olefin polymer. In particular, it has been reported that introduction of a methyl group substituent at the 2-position of the indenyl ring is effective in improving the molecular weight (Non-Patent Documents 2 and 3). The search for the 2-position substituent of the bridged bisindenyl complex having a phenyl group is continued.
Non-Patent Document 4 reports that a complex having an iPr group at the 2-position can produce a higher molecular weight polyethylene than a complex having an Me-group at the 2-position substituent in ethylene polymerization under high pressure conditions. Yes. Patent Documents 1 and 2 include a complex having a β-position branched alkyl substituent at the 2-position, Patent Document 3 includes a complex having a heteroaromatic ring substituent at the 2-position, and Patent Documents 4-7 include two bisindenyl rings. It has been reported that complexes having different 2-position substituents can produce high-molecular-weight olefin polymers and olefin copolymers, respectively.

However, studies by the present inventors have revealed that when these catalysts are polymerized at a high temperature that is preferable from the viewpoint of production efficiency, the molecular weight of the resulting polymer is insufficient.
In addition, as the 2-position substituent has a complex structure, when these complexes are produced on a large scale industrially necessary for organic synthesis, a complicated synthesis route or a multi-step synthesis route is required. This causes a problem that the cost of manufacturing the complex increases. Therefore, it is desired to develop a new complex that exhibits performance superior to that of the conventional catalyst and has a simpler complex structure than that of the conventional catalyst and can be easily synthesized.

  Under such circumstances, a metallocene compound, which is capable of producing a high-molecular-weight olefin copolymer while having excellent copolymerizability at an industrially advantageous polymerization temperature and polymerization conditions, and further, it is easy to synthesize a complex. There has been a strong demand for a method for producing an olefin polymer using a metallocene catalyst using a catalyst.

Special table 2011-500800 gazette Special table 2012-513463 gazette JP 2002-194016 A Japanese Patent No. 4901043 Japanese Patent No. 4416507 Japanese Patent No. 4288658 JP 2004-352707 A

Macromol. Chem. Phys. 1996, 197, 3091-3097. Organometallics 1994, 13, 954-963. Macromol. Chem. Phys. 2005, 206, 1675-1683. Macromol. Chem. Phys. 2005, 206, 1043-1056.

  In view of the problems of the background art, the problem to be solved by the present invention is an industrially advantageous polymerization temperature and polymerization conditions when polymerizing olefins such as ethylene, while having excellent copolymerizability, An object of the present invention is to provide a catalyst capable of producing an olefin polymer having a sufficiently high molecular weight, particularly an ethylene copolymer, and a method for producing an olefin polymer using the catalyst.

  In order to solve the above-described problems, the present inventors have achieved excellent copolymerizability under industrially advantageous conditions by a technical technique based on the improvement in a metallocene catalyst as a polymerization catalyst for an olefin copolymer. In order to obtain an olefin-based copolymer having a sufficiently high molecular weight, an experimental search was conducted from various viewpoints. In the process, an olefin polymer containing a metallocene compound having a specific structure was used. By using a catalyst, when polymerizing olefins such as ethylene, it is possible to produce olefin polymers with sufficiently high molecular weights while exhibiting excellent copolymerization at industrially advantageous polymerization temperatures and polymerization conditions. As a result, the present invention has been completed.

  That is, as a technical technique for solving the above problems, the present inventors have a hydrogen atom as a substituent at the 2-position of the indenyl ring, which is a novel metallocene compound having a specific substituent at a specific position. And a metallocene having a bridged bisindenyl skeleton having an aryl group (phenyl group skeleton which may have a substituent) at the 4-position of the indenyl ring and further having a substituent other than a hydrogen atom at the 5-position of the indenyl ring. It has been found that compounds can solve the above problems.

  Thus, the catalyst component for olefin polymerization including the metallocene compound constituting the basic structure of the present invention uses a novel specific transition metal compound, and the complex has a catalyst structure in the metallocene catalyst due to the unique arrangement of substituents in the indenyl ring. Is characterized by the chemical, steric and electronic environment structure of this ligand, thereby providing a sufficiently high molecular weight while exhibiting excellent copolymerization under industrially advantageous conditions. The olefin copolymer which has can be manufactured. In addition, the metallocene complex of the present invention has a feature that it can be synthesized relatively easily by a simple synthesis route as compared with the conventional metallocene complex, as will be apparent from the synthesis route described later. .

  The catalyst component for olefin polymerization containing the metallocene compound forms the basic invention of the present invention, and consists of a novel transition metal compound having a chemical structure represented by the following general formula [I]. In combination with a cocatalyst or the like, an olefin polymerization catalyst is formed.

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon number 6 to 20 aryl groups), provided that at least one of R ⁴ and R ¹⁴ is other than a hydrogen atom, and the adjacent groups of R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ together with the atoms connecting them. One or more aromatic rings or Or to form an aliphatic ring, or ^{R 4} and ^R 5, ^{R 4} and ^{R 9, R 14} and ^{R 15} or ^{R 14} and ^{R 19} is one together with the atoms connecting them aromatic ring or aliphatic May form a family ring;
Q is a carbon atom, a silicon atom or a germanium atom, n is a natural number of 1 to 3,
R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Aryl group, C6-C10 fluoroaryl group, C6-C10 aryloxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C7-C40 alkyl An aryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ may be combined with atoms connecting them to form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from a C1-C20 alkyl group substituted with a silyl group having a carbon number, a C1-C10 amino group, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair, Each may be the same or different, and X ¹ and X ² may be combined with the atoms connecting them to form one ring. ]

  As an invention (embodiment invention) additional to the basic invention described above, the substituent at each position of the metallocene compound in the catalyst component for olefin polymerization is specified (Claim 2-3), and a crosslinked structure (Claim 4), embodying a central metal (Claim 5), forming a metallocene compound as a main catalyst component, and forming a polymerization catalyst characterized by a promoter component (Claims 6 and 7), Each invention embodies a process for producing a (co) polymer containing an olefin, particularly ethylene, by the polymerization catalyst (claims 8-10).

By using such a metallocene compound of the present invention as a catalyst component for olefin polymerization, while demonstrating excellent copolymerizability under industrially advantageous conditions, as demonstrated by the comparison of Examples and Comparative Examples described later. An olefin-based copolymer having a sufficiently high molecular weight can be produced, but the metallocene compound represented by the general formula (I) in the present invention is in the 2-position of the indenyl ring as seen in the chemical structure of paragraph 0016. Having a phenyl group skeleton that may have a substituent at the 4-position and a substituent other than a hydrogen atom at the 5-position (R ⁴ , R ¹⁴ in the chemical structure) The basic characteristic is that the structure is unique in terms of chemical, steric and electronic environment, and it can be presumed that these characteristics bring about the specificity of the present invention.

  The reason why the catalyst for olefin polymerization of the present invention exerts the above-described effects of the present invention is more specifically considered. By introducing a substituent other than a hydrogen atom at the 5-position of the indenyl ring, 4 As a result of regulating the growing polymer chain by steric hindrance in concert with the phenyl group at the position, the reaction site of the monomer around the central metal is widened, it becomes easier to react with the bulky comonomer, and it is considered that excellent copolymerizability is exhibited. And, in the structure in which a hydrogen atom is arranged at the substituent at the 2-position of the indenyl ring, the polymer elimination reaction that causes a decrease in the molecular weight of the growing polymer chain containing many bulky comonomers is sterically suppressed, It can be considered that it acts to increase the molecular weight of the polymer produced.

On the other hand, as demonstrated by comparison of Examples and Comparative Examples described later, the indenyl ring has an alkyl group at the 2-position, a phenyl group at the 4-position, and a substituent other than a hydrogen atom at the 5-position. With no structure, it is not an arrangement environment that can sufficiently suppress the elimination reaction of the polymer. In addition, a structure in which a methyl group is located at the 2-position of the indenyl ring and a substituent other than the phenyl group is arranged at the 4-position cannot exhibit excellent copolymerizability.
In contrast to this result, the structure found in the present invention has a hydrogen atom at the 2-position of the indenyl ring, a phenyl group at the 4-position, and a substituent other than a hydrogen atom at the 5-position, as described above. It is considered that an appropriate three-dimensional environment that can achieve both excellent copolymerization performance and suppression of polymer elimination reaction (improved molecular weight) can be provided.

  By the way, the present invention is significantly different from the conventional invention according to each of the documents listed above as patent documents and non-patent documents in the structural requirements (specific matters of the invention) and the effects of the invention. In contrast, a compound in which the substituent at the 2-position of the indenyl ring has a hydrogen atom and a substituent other than a hydrogen atom at the 5-position has a higher molecular weight olefin polymer than a compound having a substituent other than a hydrogen atom at the 2-position. As a result of the present invention, a compound in which the substituent at the 2-position of the indenyl ring has a hydrogen atom and a phenyl group at the 4-position has a methyl group at the 2-position, and the 4-position has a substituent other than the phenyl group. It can be said that the results of the present invention that exhibit superior copolymerizability than the arranged compounds are insignificant from those conventional documents.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general. Here, the overall configuration of the present invention will be summarized and summarized as follows. ] To [10] invention unit group.
The metallocene compound represented by the general formula [I] is constituted as the basic invention [1], and [2] each of the following inventions adds an additional requirement to the basic invention or shows an embodiment thereof. . In particular, the invention of the polymerization catalyst of [6] and [7] and the invention of the polymerization method of [8] to [10] specify additional requirements for solving the problems of the present invention. Yes. All invention units are collectively referred to as an invention group.

（なお、各置換基などの具体的な説明は段落００１７に詳述している。） [1] A metallocene compound represented by the following general formula [I]:

(Specific explanation of each substituent and the like is detailed in paragraph 0017.)

[2] The metallocene compound in [1], wherein in the general formula [I], R ⁴ and R ¹⁴ are the same or different and are alkyl groups having 1 to 10 carbon atoms.
[3] In the general formula [I], R ^{1 to} R ³ and R ^{11 to} R ¹³ are hydrogen atoms, R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different, and hydrogen atom, carbon number The metallocene compound in [1] or [2], which is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
[4] The metallocene compound according to any one of [1] to [3], wherein in the general formula [I], n is 1.
[5] The metallocene compound according to any one of [1] to [4], wherein in the general formula [I], M is Hf.

[6] A catalyst for olefin polymerization, comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metallocene compound in any one of [1] to [5] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C): Organic Aluminum compound [7] The olefin polymerization catalyst according to [6], wherein the component (B) is a boron compound.

[8] A method for producing an olefin polymer, wherein the olefin polymerization catalyst in [6] or [7] is used to perform olefin polymerization or copolymerization.
[9] The method for producing an olefin polymer according to [8], wherein the olefin used contains ethylene.
[10] The method for producing an olefin polymer according to [8] or [9], wherein the polymerization temperature is 120 ° C. or higher.

  As is apparent from the synthesis route described later, the metallocene compound of the present invention can be synthesized relatively easily by a simple synthesis route compared to conventional metallocene compounds, and the metallocene compound of the present invention can be used as a polymerization catalyst. By using it, it is possible to obtain a high molecular weight olefin polymer while exhibiting excellent copolymerizability at an industrially advantageous polymerization temperature and polymerization conditions as compared with conventional metallocene compounds. The metallocene compound, the catalyst for olefin polymerization, and the method for producing an olefin polymer using the catalyst for olefin polymerization are very useful from an industrial viewpoint.

  Below, the metallocene compound of this invention, the catalyst for olefin polymerization, and the manufacturing method of an olefin polymer using the same are demonstrated in detail for every item.

1. Metallocene Compound (1) Metallocene Compound According to General Formula [I] The metallocene compound of the present invention is a novel metallocene compound having a specific substituent represented by the general formula [I]. The metallocene compound has optical isomers due to its chemical structure, but the olefin polymerization catalyst is preferably a racemic form rather than a meso form.

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon number 6 to 20 aryl groups), provided that at least one of R ⁴ and R ¹⁴ is other than a hydrogen atom, and the adjacent groups of R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ together with the atoms connecting them. One or more aromatic rings or Or to form an aliphatic ring, or ^{R 4} and ^R 5, ^{R 4} and ^{R 9, R 14} and ^{R 15} or ^{R 14} and ^{R 19} is one together with the atoms connecting them aromatic ring or aliphatic May form a family ring;
Q is a carbon atom, a silicon atom or a germanium atom, n is a natural number of 1 to 3,
R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Aryl group, C6-C10 fluoroaryl group, C6-C10 aryloxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C7-C40 alkyl An aryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ may be combined with atoms connecting them to form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from a C1-C20 alkyl group substituted with a silyl group having a carbon number, a C1-C10 amino group, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair, Each may be the same or different, and X ¹ and X ² may be combined with the atoms connecting them to form one ring. ]

  In the general formula [I], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably zirconium or hafnium, and particularly preferably hafnium.

  Specific examples of the alkyl group having 1 to 10 carbon atoms in the general formula [I] include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, and n-pentyl. N-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, n-heptyl, n-octyl, n-decyl and the like.

