JP5983482B2 - Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer using the same - Google Patents

Description

  The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer using the same. More specifically, the present invention relates to an α-olefin polymer having a relatively wide molecular weight distribution and a high melting point. The present invention relates to an α-olefin polymerization catalyst that enables production and an α-olefin polymer production method using the same.

  Industrially very important polyolefins are industrially produced on a large scale with the advent of Ziegler-Natta catalysts. On the other hand, a metallocene catalyst, generally composed of a group 4 metallocene complex and methylaluminoxane, discovered in 1980 has a higher activity per transition metal than a Ziegler-Natta catalyst and is a homogeneous active species. Since polyolefins with a narrow molecular weight distribution can be produced, there is a possibility that differentiated polyolefins can be produced with respect to polymers obtained with Ziegler-Natta catalysts, which has attracted attention.

  The metallocene complex initially had a simple structure having an auxiliary ligand with a transition metal atom sandwiched between cyclopentadienyl rings (conjugated 5-membered rings). However, in order to improve the olefin polymerization activity, By arranging an electron-donating substituent and connecting the conjugated ring with a bridging group, the regularity is controlled, and a substituent is added to a specific position to improve the regiospecificity at the time of α-olefin insertion. In addition, many improved catalysts have been disclosed, such as increasing the molecular weight of the polymer produced by using an indenyl ring, a fluorenyl ring, or the like.

As a representative technique, in a bridged metallocene complex having an indenyl skeleton or an azulenyl skeleton in which another conjugated ring is condensed to a conjugated 5-membered ring, a substituent is introduced at the 4-position on the indenyl skeleton or the azulenyl skeleton. It has been reported that the polymerization activity, the molecular weight of the obtained polymer, and the regularity are improved (see Patent Documents 1 and 2).
In particular, when the substituent at the 4-position is an aromatic ring such as a phenyl group, it has been reported that the improvement in the regularity and molecular weight of the polymer is remarkable. Furthermore, in order to further improve the catalyst performance, several techniques for further substituting hydrogen atoms on the aromatic ring have been reported (see, for example, Patent Documents 3 to 7).

In Patent Document 3, a substituent at the 4-position of the indenyl skeleton is an aryl group, and a complex as a catalyst component in which a hydrocarbon group or a halogen atom is further substituted on this aryl group is shown, and the catalytic activity is improved. Polypropylene with high regularity has been obtained. Patent Document 4 proposes a complex in which the substituent at the 4-position of the indenyl skeleton is a phenyl group, and the phenyl group is further substituted with a plurality of hydrocarbon groups or silyl groups, and the melting point is increased. Polypropylene has been obtained.
Furthermore, in Patent Document 5, the 4-position substituent of the azulenyl skeleton is a phenyl group, and the phenyl group is further substituted at the 4-position (para-position) of this phenyl group (the whole substituent is a biphenylyl group). ), A catalyst complex in which a hydrocarbon group or a halogen atom is substituted at the 2,6-position of the biphenylyl group has been proposed, and a polypropylene having improved regularity, melting point and molecular weight has been obtained. Further, in Patent Document 6, the substituent at the 4-position of the azulenyl skeleton is a phenyl group, and a catalytic complex in which another carbocycle is condensed to this phenyl group is shown, and the regularity, melting point and molecular weight are increased. Polypropylene has been obtained. Further, in Patent Document 7, the 4-position substituent of the azulenyl skeleton is a phenyl group, and a catalytic complex in which this phenyl group is further substituted with a silyl group is shown. Olefin polymers having an increased melting point and molecular weight have been obtained.

  In addition, the metallocene catalyst using the metallocene transition metal compound as described above has high activity, and the resulting propylene polymer is excellent in regularity, and therefore has excellent physical properties in specific applications. On the other hand, the molecular weight distribution is narrow and the molding processability is inferior. In order to solve this problem, a catalyst using a plurality of metallocene complexes, for example, Patent Document 8, discloses a technique for widening the molecular weight distribution by using two types of metallocene complexes having different 4-position substituent structures. Has been. However, since the catalyst performance of each complex varies depending on the polymerization conditions, there are problems in the controllability of the molecular weight / composition distribution.

Patent Document 9 also discloses that a polymer having a high molecular weight and a wide molecular weight distribution is highly active by an olefin polymerization catalyst containing a metallocene compound, an organoaluminum oxy compound, and a compound containing a specific metal element. It is disclosed that it can be polymerized.
However, in the catalyst as described above, a different metal component must be added in addition to the metallocene compound, and the purpose is to generate a new active site by ligand exchange as shown in Patent Document 10. Although it is considered that it was intended, in such a method, the ligand exchange reaction did not proceed sufficiently, and the effect of the improvement was not sufficient. Moreover, only the ethylene polymerization is disclosed by the said patent document 9, and when α-olefins, such as a propylene, are used, it is not suggested that the regularity regarding melting | fusing point and an elution component improves.