Examples of the halogen atom of the halogenated alkyl group having 1 to 10 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A hydrogen atom on the skeleton of the group is substituted with a halogen.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 5-chloropentyl, 5,5,5-trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoro Mention may be made of pentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl and the like.

  Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, anthryl and the like.

The fluoroalkyl group having 1 to 10 carbon atoms is obtained by substituting a fluorine atom for a hydrogen atom on the skeleton of an alkyl group having 1 to 10 carbon atoms.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentafluoropropyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6,6-trifluorohexyl and the like can be mentioned.

  Specific examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, cyclo Propoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-deoxy and the like can be mentioned.

  The fluoroaryl group having 6 to 10 carbon atoms is obtained by substituting a fluorine atom for a hydrogen atom on the skeleton of an aryl group having 6 to 10 carbon atoms. Specific examples include pentafluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, di (trifluoromethyl) phenyl, pentafluoroethylphenyl, nonafluoro-t-butylphenyl, 1-perfluoronaphthyl, Examples include 2-perfluoronaphthyl.

  The aryloxy group having 6 to 10 carbon atoms may be substituted with a hydrocarbon group having 1 to 4 carbon atoms. Specific examples include phenoxy, trimethylphenoxy, dimethylphenoxy, ethylphenoxy, t-butylphenoxy, Examples include 1-naphthoxy and 2-naphthoxy.

  Specific examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl and the like.

  Specific examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, phenylethyl, (methylphenyl) methyl, (tert-butylphenyl) methyl, and the like.

  Specific examples of the alkylaryl group having 7 to 40 carbon atoms include tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, and t-butylphenyl.

  Specific examples of the arylalkenyl group having 8 to 40 carbon atoms include vinylphenyl and (2-propenyl) phenyl groups.

  Specific examples of the alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms include a trimethylsilylmethyl group, a triethylsilylmethyl group, and a triphenylsilylmethyl group. be able to.

  Specific examples of the amino group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, and a diisopropylamino group.

  Specific examples of the silyl group having a hydrocarbon group having 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group, tert-butyl (dimethyl) silyl group, and triphenylsilyl group.

Preferred R ²¹ groups are alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms, and specific examples of preferred —NR ²¹ ₂ groups include dimethylamino group, diethylamino group, diisopropylamino group and the like. be able to.
Specific examples of the —SR ²¹ group include a methylsulfanyl group, an ethylsulfanyl group, an isopropylsulfanyl group, and a phenylsulfanyl group.
Specific examples -OSiR ²¹ ₃ group can be mentioned trimethylsiloxy group, triethyl siloxane Shiki group, triisopropylsiloxy group, triphenylsiloxy group, and tert- butyl (dimethyl) siloxy group.
-PR ²¹ ₂ specifically, dimethylphosphinoyl group as group, diethylphosphino group, diisopropylphosphino group, di-butyl phosphino group, and the like diphenylphosphino group.

  In the general formula [I], Q is a carbon atom, a silicon atom, or a germanium atom, preferably a carbon atom or a silicon atom, and particularly preferably a carbon atom. n is a natural number of 1-3, preferably 1 or 2, and particularly preferably 1.

R ¹ , R ² , R ¹¹ and R ¹² are preferably hydrogen atoms. R ³ and R ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom or carbon number. 1 to 10 alkyl groups, particularly preferably a hydrogen atom.
At least one of R ⁴ and R ¹⁴ is substituted with other than a hydrogen atom, and it is preferable that both R ⁴ and R ¹⁴ are substituted with other than a hydrogen atom. Preferred substituents for R ⁴ and R ¹⁴ are an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Further, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. 1 to 20 carbon atoms substituted by a halogenated alkyl group, an aryl group having 6 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms And more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
R ¹⁰ and R ²⁰ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 7 to 10 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, carbon An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, and an arylalkenyl group having 8 to 40 carbon atoms, and more preferably a hydrogen atom or 1 carbon atom. An alkyl group having 10 to 10 carbon atoms, an aryl group having 7 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.

X ¹ and X ² are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 2 carbon atoms. A silyl group having a C-10 alkenyl group, a C7-40 arylalkyl group, a C7-40 alkylaryl group, a C8-40 arylalkenyl group, a C1-6 hydrocarbon group. It is selected from a substituted alkyl group having 1 to 20 carbon atoms, an amino group having 1 to 10 carbon atoms, an OH group, or a halogen atom, and a neutral ligand capable of coordinating with a lone electron pair. X ¹ and X ² may be combined with atoms connecting them to form one ring.
Specifically, chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, phenyl group, benzyl group, dimethylamino group, diethylamino group or trimethylsilyl A methyl group etc. can be mentioned.
Further, as an atomic group in which X ¹ and X ² form a ring together with atoms connecting them, specifically, 1,3-butadiene, 1,4-diphenyl-1,3- Butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,3-pentadiene, 1,4-ditolyl-1,3-butadiene, 1, 4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.
More specifically, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, and a trimethylsilylmethyl group are particularly preferable. Most preferred are a chlorine atom, a methyl group, an i-butyl group, a benzyl group, and a trimethylsilylmethyl group.

(2) Specific examples of metallocene compounds Specific examples of the metallocene compounds of the present invention are shown below. These are representative examples.

[A] 5-methylindenyl metallocene compound [a-1] isopropylidene-bridged isopropylidenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-methylphenyl) -5 -Methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-butylphenyl) -5-methyl -1-Indenyl) dimethylhafnium Propylidenebis (4- (4-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-Ethylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3 , 5-Diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis ( 4- (3,5-ditrimethyl Silylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,5- Dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- Biphenylyl-5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2 ′, 6 ′ -Dimethylbiphenylyl) -5-methyl-1-indeni ) Dimethylhafnium isopropylidenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium isopropylidenebis (4-Phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[A-2] Methylene-crosslinked product methylenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4 -(3-tert-Butylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (4- Isopropylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (4-trimethylsilylphenyl)- 5-Methyl-1-indenyl) dimethylhafnium meth Bis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (2-ethylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (3 , 5-Dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5 -Di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- ( 2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafni Mumethylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) Dimethyl hafnium methylene bis (4-biphenylyl-5-methyl-1-indenyl) dimethyl hafnium methylene bis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethyl hafnium methylene bis (4- ( 2 ′, 6′-Dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- (2- Naphthyl) -5-methyl-1-indenyl) dimethylhafniummethylenebis (4- Phenanthryl -5-methyl-1-indenyl) dimethyl hafnium

[A-3] Cyclobutylidene bis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (4-trimethylsilyl) Phenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-ethylphenyl)) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-diisopropyl) Phenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -5-methyl-1-indeni ) Dimethylhafnium cyclobutylidenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,5-dimethylphenyl) -5-methyl-1) -Indenyl) dimethylhafniumcyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-biphenylyl-5-methyl-1) -Indenyl) dimethylhafnium cyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2 ', 6'-dimethylbiphenylyl)) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis ( -(1-Naphtyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-phenanthryl-5) -Methyl-1-indenyl) dimethylhafnium

[A-4] Di-n-propylmethylene bis (4-n-propylmethylenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-methylphenyl) -5 -Methyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-methyl Phenyl) -5-methyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4 -Tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium di-n Propylmethylenebis (4- (4-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (2-ethylphenyl) -5-methyl-1-indenyl) dimethylhafnium di-propylenemethylenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl ) Dimethyl hafnium di n-propylmethylenebis (4- (3,5-diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (3,5-di-tert-butyl) Phenyl) -5-methyl-1-indenyl) dimethylhafnium di-n-propi Methylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) Dimethyl hafnium di n-propylmethylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (4-tert-butyl-2-methyl-) Phenyl) -5-methyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4-biphenylyl-5-methyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (2,6-dimethylbiphenyl) Ril) -5-methyl-1-indenyl) dimethylhafnium di-n-propylme Tylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethyl Hafnium di-n-propylmethylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4-phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[A-5] Dibenzylmethylene bridged product dibenzylmethylenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium dibenzylmethylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium dibenzylmethylenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium dibenzylmethylenebis (4- (4 Trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-ethylphenyl) ) -5-Methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5- Diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4 -(3,5-ditrimethylsilylphenyl -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,5-dimethyl) Phenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4 -Biphenylyl-5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2 ' , 6′-dimethylbiphenylyl) -5-methyl-1-indenyl) Methylhafnium dibenzylmethylenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium dibenzyl Methylenebis (4-phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[A-6] Diphenylmethylene bis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium Diphenylmethylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylene Bis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis ( 4- (4 Trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2-ethylphenyl)- 5-Methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5-diisopropylphenyl)- 5-Methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5- Ditrimethylsilylphenyl -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4-biphenylyl-5) -Methyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2 ', 6'-dimethylbiphenyl) Ril) -5-methyl-1-indenyl) Methylhafnium diphenylmethylenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium diphenylmethylenebis ( 4-phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[A-7] Dimethylsilylene bis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis ( 4- (4-Trimethylsilyl Phenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2-ethylphenyl) -5 -Methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-diisopropylphenyl) -5 -Methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di-) Trimethylsilylphenyl) -5-methyl-1-indeni ) Dimethylhafnium dimethylsilylene bis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium dimethylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4-biphenylyl-5-methyl-1-indenyl) dimethyl Hafnium dimethylsilylene bis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methyl-1 -Indenyl) dimethylhafnium dimethylsilylenebis ( -(1-Naphtyl) -5-methyl-1-indenyl) dimethylhafniumdimethylsilylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4-phenanthryl-5-methyl) -1-indenyl) dimethylhafnium

[A-8] Diethylsilylene bis (diethylsilylenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium Diethylsilylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium diethylsilylene Bis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis ( 4- (4-Trimethylsilyl Phenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-ethylphenyl) -5 -Methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-diisopropylphenyl) -5 -Methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-di-) Trimethylsilylphenyl) -5-methyl-1-indeni ) Dimethylhafniumdiethylsilylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) ) Dimethylhafniumdiethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-biphenylyl-5-methyl-1-indenyl) dimethyl Hafniumdiethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methyl-1 -Indenyl) dimethylhafnium diethylsilylenebis ( -(1-Naphtyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-phenanthryl-5-methyl) -1-indenyl) dimethylhafnium

[A-9] Diphenylsilylene bis (diphenylsilylenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium Diphenylsilylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylene Bis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis ( 4- (4 Trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-ethylphenyl)- 5-methyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (3,5-diisopropylphenyl)- 5-Methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (3,5- Ditrimethylsilylphenyl -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4-biphenylyl-5) -Methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2 ', 6'-dimethylbiphenyl) Ril) -5-methyl-1-indenyl) Methylhafnium diphenylsilylenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-naphthyl) -5-methyl-1-indenyl) dimethylhafnium diphenylsilylenebis ( 4-phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[A-10] Cross-linked silacyclobutylidenebis (4-phenyl-5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium silacyclobutylidenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium silacyclobutylidenebis (4- (4-methylphenyl) -5-methyl-1-indenyl ) Dimethylhafnium silacyclobutylidenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl ) Dimethyl hafnium silacyclobutyri Bis (4- (4-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2-Ethylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (3,5-diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-methyl-1-indenyl) dimethyl Hafnium Silacyclobutylidenebis (4- (3 -Ditrimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- ( 2,5-Dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafnium Clobutylidenebis (4-biphenylyl-5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2 ′, 6′-dimethylbi Enylyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (1-naphthyl) -5-methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-naphthyl) -5 -Methyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4-phenanthryl-5-methyl-1-indenyl) dimethylhafnium

[B] 5-ethylindenyl-based metallocene compound [b-1] isopropylidene-bridged isopropylidenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-methylphenyl) -5 -Ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-butylphenyl) -5-ethyl -1-Indenyl) dimethylhafnium Propylidenebis (4- (4-trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-Ethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3 , 5-Diisopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis ( 4- (3,5-ditrimethyl Silylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,5- Dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- Biphenylyl-5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2 ′, 6 ′ -Dimethylbiphenylyl) -5-ethyl-1-indeni ) Dimethylhafnium isopropylidenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium isopropylidenebis (4-Phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[B-2] Methylene-bridged product methylenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4 -(3-tert-Butylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (4- Isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (4-trimethylsilylphenyl)- 5-ethyl-1-indenyl) dimethylhafnium meth Bis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (2-ethylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (3 , 5-Dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-diisopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5 -Di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- ( 2,3-Dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafni Mumethylenebis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) Dimethyl hafnium methylene bis (4-biphenylyl-5-ethyl-1-indenyl) dimethyl hafnium methylene bis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethyl hafnium methylene bis (4- ( 2 ′, 6′-Dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- (2- Naphthyl) -5-ethyl-1-indenyl) dimethylhafniummethylenebis (4- Phenanthryl ethyl-1-indenyl) dimethyl hafnium