Patent Document 11 discloses that a polymer having excellent operational stability and high molecular weight and broad molecular weight distribution is highly active by adding a cyclopentadiene compound during polymerization in the presence of a catalyst containing a metallocene compound and an organometallic compound. It is disclosed that it can be polymerized.
However, the above production method is intended to generate a new active site by ligand exchange as shown in Patent Document 10 by contacting the catalyst with cyclopentadiene in the presence of an olefin during polymerization. However, in the method of contacting at the time of polymerization, since the contact concentration is low, the ligand exchange reaction does not proceed sufficiently, and the improvement effect is not sufficient. Moreover, only the ethylene polymerization is disclosed by the said patent document 11, and when α-olefins, such as a propylene, are used, it is not suggested that the regularity regarding melting | fusing point and an elution component improves.

Further, Patent Document 12 discloses the production of a highly active catalyst system by a method using a metallocene compound, a first modifier containing a Group 13 element-containing compound, and a second modifier containing a cycloalkadiene. A process and an olefin polymerization process using the same are disclosed.
However, the above catalyst system production method is a method of modifying a metallocene compound activated with a co-catalyst or the like in a solution (homogeneous system) by the interaction between the first modifier and the second modifier, This is not an efficient production method using a solid catalyst. In addition, Patent Document 12 discloses only ethylene polymerization, and does not suggest that the regularity related to the melting point and the eluted components is improved when an α-olefin such as propylene is used.

Japanese Patent Application Laid-Open No. 6-100579 Japanese Patent Laid-Open No. 10-226712 Japanese Patent Laid-Open No. 7-286005 WO02 / 02576 (Japanese translations of PCT publication No. 2004-502699) Japanese Patent Laid-Open No. 2000-95791 JP 2001-48894 A JP 2002-12596 A JP 2003-119212 A JP 2009-173896 A Japanese Patent No. 40008055 JP 2011-132330 A Japanese translation of PCT publication No. 2004-514033

  In view of the above-mentioned problems of the prior art, the object of the present invention is to maintain the characteristics of a single-site catalyst having high regularity and low amorphous components, while having a relatively wide molecular weight distribution and a high melting point. To provide an α-olefin polymerization catalyst capable of producing an α-olefin polymer with a kind of metallocene complex, and a method for producing an α-olefin polymer having a wide molecular weight distribution and excellent molding processability. is there.

  As a result of intensive studies to solve the above problems, the present inventors have used a cyclopentadiene derivative, preferably a specific cyclopentadiene derivative, in a specific metallocene catalyst system. It became a catalyst for producing a polymer having a wide molecular weight distribution. For example, when propylene was polymerized, it was found that a polymer having a wide molecular weight distribution and a high melting point was obtained, and the present invention was completed.

That is, according to the first invention of the present invention, there is provided an α-olefin polymerization catalyst characterized by being prepared by contacting at least the following components [A] to [D] in the absence of an olefin: Provided.
Component [A]: a transition metal compound of Group 4 of the periodic table represented by formula (a1).

[In General Formula (a1), E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. , X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: an ionicity capable of reacting with the transition metal compound [A] carried on the solid fine particles and converted into a cation by reacting with the aluminum oxy compound [B-1] carried on the solid fine particles At least 1 type chosen from the compound group which consists of a compound or Lewis acid [B-2], and an ion exchange layered silicate [B-3].
Component [C]: an organoaluminum compound.
Component [D]: cyclopentadiene derivative.

Further, according to the second invention of the present invention, in the first invention, before the component [A] and the component [D] are contacted, the component [B] and the component [D] are contacted in advance. An α-olefin polymerization catalyst is provided.
Furthermore, according to the third invention of the present invention, there is provided an α-olefin polymerization catalyst characterized in that, in the first or second invention, an α-olefin polymer having a melting point (Tm) greater than 153 ° C. can be produced. The

According to the fourth aspect of the present invention, in any one of the first to third aspects, the temperature (Tp) at the peak position of the TREF elution curve is 105 ° C. or higher, and the 40 ° C. soluble component is 0. An α-olefin polymerization catalyst characterized by being capable of producing an α-olefin polymer of less than 3% by weight is provided.
Furthermore, according to a fifth aspect of the present invention, in any one of the first to fourth aspects, the component [D] is a cyclopentadiene derivative represented by the following general formula (2). An α-olefin polymerization catalyst is provided.