[B-3] Cross-linked cyclobutylidenecyclobutylidenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafniumcyclobutylidenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (4-trimethylsilyl) Phenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-ethylphenyl)) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-diisopropyl) Phenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -5-ethyl-1-indeni ) Dimethylhafnium cyclobutylidenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,5-dimethylphenyl) -5-ethyl-1 -Indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-biphenylyl-5-ethyl-1) -Indenyl) dimethylhafnium cyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2 ', 6'-dimethylbiphenylyl)) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis ( -(1-Naphtyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-phenanthryl-5) -Ethyl-1-indenyl) dimethylhafnium

[B-4] Di-n-propylmethylene bis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-methylphenyl) -5 -Ethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-methyl Phenyl) -5-ethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (4 -Tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium di-n Propylmethylenebis (4- (4-trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (2-ethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium di n-propylmethylenebis (4- (3,5-diisopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (3,5-di-tert-butyl) Phenyl) -5-ethyl-1-indenyl) dimethylhafnium di-n-propi Methylenebis (4- (3,5-ditrimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) Dimethyl hafnium di n-propylmethylenebis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (4-tert-butyl-2-methyl-) Phenyl) -5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4-biphenylyl-5-ethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (2,6-dimethylbiphenyl) Ril) -5-ethyl-1-indenyl) dimethylhafnium di-n-propylme Tylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethyl Hafnium di-n-propylmethylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4-phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[B-5] Dibenzylmethylene bis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) ) Dimethylhafnium dibenzylmethylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium dibenzylmethylenebis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium dibenzylmethylenebis (4- (4 Trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-ethylphenyl) ) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5- Diisopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4 -(3,5-ditrimethylsilylphenyl -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,5-dimethyl) Phenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4 -Biphenylyl-5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2 ' , 6′-dimethylbiphenylyl) -5-ethyl-1-indenyl) Methylhafnium dibenzylmethylenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumdibenzylmethylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium dibenzyl Methylenebis (4-phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[B-6] Diphenylmethylene bis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium Diphenylmethylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylene Bis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis ( 4- (4 Trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2-ethylphenyl)- 5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5-diisopropylphenyl)- 5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5- Ditrimethylsilylphenyl -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4-biphenylyl-5) -Ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2 ', 6'-dimethylbiphenyl) Ril) -5-ethyl-1-indenyl) Methylhafnium diphenylmethylenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylmethylenebis ( 4-phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[B-7] Crosslinked dimethylsilylene dimethylsilylenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis ( 4- (4-Trimethylsilyl Phenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-ethylphenyl) -5 -Ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-diisopropylphenyl) -5 -Ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di-) Trimethylsilylphenyl) -5-ethyl-1-indeni ) Dimethylhafnium dimethylsilylene bis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium dimethylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4-biphenylyl-5-ethyl-1-indenyl) dimethyl Hafnium dimethylsilylene bis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethyl hafnium dimethylsilylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -5-ethyl-1 -Indenyl) dimethylhafnium dimethylsilylenebis ( -(1-Naphtyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4-phenanthryl-5-ethyl) -1-indenyl) dimethylhafnium

[B-8] Diethylsilylene bis (diethylsilylenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium Diethylsilylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diethylsilylene Bis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis ( 4- (4-Trimethylsilyl Phenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-ethylphenyl) -5 -Ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-diisopropylphenyl) -5 -Ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-di-) Trimethylsilylphenyl) -5-ethyl-1-indeni ) Dimethylhafniumdiethylsilylenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl) ) Dimethylhafniumdiethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-biphenylyl-5-ethyl-1-indenyl) dimethyl Hafniumdiethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-ethyl-1 -Indenyl) dimethylhafnium diethylsilylenebis ( -(1-Naphtyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-phenanthryl-5-ethyl) -1-indenyl) dimethylhafnium

[B-9] Diphenylsilylene bis (diphenylsilylenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium Diphenylsilylenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylene Bis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis ( 4- (4 Trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-ethylphenyl)- 5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-diisopropylphenyl)- 5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (3,5- Ditrimethylsilylphenyl -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (2,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4-biphenylyl-5) -Ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2 ', 6'-dimethylbiphenyl) Ril) -5-ethyl-1-indenyl) Methylhafnium diphenylsilylenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2-naphthyl) -5-ethyl-1-indenyl) dimethylhafnium diphenylsilylenebis ( 4-phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[B-10] Silacyclobutylidene crosslinked silacyclobutylidenebis (4-phenyl-5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-methylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium silacyclobutylidenebis (4- (3-tert-butylphenyl) -5-ethyl-1-indenyl) dimethylhafnium silacyclobutylidenebis (4- (4-methylphenyl) -5-ethyl-1-indenyl ) Dimethylhafnium silacyclobutylidenebis (4- (4-isopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-tert-butylphenyl) -5-ethyl-1-indenyl ) Dimethyl hafnium silacyclobutyri Bis (4- (4-trimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-methylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2-Ethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (3,5-diisopropylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-ethyl-1-indenyl) dimethyl Hafnium Silacyclobutylidenebis (4- (3 -Ditrimethylsilylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,3-dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- ( 2,5-Dimethylphenyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-ethyl-1-indenyl) dimethylhafnium Clobutylidenebis (4-biphenylyl-5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2 ′, 6′-dimethylbi Enylyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (1-naphthyl) -5-ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-naphthyl) -5 -Ethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4-phenanthryl-5-ethyl-1-indenyl) dimethylhafnium

[C] 5,6-dimethylindenyl metallocene compound [c-1] isopropylidene bis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3 -Methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-Methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-Butylphenyl) -5,6-dimethyl Ru-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-methylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-dimethylphenyl) -5 6-Dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-di-) tert-butylphenyl) -5,6-dimethyl-1 Indenyl) dimethylhafnium isopropylidenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,3-dimethylphenyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-tert-butyl-2) -Methyl-phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,6-dimethyl) Biphenylyl) -5,6-dimethyl-1-y Ndenyl) dimethylhafnium isopropylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (1-naphthyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium isopropylidenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) Dimethyl hafnium

[C-2] Methylene-bridged product methylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (3-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Methylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Methylenebis (4- (4-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Methylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Methylenebis (4- (4-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Methylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl -1-indenyl) dimethylhafniummethylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (2-ethylphenyl) -5,6-dimethyl-1 -Indenyl) dimethylhafnium methylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl -1-indenyl) dimethylhafniummethylenebis (4- (3,5-di-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-ditrimethylsilylphenyl) ) -5,6-Dimethyl-1-indenyl) dimethylhafnium methylenebis 4- (2,3-Dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylene Bis (4- (4-tert-butyl-2-methyl-phenyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafniummethylene Bis (4- (2,6-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafniummethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1 -Indenyl) dimethylhafnium methylenebis (4- (1-naphthyl) -5,6-dimethyl-1-indenyl Dimethyl hafnium methylene bis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethyl hafnium methylene bis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethyl hafnium

[C-3] Cyclobutylidene bis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3-methylphenyl) -5,6-dimethyl -1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-methylphenyl) -5 , 6-Dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butyl) Phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobuty Denbis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumcyclobutylidenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumcyclo Butylidenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5,6-Dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebi (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium cyclobutylidenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) ) -5,6-Dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,6-dimethylbiphenylyl) ) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis ( 4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (1-naphthyl) -5,6-dimethyl-1-indenyl) dimethyl Hafnium cyclobutylidenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-4] Di-n-propylmethylene bis (di-n-propylmethylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (3-methylphenyl)) -5,6-dimethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis ( 4- (4-Methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- (4-tert-butylphenyl) -5,6-dimethyl-1 Indenyl) dimethylhafnium di n-propylmethylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (2-methylphenyl) -5 6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3 5-Dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium din -Propylmethylenebis (4- (3,5-di-tert-butylphenol) ) -5,6-Dimethyl-1-indenyl) dimethylhafnium di n-propylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di n-propyl Methylenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- Biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,6-Dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6- Dimethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (1-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (2-naphthyl)- 5,6-Dimethyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-5] Dibenzylmethylene bis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-methylphenyl) -5,6-dimethyl -1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-methylphenyl) -5 , 6-Dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butyl) Phenyl) -5,6-dimethyl-1-indenyl) dimethylhafni Mudibenzylmethylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) Dimethyl hafnium dibenzylmethylenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-di-tert- Butylphenyl) -5,6-dimethyl-1-indenyl) dimethyl Nitrodibenzylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdibenzylmethylenebis (4- (2,3-dimethylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-tert-butyl- 2-Methyl-phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2, 6-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) di Methylhafnium dibenzylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (1-naphthyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4-phenanthryl-5,6-dimethyl-1- Indenyl) dimethyl hafnium

[C-6] Diphenylmethylene crosslinked diphenylmethylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3-methylphenyl) -5,6-dimethyl-1- Indenyl) dimethylhafnium diphenylmethylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (4-methylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (4-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethyl hafni Mudiphenylmethylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethyl Hafnium diphenylmethylenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium diphenylmethylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5-di-tert-butylphenyl) -5 , 6-Dimethyl-1-indenyl) dimethylha Nitrodiphenylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (4-tert-butyl-2-methyl- Phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,6-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) di Methylhafnium diphenylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (1-naphthyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-7] Crosslinked dimethylsilylene dimethylsilylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-methylphenyl) -5,6-dimethyl-1- Indenyl) dimethylhafnium dimethylsilylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-methylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium dimethylsilylene bis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (4-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium dimethyl Renbis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebi (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl) Dimethylhafnium dimethylsilylene bis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -5 , 6-Dimethyl-1-indenyl) dimethylhafniumdimethylsilylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis ( 4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (1-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-8] Diethylsilylene crosslinked product diethylsilylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3-methylphenyl) -5,6-dimethyl-1- Indenyl) dimethylhafniumdiethylsilylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-methylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafniumdiethyl Renbis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylene Bis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Diethylsilylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium diethylsilylenebi (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl) Dimethylhafniumdiethylsilylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5 , 6-Dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium diethylsilylenebis ( 4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diethylsilylenebis (4- (1-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Diethylsilylenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafnium Diethylsilylenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-9] Diphenylsilylene crosslinked diphenylsilylenebis (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3-methylphenyl) -5,6-dimethyl-1- Indenyl) dimethylhafniumdiphenylsilylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (4-methylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylsilylene bis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (4-tert-butylphenyl) -5,6- Dimethyl-1-indenyl) dimethyl hafni Mudiphenylsilylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethyl Hafnium diphenylsilylene bis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium diphenylsilylene bis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (3,5-di-tert-butylphenyl) -5 , 6-Dimethyl-1-indenyl) dimethylha Nitrodiphenylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylsilylene bis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (4-tert-butyl-2-methyl-) Phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2,6-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) di Methylhafnium diphenylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (1-naphthyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[C-10] Silacyclobutylidene bis (silacyclobutylidenebis) (4-phenyl-5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-methylphenyl) -5,6-dimethyl -1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-tert-butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-methylphenyl) -5 , 6-Dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-tert-butyl) Phenyl) -5,6-dimethyl-1-indenyl Dimethyl hafnium silacyclobutylidenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium silacyclobutylidenebis (4- (2-methylphenyl) -5,6-dimethyl-1- Indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-dimethylphenyl) -5,6- Dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-di-) tert-butylphenyl) -5,6-dimethyl 1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4 -Tert-butyl-2-methyl-phenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2,6-Dimethylbiphenylyl ) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (1-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-naphthyl) -5,6-dimethyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4-phenanthryl-5,6-dimethyl-1-indenyl) dimethylhafnium

[D] Tetrahydroindacenyl metallocene compound [d-1] Isopropylidene bis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- ( 3-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl ) Dimethylhafnium isopropylidenebis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (4-isopropylphenyl) -1,5,6 , 7-Tetrahydro-s-indacenyl) dimethylhafnium iso Ropyridenebis (4- (4-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (4-trimethylsilylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2-ethylphenyl)- 1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (3,5-diisopropylphenyl) -1 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropyl Ridenbis (4- (3,5-ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2,3-dimethylphenyl) -1,5 6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- ( 4-tert-butyl-2-methyl-phenyl) -1,5,6,7-teto Lahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2,6-dimethylbiphenylyl) -1, 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidene Bis (4- (1-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium isopropylidenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s- Indacenyl) dimethylhafnium isopropylidenebis (4-phenanthryl) 1,5,6,7- tetrahydro -s- indacenyl) dimethyl hafnium

[D-2] Methylene bridged product methylenebis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (3-methylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (4-methylphenyl)- 1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- ( 4-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) Methylhafniummethylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (2-methylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (2-ethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (3,5-dimethylphenyl)- 1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (3,5-diisopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4 -(3,5-di-tert-butylphenyl) -1,5,6,7-teto Hydro-s-indacenyl) dimethylhafniummethylenebis (4- (3,5-ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (2,3-dimethyl) Phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylene Bis (4- (4-tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4-biphenylyl-1,5,6,7-tetrahydro -S-indacenyl) dimethylhafniummethylenebis (4- (2,6-dimethylbifu) Enylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniummethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) Dimethyl hafnium methylene bis (4- (1-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl hafnium methylene bis (4- (2-naphthyl) -1,5,6,7-tetrahydro- s-indacenyl) dimethylhafniummethylenebis (4-phenanthryl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

[D-3] Cyclobutylidene bis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (3-methylphenyl) -1 , 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidene Bis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro -S-indacenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butylphen L) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumcyclobutylidenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumcyclo Butylidenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumcyclobutylidenebis (4- (2-ethylphenyl) -1,5,6,7 -Tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (3 , 5-Diisopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) di Tylhafnium cyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (3,5- Ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl ) Dimethylhafnium cyclobutylidenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butyl-2) -Methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Clobutylidenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumcyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro -S-indacenyl) dimethylhafnium cyclobutylidenebis (4- (2 ', 6'-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- ( 1-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium cyclobutylidenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Cyclobutylidenebis (4-phenanthryl-1,5,6,7-tetrahydro-s-indacenyl Dimethyl hafnium

[D-4] di-n-propylmethylene bis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3 -Methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s -Indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-isopropyl Phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylme Renbis (4- (4-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-trimethylsilylphenyl) -1,5,6 , 7-Tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis ( 4- (2-Ethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-dimethylphenyl) -1,5,6,7 -Tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-dii) Propylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis ( 4- (2,3-Dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,5-dimethylphenyl) -1,5,6 , 7-Tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-tert -Butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) ) Dimethyl hafnium di n-propylmethylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di n-propylmethylenebis (4- (2 ′ , 6'-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (1-naphthyl) -1,5,6,7-tetrahydro- s-Indacenyl) dimethylhafnium di-n-propylmethylenebis (4- (2-naphthyl) -1,5,6,7-tetra Mud -s- indacenyl) dimethyl hafnium di n- propyl methylene bis (4-phenanthryl-1,5,6,7-tetrahydro -s- indacenyl) dimethyl hafnium

[D-5] Dibenzylmethylene bis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3-methylphenyl) -1 , 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylene Bis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro -S-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (4-ter -Butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium dibenzylmethylenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2-ethylphenyl) -1,5,6 , 7-Tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-diisopropylphenyl) -1,5,6,7-tetrahydride -S-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2,3-dimethylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (4- tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s- Indacenyl) dimethylhafnium dibenzylmethylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2,6-dimethylbiphenylyl) -1,5 6,7-Tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylene Bis (4- (1-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dibenzylmethylenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s -Indacenyl) dimethylhafnium dibenzylmethylenebis (4-phenanthryl- , 5,6,7-tetrahydro -s- indacenyl) dimethyl hafnium

[D-6] Diphenylmethylene crosslinked diphenylmethylenebis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (3-methylphenyl) -1,5 6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylmethylenebis (4- ( 4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium diphenylmethylenebis (4- (4-ter -Butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Diphenylmethylenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (2-ethylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylmethylenebis (4- (3,5- Diisopropylphenyl) -1,5,6,7-tetrahydride -S-indacenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (3 , 5-Ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s -Indacenyl) dimethylhafnium diphenylmethylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylmethylenebis (4- (4-tert-butyl-2 -Methyl-phenyl) -1,5,6,7-tetrahydro-s- Indacenyl) dimethylhafnium diphenylmethylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylmethylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6 7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (1-Naphtyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylmethylenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Diphenylmethylenebis (4-phenanthryl- , 5,6,7-tetrahydro -s- indacenyl) dimethyl hafnium

[D-7] Crosslinked dimethylsilylene dimethylsilylenebis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3-methylphenyl) -1,5 6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- ( 4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium dimethylsilylene bis (4- (4-tert-butylphenol) L) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene Bis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2-ethylphenyl) -1,5,6,7-tetrahydro- s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-diisopropylphenyl) ) -1,5,6,7-tetrahydro-s-indacenyl) di Tylhafnium dimethylsilylene bis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-ditrimethylsilyl) Phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Dimethylsilylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdi Methylsilylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro- s-Indacenyl) dimethylhafnium dimethylsilylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (1-naphthyl) ) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis ( 4-phenanthryl-1,5,6,7-tetrahydro-s-indacenyl Dimethyl hafnium

[D-8] Diethylsilylene bis (diethylsilylenebis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (3-methylphenyl) -1,5 6,7-Tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- ( 4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium diethylsilylenebis (4- (4-tert-butylphenol) L) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylene Bis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (2-ethylphenyl) -1,5,6,7-tetrahydro- s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-diisopropylphenyl) ) -1,5,6,7-tetrahydro-s-indacenyl) di Tylhafniumdiethylsilylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-ditrimethylsilyl) Phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diethylsilylenebis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Diethylsilylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdi Ethylsilylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro- s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (1-naphthyl) ) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiethylsilylenebis ( 4-phenanthryl-1,5,6,7-tetrahydro-s-indacenyl Dimethyl hafnium

[D-9] Diphenylsilylene cross-linked diphenylsilylenebis (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3-methylphenyl) -1,5 6,7-Tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- ( 4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium diphenylsilylene bis (4- (4-ter -Butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Diphenylsilylenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (2-ethylphenyl) -1,5,6,7- Tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3,5- Diisopropylphenyl) -1,5,6,7-tetrahydride -S-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (3 , 5-Ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s -Indacenyl) dimethylhafnium diphenylsilylenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylsilylenebis (4- (4-tert-butyl-2) -Methyl-phenyl) -1,5,6,7-tetrahydro-s- Indacenyl) dimethylhafnium diphenylsilylenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumdiphenylsilylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6 7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylene bis (4- (1-Naphtyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium diphenylsilylenebis (4- (2-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium Diphenylsilylenebis (4-phenanthryl- , 5,6,7-tetrahydro -s- indacenyl) dimethyl hafnium

[D-10] Silacyclobutylidene bis (silacyclobutylidenebis) (4-phenyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-methylphenyl) -1 , 5,6,7-Tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidene Bis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro -S-indacenyl) dimethylhafniumsilacyclobutylidenebis ( -(4-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro- s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-ethylphenyl)- 1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobuty Redenbis (4- (3,5-diisopropylphenyl)- , 5,6,7-Tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafniumsilacyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,3-dimethylphenyl)- 1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobuty Redenbis (4- (4-tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4-biphenylyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- ( 2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1,5,6 7-Tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (1-naphthyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-naphthyl) ) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafniu Sila cyclobutylidene bis (4-phenanthryl-1,5,6,7-tetrahydro -s- indacenyl) dimethyl hafnium

[E] 5-methoxyindenyl-based metallocene compound [e-1] isopropylidene-crosslinked isopropylidenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-Methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium isopropylidenebis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-isopropylphenyl) -5-methoxy- 6-tert-butyl-1-indenyl) dimethyl Ruhafnium isopropylidenebis (4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (4-trimethylsilylphenyl) -5-methoxy- 6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2- Ethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium isopropylidenebis (4- 3,5-diisopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert -Butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2, 3-Dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) ) Dimethylhafnium isopropylidenebis (4- (4-te rt-butyl-2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium isopropylidenebis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium isopropylidenebis (4 -(2-Naphthyl) -5-methoxy-6-tert- Chill-1-indenyl) dimethyl hafnium isopropylidene bis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-2] Methylene bridged product methylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium methylenebis (4- (3-methylphenyl) -5-methoxy-6-tert- Butyl-1-indenyl) dimethylhafniummethylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (4-methylphenyl)- 5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- ( 4-tert-butylphenyl) -5-methoxy-6-tert- Til-1-indenyl) dimethylhafniummethylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (2-methylphenyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (2-ethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (3 5-Dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium methylenebis (4- (3,5-diisopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethyl hafnium methylene bis (4- (3,5-di-te t-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl ) Dimethyl hafnium methylene bis (4- (2,3-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl hafnium methylene bis (4- (2,5-dimethylphenyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4-Biphenylyl-5-methoxy-6-tert-butyl-1-y Ndenyl) dimethylhafniummethylenebis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) ) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4- (2-Naphtyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniummethylenebis (4-phenanthryl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium

[E-3] Cyclobutylidene bis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3-methylphenyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidene Bis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4- ert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethylhafnium cyclobutylidenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-ethylphenyl) -5-methoxy- 6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4 -(3,5-diisopropylphenyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethylhafniumcyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumcyclo Butylidenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,3-dimethylphenyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-meth Xyl-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2,6 -Dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2 ', 6'-dimethylbiphenylyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium cyclobutylidenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium cyclobutylidenebis (4- (2-naphthyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium Butylidenebis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-4] Di-n-propylmethylene bis (di-n-propylmethylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3 -Methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1 -Indenyl) dimethylhafnium di-n-propylmethylenebis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-isopropyl Phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafni Mudi-n-propylmethylenebis (4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (4-trimethylsilylphenyl)- 5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdin -Propylmethylenebis (4- (2-ethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4- (3,5-dimethylphenyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n- L-propylmethylenebis (4- (3,5-diisopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-di-tert- Butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1 -Indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2 , 5-Dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Tylhafnium di-n-propylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- Biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium di-n-propylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl ) Dimethylhafnium di n-propylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi n-propylmethylenebis (4- ( 1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylha Ni-di-n-propylmethylenebis (4- (2-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi-n-propylmethylenebis (4-phenanthryl-5-methoxy-6-tert-) Butyl-1-indenyl) dimethylhafnium

[E-5] Dibenzylmethylene crosslinked dibenzylmethylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-methylphenyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylene Bis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium dibenzylmethylenebi (4- (4-tert-Butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert- Butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-ethylphenyl) ) -5-Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium Dibenzylmethylenebis (4- (3,5-diisopropyl Phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1 -Indenyl) dimethylhafnium dibenzylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,3- Dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethyl hafnium dibenzylmethylene bis (4- (4-tert-butyl -2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdi Benzylmethylenebis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dibenzylmethylenebis (4- (2-Naphtyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethyl hafnium dibenzyl methylene bis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-6] Diphenylmethylene crosslinked diphenylmethylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3-methylphenyl) -5-methoxy- 6-tert-Butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- ( 4-Methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium diphenylmethylene bi (4- (4-tert-Butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2-ethylphenyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis ( 4- (3,5-diisopropyl Phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium diphenylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiphenylmethylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylene Bis (4- (4-tert-butyl 2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylene Bis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylmethylenebis (4- (2 -Naphthyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethyl hafnium diphenylmethylene-bis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-7] Crosslinked dimethylsilylene dimethylsilylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-methylphenyl) -5-methoxy- 6-tert-Butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- ( 4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium dimethylsilylene bis (4- (4- ert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium dimethylsilylene bis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2-ethylphenyl) -5-methoxy-6-tert -Butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5 -Diisopropylphenyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6 -Tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4 -Tert-butyl-2-methyl-phenyl) -5-meth Xyl-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethyl) Biphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium dimethylsilylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-naphthyl) -5-methoxy-6 tert-butyl-1-indenyl) dimethylhafnium dimethyl Rushirirenbisu (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-8] Diethylsilylene crosslinked product diethylsilylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3-methylphenyl) -5-methoxy- 6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- ( 4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium diethylsilylene bis (4- (4- ert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafniumdiethylsilylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-ethylphenyl) -5-methoxy-6-tert -Butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5 -Diisopropylphenyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylene Bis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6 -Tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (4 -Tert-butyl-2-methyl-phenyl) -5-meth Xyl-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2,6-dimethyl) Biphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafniumdiethylsilylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiethylsilylenebis (4- (2-naphthyl) -5-methoxy-6 tert-butyl-1-indenyl) dimethylhafnium die Rushirirenbisu (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-9] Diphenylsilylene crosslinked diphenylsilylenebis (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3-methylphenyl) -5-methoxy- 6-tert-Butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- ( 4-Methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium diphenylsilylenebi (4- (4-tert-Butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2-ethylphenyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylene bis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylene bis ( 4- (3,5-diisopropyl Phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium diphenylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumdiphenylsilylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylene Bis (4- (4-tert-butyl -2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4-biphenylyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylene Bis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium diphenylsilylenebis (4- (2 -Naphthyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethyl hafnium diphenyl silylene-bis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

[E-10] Silacyclobutylidene bis (silacyclobutylidenebis) (4-phenyl-5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-methylphenyl) -5 -Methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidene Bis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl -1-indenyl) dimethylhafnium Robutylidenebis (4- (4-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert -Butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2-ethyl Phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl Hafnium Silacyclobutylidenebis ( -(3,5-diisopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy- 6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis ( 4- (2,3-Dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,5-dimethylphenyl) -5-methoxy-6-tert -Butyl-1-indenyl) dimethylhafnium silacyclobutylyl Denbis (4- (4-tert-butyl-2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4-biphenylyl-5-methoxy-6-tert) -Butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- ( 2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- (1-naphthyl) -5-methoxy-6-tert-butyl- 1-indenyl) dimethylhafniumsilacyclobutylidenebis (4- ( - naphthyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium sila cyclobutylidene bis (4-phenanthryl-5-methoxy -6-tert-butyl-1-indenyl) dimethyl hafnium

In addition to the above, M in the exemplified compound is replaced with titanium or zirconium instead of hafnium, or one or both of the compounds represented by X ¹ and X ² are substituted with a chlorine atom or bromine atom instead of the exemplified methyl group. Further, compounds substituted for iodine atom, phenyl group, benzyl group, dimethylamino group, diethylamino group, trimethylsilylmethyl group and the like can also be exemplified.

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

  In the above synthetic route, 2 is obtained by performing a coupling reaction between 1 and phenylboronic acid in the presence of a palladium catalyst. The crosslinking reaction from 2 to 3 can be carried out by the method described in the literature (Japanese Patent No. 3835846). After 2 is anionized with potassium hydroxide or the like, 3 is obtained by reaction with acetone. After metal 3 is dianionized with 2 equivalents of n-butyllithium or the like, metallocene compound 4 can be obtained by reaction with hafnium tetrachloride. Generally, 4 is a mixture of a racemate and a meso isomer, and a racemate having excellent catalytic performance is concentrated by purification. In addition, the meso form can be isomerized into a racemate by the method described in the literature (WO2000 / 017213) and the yield of the racemate can be improved. The dimethyl body 5 can be obtained by treating 4 with 2 equivalents or more of MeMgBr.

The synthesis of the metallocene compound into which a substituent is introduced can be synthesized by using a corresponding substitution raw material. Instead of phenylboronic acid, a corresponding boronic acid such as 4-isopropylphenylboronic acid, 3,5- By using dimethylphenylboronic acid or the like, a (R ⁵ -R ⁹ , R ¹⁵ -R ¹⁹ ) substituent can be introduced on the 4-position phenyl group of the indenyl ring.
The synthesis of metallocene compounds having different substituents on the bridging group can be synthesized by using corresponding substitution raw materials, and by using corresponding ketones such as cyclobutanone and 4-heptenone instead of acetone, Substituents (R ¹⁰ , R ²⁰ ) can be introduced on the bridging group.
Also, the synthesis of the crosslinking group are different metallocene compounds can be synthesized by using the corresponding cross-linking agent and the reagent, dichlorosilane instead of ^{acetone, R 10 (R 20) SiCl} 2 and dichloro germane R ¹⁰ ( By using R ²⁰ ) GeCl ₂ and using n-butyllithium or the like instead of potassium hydroxide as the anionizing agent at the time of crosslinking, different crosslinking groups can be introduced.

3. Olefin Polymerization Catalyst (1) Olefin Polymerization Catalyst Component The metallocene compound of the present invention forms an olefin polymerization catalyst component, and the catalyst component can be used as an olefin polymerization catalyst. For example, the metallocene compound is preferably used as an olefin polymerization catalyst described below that contains the component (A).

The olefin polymerization catalyst of the present invention contains the following components (A), (B) and optionally (C).
Component (A): Metallocene compound represented by general formula [I] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate Component (C): Organoaluminum compound

(2) About each component (2-1) Component A
As the metallocene compound represented by the general formula [I] of the component (A), two or more compounds represented by the same or different general formula [I] may be used.

(2-2) Component B
The component (B) is a compound or ion-exchange layered silicate that reacts with the component (A) to form an ion pair.
Examples of the compound that reacts with the component (A) to form an ion pair include an organoaluminum oxy compound, a boron compound, and a zinc compound, preferably an organoaluminum oxy compound or a boron compound, more preferably a boron compound. It is. These components (B) may be used alone or in combination of two or more.

(2-2-1) Organoaluminumoxy compound The organoaluminumoxy compound which is one of the components (B) has Al-O-Al bonds in the molecule, and the number of bonds is usually 1 to 100, preferably Is in the range of 1-50. Such an organoaluminum oxy compound is usually obtained by reacting an organoaluminum compound with water or an aromatic carboxylic acid.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula [II] can be used, but trialkylaluminum is preferably used.
^{_{R a t AlX a 3-t}} [II]
(In the formula, R ^a represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ^a represents a hydrogen atom or a halogen atom. , T represents an integer of 1 ≦ t ≦ 3.)
The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. A methyl group and an isobutyl group are preferable, and a methyl group is more preferable. Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is usually It is in the range of −70 to 100 ^° C., preferably −20 to 20 ^° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can be used in combination, and a solution in which the organoaluminum oxy compound is dissolved or dispersed in the above-described inert hydrocarbon solvent. You may use.

  In an organoaluminum oxy compound, what is represented by the following general formula can also be illustrated.

The compound represented by the general formula [III] is 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the general formula: R ^c B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

(2-2-2) Boron compound Examples of the boron compound that is one of the components (B) include boron compounds such as borane compounds and borate compounds.
Specific examples of the borane compound include triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tris (o-fluorophenyl) borane, tris (p- Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3 , 5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenylyl) borane, tris ( Perfluoroanthryl) borane, tris (par Le Oro binaphthyl) such as borane.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenylyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) borane are more preferred, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (Perfluoronaphthyl) borane and tris (perfluorobiphenylyl) borane are preferred.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula [IV].
^{[L 1 -H] + [BR} d R e X b X c] - [IV]
In the formula [IV], L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In the formula [IV], R ^d and R ^e are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and linked to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Furthermore, ^Xb and ^Xc are a hydride group, a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula [IV] include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophene) L) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5 -Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium Tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl Ammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

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

Moreover, the 2nd example of a borate compound is represented by the following general formula [V].
^{[L 2] + [BR d} R e X b X c] - [V]
In the formula [V], L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. Examples include cations and protons. R ^d , R ^e , X ^b and X ^c are the same as defined in the general formula [IV].

  Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 -Ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, sodium tetraphenyl borate, sodium tetra (o-tolyl) borate, sodium tetra (p-tolyl) borate, sodium Tora (m-tolyl) borate, sodium tetra (o-fluorophenyl) borate, sodium tetra (p-fluorophenyl) borate, sodium tetra (m-fluorophenyl) borate, sodium tetra (3,5-difluorophenyl) borate, sodium tetra (pentafluoro) Phenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodiumtetra (3,5-ditrifluoromethylphenyl) borate, sodiumtetra (perfluoronaphthyl) borate, hydrogentetraphenylborate-2diethylether, hydrogentetra ( 3,5-difluorophenyl) borate-2 diethyl ether, hydrogen tetra (pentafluorophenyl) borate-2 diethyl ether, hydride Examples include logentetra (2,6-ditrifluoromethylphenyl) borate-2 diethyl ether, hydrogentetra (3,5-ditrifluoromethylphenyl) borate-2 diethylether, hydrogentetra (perfluoronaphthyl) borate-2 diethylether, etc. can do.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, Sodium tetra (pentafluorophenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodium tetra (3,5-ditrifluoromethylphenyl) borate, soji Mutetra (perfluoronaphthyl) borate, hydrogentetra (pentafluorophenyl) borate-2 diethyl ether, hydrogentetra (2,6-ditrifluoromethylphenyl) borate-2 diethylether, hydrogentetra (3,5-ditrifluoromethylphenyl) ) Borate · 2 diethyl ether and hydrogen tetra (perfluoronaphthyl) borate · 2 diethyl ether are preferred.
More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, sodium tetra (pentafluorophenyl) borate, sodiumtetra (2,6-ditrifluoromethylphenyl) borate, hydrogentetra (pentafluorophenyl) borate-2diethyl ether, hydrogentetra (2,6-ditrifluoromethylphenyl) ) Borate-2 diethyl ether and hydrogen tetra (3,5-ditrifluoromethylphenyl) borate-2 diethyl ether.

  Further, as the component (B) of the olefin polymerization catalyst, a mixture of the organoaluminum oxy compound and the borane compound or borate compound can be used. Furthermore, two or more of the above borane compounds and borate compounds can be used in combination.

(2-2-3) Ion-exchangeable layered silicate Ion-exchangeable layered silicate (hereinafter sometimes abbreviated simply as “silicate”) has a surface composed of ionic bonds and the like with bonding force. It refers to a silicate compound that has a crystal structure that is stacked in parallel and that allows the contained ions to be exchanged.
Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the smectite group, and specific examples include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite. Among these, montmorillonite is preferable in terms of the activity and molecular weight of the rubber component.
Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.

Granulation of ion-exchange layered silicate:
Silicates may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the use of granulated silicate is particularly preferred because it gives good polymer particle properties.
The shape processing of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferred examples include agitation granulation method, spray granulation method, rolling granulation method, and fluidization granulation method, and particularly preferred are agitation granulation method and spray granulation method.
When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (B) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . Although the inlet temperature of the hot air of spray granulation from which spherical particles are obtained varies depending on the dispersion medium, taking water as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

In granulation, in order to obtain a carrier having high particle strength and to improve the olefin polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferable is wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a method by forced stirring using polytron or the like, a method by dyno mill, pearl mill or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder to be used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol and the like.
The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1,000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

Acid treatment:
The silicate used in the present invention is used after being subjected to an acid treatment, but may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment, and the like.
The acid treatment of the silicate can change the acid strength of the solid. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment also has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Two or more of these may be used simultaneously. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid, and nitric acid are preferable, and sulfuric acid is more preferable.
In addition, a method in which acid treatment and salt treatment are combined is particularly preferable, a method in which acid treatment is performed after salt treatment, a method in which salt treatment is performed after acid treatment, a method in which salt treatment and acid treatment are performed simultaneously, salt treatment There is a method of performing salt treatment and acid treatment at the same time after the treatment.

The treatment conditions with the acid are usually selected from the conditions where the acid concentration is 0.1 to 30% by weight, the treatment temperature is the temperature range from room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the conditions under which at least a part is eluted. The acid is generally used as an aqueous solution. For example, when sulfuric acid is used, the treatment temperature is preferably 80 ° C. to 100 ° C., and the treatment time is preferably 0.5 hours or more and less than 5 hours.
By performing the salt treatment at the same time, the surface area and interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, or the like. For example, a layered substance in a state where the layers are expanded can be obtained by replacing the exchangeable ions between the layers with other large and bulky ions using ion exchange.
When the acid treatment is performed, shape control may be performed by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organometallic treatment may be used in combination.

The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of 1 to 14 atoms, and preferably selected from the group consisting of 1 to 14 atoms. And a compound comprising a cation containing at least one atom and an anion derived from at least one atom or atomic group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. Is a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOC It is a compound comprising at least one anion selected from the group consisting of H, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Two or more of these salts may be used simultaneously.

The silicate thus obtained preferably has a pore volume with a radius of 20 mm or more measured by a mercury intrusion method of 0.1 cc / g or more, particularly 0.3 to 5 cc / g. Such silicates contain adsorbed water and interlayer water when treated in aqueous solution. Here, adsorbed water is water adsorbed on the silicate surface or crystal fracture surface, and interlayer water is water existing between crystal layers.
The silicate is preferably used after removing adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is a temperature range in which the adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the weight loss of the silicate after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when a silicate having a weight loss adjusted to 3% by weight or less is used, the same weight loss state is maintained even when contacting the component (A) and the component (C). It is preferable to handle them.

Composition of silicate after acid treatment:
The acid-treated silicate which is the component (B) according to the present invention has an Al / Si atomic ratio of 0.01 to 0.29, preferably 0.03 to 0.25, and more preferably. Is preferably in the range of 0.05 to 0.23 in view of the activity of the polymerization catalyst and the molecular weight of the olefin polymer.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and the method for controlling the Al / Si atomic ratio is controlled by adjusting the acid species for acid treatment, the acid concentration, the acid treatment time, and the temperature. can do.
Aluminum and silicon in the silicate are measured by a method in which a calibration curve is prepared by a chemical analysis method by JIS method and quantified by fluorescent X-rays.

(2-3) Organoaluminum Compound An example of the organoaluminum compound is represented by the following general formula (VI).
AlR _a X _3-a [VI]
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, diethylaluminum monochloride, diethylaluminum mono Examples include halogens such as methoxide or alkoxy-containing alkylaluminum. Of these, trialkylaluminum is preferred, and most preferred is trihexylaluminum or trioctylaluminum. Two or more of the above organoaluminum compounds may be used in combination.

(3) Catalyst preparation method In the preparation method of the catalyst for olefin polymerization according to the present invention, the contact method of component (A), component (B) and component (C) is not particularly limited, but the following method: Can be illustrated.
(I) Method of contacting component (A) and component (B) (ii) Method of adding component (C) after contacting component (A) and component (B) (iii) Component (A ) And component (C) are contacted and then component (B) is added (iv) Component (B) and component (C) are contacted and then component (A) is added (v) ) Each component (A), (B), (C) is contacted simultaneously.

Furthermore, different types of components may be used as a mixture in each component, or the components may be contacted in different orders. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
Alternatively, the component (B) and the component (C) may be contacted and then the mixture of the component (A) and the component (C) may be added, and the components may be divided and brought into contact with each component.
The contact of each of the components (A), (B), and (C) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. The contact can be performed at a temperature between −20 ° C. and the boiling point of the solvent, and is preferably performed at a temperature between room temperature and the boiling point of the solvent.

(3-1) Catalyst preparation method when a boron compound or an organoaluminum oxy compound is used as the component (B) In the polymerization catalyst according to the present invention, a preferred component (B) is a boron compound or an organoaluminum oxy compound. Particularly preferred are boron compounds.
When component (B) is an organoaluminum oxy compound, the molar ratio of component (A) to component (B) is 1: 0.1 to 1: 100,000. When component (B) is a boron compound, the molar ratio of component (A) to component (B) is preferably in the range of 1: 0.1 to 1: 100. When component (C) is used, the molar ratio of component (A) to component (C) is preferably in the range of 1: 0.1 to 1: 10,000.

(3-2) Catalyst preparation method when silicate is used as component (B) In the polymerization catalyst according to the present invention, when component (B) is silicate, preferred component (A), component (B) and component The amount of (C) used is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol for the metallocene compound of component (A) with respect to 1 g of component (B). The amount of the component (C) used is an Al / metallocene compound molar ratio of 0.1 to 100,000, preferably 1 to 10,000. These use ratios show examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

(3-3) Catalyst preparation method when a fine particle carrier other than silicate is used When component (B) is other than silicate, the component (A), component (B) and / or component (C) of the present invention is added. It can be used for polymerization by being supported on a fine particle carrier other than silicate.
Examples of the fine particle carrier to be used include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.

Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.
Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Table 1-14 Group elements include, for _{example, SiO 2, Al 2 O 3} , MgO, CaO, B 2 O 3, TiO 2, _{ZrO 2, Fe 2 O 3,} Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · S i O 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2 Examples include various natural or synthetic single oxides or composite oxides such as Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO.
Here, the above formula represents not a molecular formula but only a composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited.
In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides, silica, alumina and the like is particularly preferable.

These inorganic carriers are usually baked in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl group is 0.8 to 1.5 mmol / g. It is preferable to adjust to use.
The properties of these inorganic carriers are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1,000 mm, preferably 50 to 500 mm, and the specific surface area is 150. ˜1,000 m ² / g, preferably 200 to 700 m ² / g, pore volume is 0.3 to 2.5 cm ³ / g, preferably 0.5 to 2.0 cm ³ / g, and apparent specific gravity is 0 It is preferable to use an inorganic carrier having 20 to 0.50 g / cm ³ , preferably 0.25 to 0.3, 5 g / cm ³ .
Of course, the above-mentioned inorganic carrier can be used as it is, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum It can be used after contacting an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

The contact method of each component when obtaining a catalyst for olefin polymerization comprising a component (A), a compound that reacts with the component (A) to form an ion pair (component B), and a fine particle carrier is not particularly limited, For example, the following method can be arbitrarily adopted.
(I) After contacting the component (A) and the component (B), the fine particle carrier is contacted.
(II) After contacting the component (A) and the fine particle carrier, the component (B) is contacted.
(III) The component (B) and the fine particle carrier are contacted, and then the component (A) is contacted.
Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane or dodecane is usually used in an inert atmosphere such as nitrogen or argon. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.

This contact is usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.
In contacting the component A and the component B with the fine particle carrier, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble and an aliphatic in which some component is insoluble or hardly soluble, or Any alicyclic hydrocarbon solvent can be used.
In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the preceding catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid, or part or all of the soluble solvent is once removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

In the present invention, the proportions of component A, component B, and particulate carrier are not particularly limited, but the following ranges are preferred.
When an organoaluminum oxy compound is used as component B, the atomic ratio (Al / M) of the organoaluminum oxy compound aluminum to the transition metal (M) in component A is usually 1 to 100,000, preferably 5 to 1,000, more preferably in the range of 50 to 400, and when a borane compound or a borate compound is used, the atomic ratio (B / M) of boron to the transition metal (M) in Component A is usually It is desirable to select in the range of 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (component B) that forms an ion pair, for each compound in the mixture, with respect to the transition metal (M) It is desirable to select at the same usage ratio as above.
The amount of the particulate carrier used is 1 g per 0.0001 to 5 mmol of transition metal in component A, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol.

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

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

(4) Prepolymerization Before using the catalyst containing components (A), (B) and (C) as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, You may perform the prepolymerization process which prepolymerizes small amounts of olefins, such as 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene. As the prepolymerization method, a known method can be used.

4). Production Method of Olefin Polymer (1) Polymerization Mode In the present invention, the polymerization mode is such that the polymerization catalyst containing the metallocene compound represented by the general formula [I] and the monomer efficiently contact each other to polymerize or copolymerize olefin. Any style can be adopted if it can be done.
Specifically, a slurry method and a solution method using an inert solvent, a bulk polymerization method using a olefin monomer as a solvent without using an inert solvent, and a high-pressure ion polymerization, or each monomer using substantially no liquid solvent. For example, a gas phase polymerization method for keeping the gas in a gaseous state can be employed. Preferably, solution polymerization and high pressure ionic polymerization can be mentioned.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. The combination of polymerization types is not particularly limited, and can be a solution polymerization two-stage, a bulk polymerization two-stage, a gas phase polymerization after bulk polymerization, a two-stage gas phase polymerization, and the number of polymerization stages more than that. It is also possible to manufacture with.

Moreover, even if a component for removing water, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, the organoaluminum oxy compound, and modified by modifying the organoaluminum compound with alcohols or phenols. Organic aluminum compounds, organic zinc compounds such as diethyl zinc and dibutyl zinc, organic magnesium compounds such as diethyl magnesium, dibutyl magnesium and ethyl butyl magnesium, and Grignard compounds such as ethyl magnesium chloride and butyl magnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum are preferable, and triisobutylaluminum, trihexylaluminum, and trioctylaluminum are particularly preferable.

The molecular weight of the produced polymer can be adjusted by changing the polymerization conditions such as the polymerization temperature, the concentration of the olefin monomer, and the molar ratio of the catalyst. Further, the molecular weight can be adjusted effectively by adding hydrogen, the above-mentioned scavengers or the like as a chain transfer agent to the polymerization reaction system.
The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure and polymerization temperature without any trouble.

(2) Polymerization monomer
In the present invention, the olefin refers to an unsaturated hydrocarbon, and the “α-olefin” refers to an olefin having a double bond in the α-position (between the extreme carbon and the next carbon). Specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1- Examples include pentene, styrene, vinylcyclohexane, diene, triene, and cyclic olefin.

(3) Ethylene Homopolymerization Method and Copolymerization Method In the present invention, ethylene polymerization or ethylene / α-olefin copolymerization may be mentioned as a more preferable polymerization using the above-mentioned catalyst for olefin polymerization.
Further, as a preferable polymerization method, a solution method using an inert solvent or a polymerization method using an olefin monomer as a solvent without substantially using an inert solvent, for example, high pressure ion polymerization is preferable. The polymerization temperature is generally 0-300 ^° C.
In the gas phase polymerization method, bulk polymerization method, and slurry polymerization method, a preferable polymerization temperature is 40 to 120 ° C., more preferably 50 to 100 ° C., and a preferable polymerization pressure is 0.1 MPa to 10 MPa, preferably 1 to 5 MPa. is there.
In the solution polymerization, a preferable polymerization temperature is 0 to 170 ° C., more preferably 50 to 170 ° C., further preferably 120 to 170 ° C., and a preferable polymerization pressure is 0.1 MPa to 10 MPa, preferably 1 to 5 MPa.
In the high-pressure ion polymerization, a preferable polymerization temperature is 140 to 300 ° C, more preferably 160 to 260 ° C, and a preferable polymerization pressure is 40 to 150 MPa, and more preferably 50 to 100 MPa.

(4) Comonomers The α-olefins which are comonomers include those having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms, specifically, propylene, 1-butene, 1-hexene, 1-octene, Examples include 4-methyl-1-pentene.
As for the α-olefins, two or more types of α-olefins can be copolymerized with ethylene.
The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. When ethylene and another α-olefin are copolymerized, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers, but is preferably 50 mol% or less. Of course, a small amount of a comonomer other than ethylene or α-olefin can be used. In this case, aromatic vinyls such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1, Dienes such as 5-hexadiene, 1,4-hexadiene, 1,7-octadiene, 4-vinyl-1-cyclohexene, 5-vinyl-norbornene, 5-ethylidene-2-norbornene and norbornadiene, and cyclic such as norbornene and cyclopentene A compound etc. can be mentioned.

In the following, the present invention will be described in more detail with reference to examples and comparative examples, and the superiority of the present invention and the superiority in the configuration of the present invention will be demonstrated, but the present invention is limited by these examples. It is not a thing.
In addition, the measuring methods of various physical properties of the polymers obtained in the examples and comparative examples are as follows.

(1) Melt flow rate (MFR)
According to JIS K7210 (2004 edition), Annex A, Table 1-Condition D, a measured value at a test temperature of 190 ° C. and a nominal load of 2.16 kg is shown as MFR.

(2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The generated ethylene polymer was subjected to gel permeation chromatography (GPC) under the following conditions to determine the number average molecular weight (Mn) and the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) was calculated.
[Gel permeation chromatograph measurement conditions]
Apparatus: Waters Alliance GPC2000 model Column: Shodex-HT806M Solvent: 1,2-dichlorobenzene Flow rate: 1 ml / min Temperature: 145 ° C. Universal evaluation was performed using a monodisperse polystyrene fraction.
Measurement was performed under the above-mentioned conditions, and a chromatogram was recorded at a sampling interval of 1 second. This chromatogram is shown in “Size Exclusion Chromatography” written by Sadao Mori, Chapter 4 p. The differential molecular weight distribution curve and average molecular weight (Mn, Mw) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram was corrected by the following equation.
H ′ = [1.032 + 189.2 / M (PE)] × H
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

(3) Density The density was measured in accordance with Method A (underwater substitution method) among the test methods described in JIS K7112 (2004 edition).

(4) Comonomer content The monomer composition of the ethylene / 1-hexene copolymer is described in the literature (Anal. Chem. 20).
04, 5734-5747) and calculated by NMR analysis.
[NMR measurement conditions]
As the solvent, a 1,2-dichlorobenzene / heavy bromobenzene (4/1) mixed solvent was used. The sample concentration was 150 mg / 2.4 mL. After introducing the sample into the NMR sample tube, the sample was sufficiently substituted with nitrogen, and then dissolved in a 130 ° C. heat block to obtain a uniform solution. Measurement was performed at 130 ° C. using a Bruker Avance III Cryo-NMR, 10 mmφ cryoprobe.
Measurement conditions are as follows: 1H-NMR: solvent presaturation method, 18 ° pulse, total 256 times, 13C-NMR: proton complete decouple condition, 90 ° pulse, total 512 times.

(5) Melting point (Tm)
Using an EXSTAR6000 DSC differential scanning calorimeter manufactured by Seiko Denshi Co., Ltd., a sample (about 5 mg) was melted at 180 ° C. for 5 minutes, cooled to −20 ° C. at a rate of 10 ° C./min, and then at −20 ° C. for 5 minutes After being held, the melting curve was obtained by heating up to 180 ° C. at a rate of 10 ° C./min. The peak top temperature of the main endothermic peak in the final temperature increase stage performed to obtain the melting curve was defined as the melting point Tm.

(6) Evaluation of measurement The molecular weight of the obtained polymer can be evaluated by carrying out the above measurements (1) and (2). That is, it can be said that the smaller the MFR value obtained from the measurement (1), and the higher the number average molecular weight obtained in the measurement (2), the higher the molecular weight.
In addition, by carrying out the above measurements (3), (4) and (5), the magnitude of the comonomer in the copolymer, 1-hexene which is an α-olefin in this example and comparative example, is evaluated. be able to. It can be said that the smaller the density value obtained from the measurement (3), the higher the hexene content obtained in (4), and (5) the lower the melting point, the higher the comonomer content. In other words, the lower the density of the polymer obtained under the same polymerization temperature and the same monomer ratio using different catalysts, the higher the hexene content or the lower the melting point, It can be said that the performance that can be taken in is excellent.

1. Synthesis of metallocene compounds Metallocene compound A: Synthesis of isopropylidenebis (5-methyl-4-phenyl-1-indenyl) dimethylhafnium

(1) Synthesis of 5-methyl-4phenylindene Synthesized according to the method described in JP 2012-167032 A.

(2) Synthesis of 2,2-bis (5-methyl-4-phenyl-inden-1-yl) propane In a 200 mL glass reaction vessel, 10.6 g (51.4 mmol) of 5-methyl-4-phenylindene , 85 mL of DME and 3.89 g (69.3 mmol) of potassium hydroxide were added, and the mixture was heated to reflux at 90 ° C. for 2 hours. The reaction solution was cooled to 0 ° C., 1.90 mL (25.8 mmol) of acetone was added, and the mixture was heated to reflux at 90 ° C. for 5 hours. The reaction solution was cooled to room temperature, then cooled to 0 ° C. with an ice bath, 6.0 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 15 minutes. The solvent was distilled off under reduced pressure, 30 mL of distilled water and 30 mL of n-hexane were added and stirred, then filtered through filter paper, and the solid on the filter paper was washed with distilled water, ethanol, and hexane in this order to obtain 2,2-bis ( 6.91 g of 5-methyl-4-phenyl-inden-1-yl) propane was obtained as a white solid (yield 59%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.43 (t, 4H), 7.35 (t, 2H), 7.30-7.20 (m, 6H), 7.00 (t, 2H) , 6.42 (t, 2H), 3.11 (d, 4H), 2.08 (s, 6H), 1.75 (s, 6H).

(3) Synthesis of racemic-isopropylidenebis (5-methyl-4-phenyl-1-indenyl) hafnium dichloride Into a 200 mL glass reaction vessel, 2,2-bis (5-methyl-4-phenyl-indene-1 -Yl) Propane (2.72 g, 6.00 mmol) and diethyl ether (60 ml) were added, and the mixture was cooled to 0 ° C. in an ice bath. To this, 7.8 ml (12.3 mmol) of a 1.58 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 60 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. Thereto was added 1.92 g (6.00 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 16 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 35:65.
The solvent of the reaction solution was distilled off under reduced pressure, 15 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, filtered through a glass frit, and the solid was washed twice with 3 mL of DME, whereby a racemic isopropylidenebis (5-methyl-4-phenyl-1-indenyl) hafnium dichloride containing lithium chloride was obtained. Was obtained as an orange solid.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.63 (d, 2H), 7.54 (d, 2H), 7.40-7.30 (m, 6H), 7.18 (d, 2H) 6.97 (d, 2H), 6.17 (d, 2H), 6.01 (d, 2H), 2.34 (s, 6H), 2.27 (s, 6H).

(4) Synthesis of isopropylidenebis (5-methyl-4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, isopropylidenebis (5-methyl-4-phenyl-) containing the above lithium chloride was added. 1-Indenyl) hafnium dichloride (1.00 g, content is 1.43 mmol or less) and toluene (50 mL) were added. A 3.0 mol / L methylmagnesium bromide-diethyl ether solution (4.8 mL, 14.4 mmol) was added at room temperature. After dropwise addition, the mixture was stirred at 90 ° C. for 1.5 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 1.45 mL (11.5 mmol) of chlorotrimethylsilane was added, and the mixture was stirred at room temperature for 15 minutes, followed by 3.0 mL (35.1 mmol) of 1,4-dioxane. The mixture was further stirred at room temperature for 30 minutes. The suspension was filtered through celite, and the solvent was evaporated under reduced pressure. The obtained yellow solid was suspended in 5 mL of hexane, filtered through a glass frit, and the solid was washed twice with 3 mL of hexane, whereby a racemic isopropylidenebis (5-methyl-4-phenyl-1-indenyl) dimethylhafnium was obtained. 703 mg of the product was obtained as a yellow solid. The yield was 63% from the ligand (assuming that all dichloro form was used).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.66 (d, 2H), 7.30 (d, 4H), 7.24 (br, 4H), 7.12 (dt, 4H), 6 .79 (d, 2H), 6.38 (d, 2H), 5.58 (d, 2H), 2.22 (s, 6H), 1.79 (s, 6H), -0.93 (s , 6H).

  2. Metallocene compound B (comparative example): Synthesis of dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) dimethylhafnium

(1) Synthesis of racemic-dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) hafnium dichloride was synthesized according to the method described in JP-A-2001-253913.

(2) Synthesis of racemic-dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) hafnium After adding 1.48 g (2.07 mmol) of dichloride and 60 mL of toluene, 14.0 mL (13.9 mmol) of a 0.99 mol / L methylmagnesium bromide-tetrahydrofuran solution was added dropwise at room temperature, and then 3 ° C. at 80 ° C. Stir for 5 hours. After cooling the reaction solution to 0 ° C. with an ice bath, 1.0 mL (7.9 mmol) of chlorotrimethylsilane was added, and the mixture was stirred at room temperature for 30 minutes, followed by addition of 2.7 mL (32 mmol) of 1,4-dioxane, Stir at room temperature for another 30 minutes. The suspension was filtered through Celite, and the filtrate was concentrated under reduced pressure, and then allowed to stand at -20 ° C. and recrystallized, whereby a racemic dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) dimethylhafnium was obtained. Was obtained as yellow crystals (yield 23%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.75 (dd, 4H), 7.49 (d, 2H), 7.27 (d, 2H) 7.23 (t, 4H), 7. 12 (t, 2H), 7.03 (s, 2H), 6.85 (dd, 2H), 2.00 (s, 6H), 0.80 (s, 6H), -0.83 (s, 6H).

  3. Metallocene Compound C (Comparative Example): Synthesis of dimethylsilylene bis (2-isopropyl-4-phenyl-1-indenyl) dimethylhafnium

(1) Synthesis of dimethylbis (2-isopropyl-4-phenylinden-1-yl) silane In a 200 ml glass reaction vessel, 2-isopropyl-4-phenyl-indene 2.0
0 g (8.52 mmol) and 30 ml of THF were added, and the mixture was cooled to −78 ° C. in a dry ice-methanol bath. To this, 4.10 ml (10.2 mmol) of a 2.5 mol / L n-butyllithium-hexane solution was added dropwise and stirred at room temperature for 4 hours. The mixture was cooled to −78 ° C., 0.34 mg (0.42 mmol) of 1-methylimidazole and 0.50 mL (4.26 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred at room temperature for 1 hour. The solvent was distilled off under reduced pressure, 30 mL of hexane was added, the suspension was filtered, and the solvent of the filtrate was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent, petroleum ether) to obtain 1.00 g (yield 45) of a light yellow solid of dimethylbis (2-isopropyl-4-phenylinden-1-yl) silane. %).

(2) Synthesis of racemic-dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, dimethylbis (2-isopropyl-4-phenylinden-1-yl) silane 3.34 g (6.36 mmol) and 50 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To this, 8.0 ml (12.8 mmol) of 1.62 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred for 2.5 hours. The solvent of the reaction solution was distilled off under reduced pressure, 65 ml of toluene was added, and the solution was cooled to −70 ° C. in a dry ice-heptane bath. Thereto was added 2.04 g (6.37 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 17 hours while gradually returning to room temperature.
The reaction solution was filtered through celite, and the filtrate was repeatedly concentrated and recrystallized to obtain a mixture of racemic mesyl: meso isomer 77:23 of dimethylsilylenebis (2-isopropyl-4-phenyl-indenyl) hafnium dichloride. .20 g was obtained.
To this mixture, 60 mg of anhydrous lithium chloride and 6 mL of 1,2-dimethoxyethane were added and stirred at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, filtered through a glass frit, and the solid was washed twice with 5 mL of DME, whereby the racemic dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) hafnium dichloride was converted into an orange solid. 464 mg was obtained (yield 10%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.74-7.70 (m, 6H), 7.44 (t, 4H), 7.40-7.28 (m, 4H), 7.07 ( dd, 2H), 6.89 (s, 2H), 3.31 (sep, 2H), 1.36 (s, 6H), 1.14 (d, 6H), 1.11 (d, 6H).

(3) Synthesis of racemic-dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) hafnium 444 mg (0.575 mmol) of dichloride and 20 mL of toluene were added, and 4.3 mL (4.6 mmol) of a 1.06 mol / L methyl lithium-diethyl ether solution was added dropwise at room temperature, followed by stirring at 80 ° C. for 5 hours. . The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure, and then allowed to stand at -20 ° C and recrystallized, whereby a racemic dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) dimethylhafnium was obtained. Was obtained as yellow crystals (yield 48%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.80 (dd, 4H), 7.50 (d, 2H), 7.36-7.16 (m, 8H) 7.11 (t, 2H) ), 6.85 (t, 2H), 3.06 (sep, 2H), 1.15 (d, 6H), 0.95 (d, 6H), -0.83 (s, 6H).

  4). Metallocene Compound D (Comparative Example): Synthesis of dimethylsilylene bis (2,4-dimethyl-1-indenyl) dimethylhafnium

(1) Synthesis of dimethylbis (2,4-dimethyl-inden-1-yl) silane Synthesized according to the method described in Japanese Patent No. 3389265.

(2) Synthesis of racemic-dimethylsilylenebis (2,4-dimethyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, dimethylbis (2-methyl-4-methyl-inden-1-yl) silane 5 .50 g (16.0 mmol) and 60 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To this, 14.0 ml (35.2 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution was added dropwise, followed by stirring at room temperature for 2 hours and at 50 ° C. for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 60 ml of diethyl ether was added, and the solution was cooled to −70 ° C. in a dry ice-heptane bath. Thereto was added 5.60 g (17.6 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 4 hours while gradually returning to room temperature.
After adding 150 mL of dichloromethane and filtering through Celite, the filtrate was concentrated and recrystallized to obtain 0.30 g of a racemic dimethylsilylene bis (2,4-dimethyl-indenyl) hafnium dichloride as a yellow solid.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.56 (d, 2H), 7.10 (d, 2H), 6.93 (dd, 2H), 6.70 (s, 2H), 2.37 (S, 6H), 2.33 (s, 6H), 1.31 (s, 6H).

(3) Synthesis of racemic-dimethylsilylenebis (2,4-dimethyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, dimethylsilylenebis (2,4-dimethyl-indenyl) hafnium dichloride 0.592 g (1 0.000 mmol) and 30 mL of toluene were added. To this, 6.8 mL (6.7 mmol) of a 0.99 mol / L methylmagnesium bromide-tetrahydrofuran solution was added dropwise at room temperature, followed by stirring at 80 ° C. for 7.5 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 0.60 mL (4.7 mmol) of chlorotrimethylsilane was added, stirred at room temperature for 30 minutes, and then 1.3 mL (15 mmol) of 1,4-dioxane was added, Stir at room temperature for another 30 minutes. The suspension was filtered through celite, and the solvent was distilled off under reduced pressure. The resulting yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed twice with 3 mL of hexane. A racemic form of silylene bis (2,4-dimethyl-indenyl) dimethylhafnium was obtained as a white solid (310 mg, yield 56).
%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.39 (d, 2H), 6.96 (d, 2H), 6.79 (dd, 2H), 6.57 (s, 2H), 2 .28 (s, 6H), 2.03 (s, 6H), 0.80 (s, 6H), -1.08 (s, 6H).

  5. Metallocene compound E (comparative example): Synthesis of dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl) dimethylhafnium

(1) Synthesis of dimethylbis (2-methyl-4-isopropylinden-1-yl) silane The compound was synthesized according to the method described in Japanese Patent No. 3482412.

(2) Synthesis of racemic-dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, dimethylbis (2-methyl-4-isopropylinden-1-yl) silane 3.15 g (7.86 mmol) and 45 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To this was added dropwise 6.6 ml (16.5 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred at room temperature for 2 hours and at 50 ° C. for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 45 ml of diethyl ether was added, and the solution was cooled to -70 ° C in a dry ice-heptane bath. Thereto was added 2.64 g (8.26 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 16 hours while gradually returning to room temperature.
The reaction solution was filtered, and the resulting solid was extracted with 20 mL of dichloromethane and filtered again. Then, the solvent of the filtrate was distilled off under reduced pressure, thereby dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl) hafnium. 0.50 g of a racemic dichloride as a yellow solid was obtained.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.54 (d, 2H), 7.16 (d, 2H), 6.98 (dd, 2H), 6.76 (s, 2H), 3.06 (Sep, 2H), 2.34 (s, 6H), 1.34 (d, 6H), 1.28 (s, 6H), 1.25 (d, 6H).

(3) Synthesis of racemic-dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl) hafnium was added. Dichlorochloride (0.573 g, 0.884 mmol) and toluene (27 mL) were added. 6.2 mL (6.1 mmol) of a 0.99 mol / L methylmagnesium bromide-tetrahydrofuran solution was added dropwise thereto at room temperature, and the mixture was stirred at 80 ° C. for 5 hours. After cooling the reaction solution to 0 ° C. with an ice bath, 0.45 mL (3.6 mmol) of chlorotrimethylsilane was added, stirred at room temperature for 30 minutes, and then 0.90 mL (11 mmol) of 1,4-dioxane was added, Stir at room temperature for another 30 minutes. The suspension was filtered through celite, and the solvent was distilled off under reduced pressure. The resulting yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed twice with 3 mL of hexane. 382 mg of a racemic form of silylene bis (2-methyl-4-isopropyl-1-indenyl) dimethylhafnium was obtained as a white solid (yield 71%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.41 (d, 2H), 7.10 (d, 2H), 6.82 (t, 2H), 6.73 (s, 2H), 3 .11 (sep, 2H), 2.07 (s, 6H), 1.36 (d, 2H), 1.27 (d, 6H), 0.83 (s, 6H), -1.06 (s , 6H).

  5. Metallocene compound F (comparative example): Synthesis of cyclobutylidenebis (1-indenyl) dimethylhafnium

(1) Synthesis of 1,1-bis (1-indenyl) cyclobutane Into a 200 mL glass reaction vessel, 25.0 g (215 mmol) of indene, 250 mL of DME, and 27.0 g (480 mmol) of potassium hydroxide were added. Heated to reflux for hours. The reaction solution was cooled to 0 ° C., 8.40 g (120 mmol) of cyclobutanone was added, and the mixture was heated to reflux at 90 ° C. for 6 hours. The reaction solution is cooled to room temperature, 200 mL of distilled water is added, and then transferred to a separatory funnel and extracted twice with ethyl acetate. The resulting ethyl acetate solution is washed successively with saturated brine and distilled water, and sodium sulfate. And dried. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent, petroleum ether) to obtain 1,1-bis (1-indenyl) cyclobutane. 12.0 g was obtained as a white solid (39% yield).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.39 (t, 4H), 7.11 (quint, 4H), 6.62 (s, 2H), 3.40 (s, 4H), 2.73 (T, 4H), 2.09 (quint, 2H).

(2) Synthesis of racemic-cyclobutylidenebis (1-indenyl) hafnium dichloride In a 200 mL glass reaction vessel, 2.84 g (10.0 mmol) of 1,1-bis (1-indenyl) cyclobutane and 100 ml of diethyl ether were added. In addition, it was cooled to -70 ° C. with a dry ice-heptane bath. To this, 12.4 ml (20.5 mmol) of a 1.64 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 115 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. Thereto was added 3.20 g (10.0 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 17 hours while gradually returning to room temperature.
The solvent of the reaction solution was distilled off under reduced pressure, 26 mL of 1,2-dimethoxyethane was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, filtered through a glass frit, and the resulting solid was extracted with 130 mL of dichloromethane and filtered through celite. The filtrate was dried under reduced pressure to obtain 3.76 g of a racemic form of cyclobutylidenebis (1-indenyl) hafnium dichloride as a yellow solid (yield 71%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.51 (d, 2H), 7.48 (d, 2H), 7.27 (dd, 2H), 6.98 (dd, 2H), 6.53 (D, 2H), 5.97 (d, 2H), 3.54 (quart, 2H), 3.12 (quart, 2H), 2.46 (quint, 2H).

(3) Cyclobutylidenebis (1-indenyl) dimethylhafnium synthesis Here, 1.50 g (2.82 mmol) of cyclobutylidenebis (1-indenyl) hafnium dichloride and 70 mL of toluene were added to a 200 ml glass reaction vessel. 3.
After dropwise addition of 6.6 mL (19.8 mmol) of a 0 mol / L methylmagnesium bromide-diethyl ether solution at room temperature, the mixture was stirred at 80 ° C. for 7 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 1.75 mL (13.9 mmol) of chlorotrimethylsilane was added and stirred at room temperature for 30 minutes, followed by 3.50 mL (40.9 mmol) of 1,4-dioxane. The mixture was further stirred at room temperature for 1 hour. The suspension was filtered through celite, and the solvent was evaporated under reduced pressure. The obtained yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed twice with 5 mL of hexane to obtain 810 mg of a racemic cyclobutylidenebis (indenyl) dimethylhafnium as a yellow solid. (Yield 59%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.37 (d, 2H), 7.11 (dd, 2H), 7.05 (dd, 2H), 7.23 (dd, 2H), 6 .33 (d, 2H), 5.42 (d, 2H), 2.98 (quart, 2H), 2.54 (quart, 2H), 2.02 (quant, 2H), -1.16 (s) , 6H).

6). Batch Solution Polymerization: Ethylene / 1-hexene copolymerization (Example 1) Ethylene / 1-hexene copolymerization using metallocene compound A 2.3L stainless steel autoclave thoroughly dried and replaced with nitrogen (stirring, temperature control) Toluene 1,000 mL and 1-hexene 58 mL were added to the apparatus and heated to 150 ° C. After the temperature in the reactor was stabilized, the pressure was increased to 0.7 MPaG with nitrogen and further to 2.7 MPaG with ethylene. Thereafter, 0.1 mmol of tri (n-octyl) aluminum was injected with nitrogen, and a metallocene compound A 0.08 μmol-toluene 1 mL solution and a cocatalyst [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F _{5 4} ] A 0.04 μmol-toluene 1 mL solution was contacted at room temperature under nitrogen and then a solution stirred for 10 minutes at room temperature was injected with nitrogen to initiate polymerization. Then, after stirring for 5 minutes while controlling the internal pressure to be 2.7 MPa, the reaction was stopped by injecting ethanol with nitrogen, and the polymer was obtained by drying after cooling. Polymer yield 2.8 g.
Polymer index: density = 0.816 g / cm ³ , MFR = 0.69 g / 10 min, weight average molecular weight Mw = 131,000, number average molecular weight Mn = 75,700, Mw / Mn = 1.73, Tm = 62. 6 ° C, 1-hexene content 11.0 mol%

(Comparative Example 1)
A polymerization operation similar to that of Example 1 was carried out except that 0.48 μmol of metallocene compound B was used instead of metallocene compound A and 0.24 μmol of promoter was used. Polymer yield 13.6 g.
Polymer index: Density = 0.8764 g / cm ³ , MFR = 51 g / 10 min, Mw = 41,800, Mn = 10,300, Mw / Mn = 4.04, Tm = 67.0
° C, 1-hexene content 12.3 mol%.

(Comparative Example 2)
The same polymerization operation as in Example 1 was carried out except that 0.70 μmol of metallocene compound C was used instead of metallocene compound A, 0.35 μmol of cocatalyst was used, and the polymerization time was 18 minutes. Polymer yield 6.0 g.
Polymer index: Mw = 6,800, Mn = 3,100, Mw / Mn = 2.17
, Tm = 62.0 ° C.

(Comparative Example 3)
The same polymerization operation as in Example 1 was carried out except that 0.10 μmol of metallocene compound D was used instead of metallocene compound A and 0.05 μmol of promoter was used. Polymer yield 6.0 g.
Polymer index: density = 0.9053 g / cm ³ , MFR = 0.47 g / 10 min, Mw = 131,900, Mn = 32,500, Mw / Mn = 4.06, Tm = 88
. 3 ° C.

(Comparative Example 4)
The same polymerization operation as in Example 1 was carried out except that 0.20 μmol of metallocene compound E was used instead of metallocene compound A, 0.10 μmol of cocatalyst was used, and the polymerization time was 12 minutes. Polymer yield 6.8g.
Polymer index: density = 0.0903 g / cm ³ , MFR = 0.35 g / 10 min, Mw = 144,100, Mn = 12,800, Mw / Mn = 11.99, Tm = 95.8 ° C.

(Comparative Example 5)
The same polymerization operation as in Example 1 was performed except that 0.10 μmol of metallocene compound F was used instead of metallocene compound A and 0.05 μmol of promoter was used. Polymer yield 7.0 g.
Polymer index: density = 0.8962 g / cm ³ , MFR = 0.51 g / 10 min, Mw = 120,900, Mn = 63,600, Mw / Mn = 1.90, Tm = 83
. 7 ° C.

(Example 2)
The same polymerization operation as in Example 1 was carried out except that 0.10 μmol of metallocene compound A and 0.05 μmol of promoter were used, the amount of 1-hexene used was 62 mL, the polymerization temperature was 125 ° C., and the polymerization time was 10 minutes. . Polymer yield 5.0 g.
Polymer index: density = 0.8868 g / cm ³ , MFR = 0.10 g / 10 min, Mw = 234,800, Mn = 111,100, Mw / Mn = 2.11, Tm = 63.0 ° C., 1-hexene Content 10.5 mol%

(Comparative Example 6)
Example 1 except that 0.10 μmol of metallocene compound B was used instead of metallocene compound A, 0.05 μmol of cocatalyst was used, the amount of 1-hexene used was 62 mL, the polymerization temperature was 125 ° C., and the polymerization time was 4 minutes. The same polymerization operation was carried out. Polymer yield 10.9 g.
Polymer index: density = 0.8750 g / cm ³ , MFR = 0.44 g / 10 min, Mw = 147,200, Mn = 68,100, Mw / Mn = 2.16, Tm = 58.6 ° C.

  Table 1. Performance comparison between metallocene compounds under the same polymerization temperature (150 ° C)

  Table 2 Performance comparison between metallocene compounds at different polymerization temperatures

[Consideration of Comparison Results of Examples and Comparative Examples]
As is clear from Table 1, the catalyst of the present invention has a relatively low density and Tm by comparing Example 1 which is a polymerization result of the same polymerization temperature and the same monomer ratio with Comparative Examples 1 to 5. It is clear that it is possible to give a high molecular weight ethylene copolymer while exhibiting excellent copolymerizability.
Catalysts B and C having an alkyl group at the 2-position of the indenyl ring and a phenyl group at the 4-position have a relatively low density and Tm, so that the copolymerizability is excellent but a high molecular weight polymer cannot be provided.
On the other hand, Catalyst F, which has no phenyl group at the 4-position of the indenyl ring and the substituent at the 2-position is a hydrogen atom, gives a high molecular weight polymer, but has a relatively high Tm, and therefore exhibits excellent copolymerizability. Absent. Further, the catalysts D and E in which the 4-position substituent does not have a phenyl group and the 2-position substituent is an alkyl group are neither copolymerizable nor the molecular weight of the produced polymer is sufficient.
That is, only the catalyst of the present invention, which is a hydrogen atom at the 2-position of the indenyl ring, a phenyl group at the 4-position, and a substituent at the 5-position, produces a high molecular weight polymer and has excellent copolymerization. It can be seen that both sexes can be achieved.
Also, in Table 2, it is clear that the superiority of the catalyst of the present invention extends over a wide range of polymerization temperatures by comparing Example 2 and Comparative Example 6 which are polymerization results at different polymerization temperatures.

As is clear from the above, by using the metallocene compound of the present invention as a polymerization catalyst, in the olefin copolymerization, a high molecular weight olefin copolymer is maintained while maintaining excellent olefin copolymerization compared to conventional complex catalyst systems. A polymer can be obtained. In particular, a low density and high molecular weight ethylene copolymer can be produced.
As a result, the olefin polymerization catalyst of the present invention and the olefin polymer production method using the olefin polymerization catalyst can be polymerized at industrially advantageous polymerization temperatures and conditions, and have extremely high industrial value. large.

Claims (10)

A metallocene compound represented by the following general formula [I]:

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon number 6 to 20 aryl groups), provided that at least one of R ⁴ and R ¹⁴ is other than a hydrogen atom, and the adjacent groups of R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ together with the atoms connecting them. One or more aromatic rings or Or to form an aliphatic ring, or ^{R 4} and ^R 5, ^{R 4} and ^{R 9, R 14} and ^{R 15} or ^{R 14} and ^{R 19} is one together with the atoms connecting them aromatic ring or aliphatic May form a family ring;
Q is a carbon atom, a silicon atom or a germanium atom, n is a natural number of 1 to 3,
R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Aryl group, C6-C10 fluoroaryl group, C6-C10 aryloxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C7-C40 alkyl An aryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ may be combined with atoms connecting them to form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from a C1-C20 alkyl group substituted with a silyl group having a carbon number, a C1-C10 amino group, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair, Each may be the same or different, and X ¹ and X ² may be combined with the atoms connecting them to form one ring. ] 2. The metallocene compound according to claim 1, wherein in general formula [I], R ⁴ and R ¹⁴ are the same or different and are alkyl groups having 1 to 10 carbon atoms. In the general formula [I], R ^{1 to} R ³ and R ^{11 to} R ¹³ are hydrogen atoms, R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different, and are a hydrogen atom and 1 to 10 carbon atoms. The metallocene compound according to claim 1, wherein the metallocene compound is an alkyl group having a carbon number of 6 to 10 and an aryl group having 6 to 10 carbon atoms. The metallocene compound according to claim 1, wherein n is 1 in the general formula [I]. In general formula [I], M is Hf, The metallocene compound of any one of Claims 1-4 characterized by the above-mentioned. An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metallocene compound component (B) according to any one of claims 1 to 5: Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C) : Organoaluminum compound The catalyst for olefin polymerization according to claim 6, wherein component (B) is a boron compound. A method for producing an olefin polymer, wherein the olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst according to claim 6 or 7. The method for producing an olefin polymer according to claim 8, wherein the olefin used contains ethylene. The method for producing an olefin polymer according to claim 8 or 9, wherein the polymerization temperature is 120 ° C or higher.