[In General Formula (2), E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the component [B] is an ion-exchange layered silicate [B-3]. A catalyst is provided.
According to the seventh invention of the present invention, in any one of the first to sixth inventions, the ion-exchange layered silicate [B-3] is a smectite group, for α-olefin polymerization A catalyst is provided.
Furthermore, according to the eighth invention of the present invention, in any one of the first to seventh inventions, the olefin is prepolymerized in a weight ratio of 0.01 to 100 with respect to the component [B]. An olefin polymerization catalyst is provided.

  According to a ninth aspect of the present invention, an α-olefin polymerization is carried out using the α-olefin polymerization catalyst according to any one of the first to eighth aspects of the invention to polymerize the α-olefin. A method for producing a coalescence is provided.

ADVANTAGE OF THE INVENTION According to this invention, there exists a remarkable effect that the catalyst for alpha-olefin polymerization which can manufacture the alpha-olefin polymer with wide molecular weight distribution and high regularity can be provided. The high regularity could be evaluated from the mm fraction, the amount of heterogeneous bonds, the TREF 40 ° C. soluble matter, and the like.
In addition, according to the method for producing an α-olefin polymer of the present invention, it is possible to obtain an α-olefin polymer having a wide molecular weight distribution and excellent molding processability and a high regularity, so that the melting point is high and the heat resistance is high. it can.

It is a figure of the description of the baseline of a chromatogram in GPC, and an area.

  Hereinafter, the α-olefin polymerization catalyst of the present invention and the method for producing an α-olefin polymer using the same will be described in detail for each item.

1. Catalyst Component of α-Olefin Polymerization Catalyst The α-olefin polymerization catalyst of the present invention, for example, a propylene polymerization catalyst, contains at least the following components [A], [B], [C] and [D], It is essential to contact in the presence.

(1) Component [A]
Component [A] is a group 4 transition metal compound represented by the following general formula (a1), that is, a metallocene compound.

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

E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent.
Of these, a substituted cyclopentadienyl group, a substituted indenyl group, and a substituted azulenyl group are preferable. More preferably, E ¹¹ and E ¹² are substituted azulenyl groups.
In the case where E ¹¹ and E ¹² are substituted cyclopentadienyl groups, the following structures can be exemplified.

[In General Formula (a3), R ²¹ and R ²⁴ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ²² , R ²³ , R ²⁵ and R ²⁶ are each independently And a hydrocarbon group having 1 to 6 carbon atoms. X ²¹ and Y ²¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms, Q ²¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms; Represents a silylene group or a germylene group, and M ²¹ represents zirconium or hafnium. ]

R ²¹ and R ²⁴ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl and n-propyl, particularly preferably a methyl group.
R ²² , R ²³ , R ²⁵ and R ²⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl having 1 to 4 carbon atoms. Group, particularly preferably a methyl group.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. Preferred are methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl.

In the general formula (a3), X ²¹ and Y ²¹ are auxiliary ligands, and react with the component [B] as a cocatalyst to generate an active metallocene having olefin polymerization ability. As this object is achieved, X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms is represented.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, or triarylsilyl group having 1 to 20 carbon atoms.

In general formula (a3), Q ²¹ is a divalent valence having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. Or a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ²¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Non-limiting examples of the metallocene compound represented by the general formula (a3) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound in which the central metal is hafnium has been described, it is obvious that the same zirconium compound can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used.
(1) dichloro {dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(2) dichloro {diphenylsilylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(3) dichloro {dimethylgermylenebis (2,3,5-trimethylcyclopentadienyl)} hafnium,
(4) dichloro {dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl)} hafnium,
(5) dichloro {dimethylsilylenebis (2-ethyl-3-phenyl-5-methylcyclopentadienyl)} hafnium,
(6) dichloro {dimethylsilylenebis (2,3,5-triethylcyclopentadienyl)} hafnium,
(7) dichloro {dimethylsilylenebis (2,5-dimethyl-3-ethylcyclopentadienyl)} hafnium,
(8) dichloro {dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl)} hafnium,
(9) Dichloro {dimethylsilylenebis (2,5-dimethyl-3-i-propylcyclopentadienyl)} hafnium,
Etc.

In addition, when E ¹¹ and E ¹² are substituted indenyl groups, the following structures can be exemplified.

[In General Formula (a4), R ³¹ and R ³³ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group having 6 to 12 carbon atoms, An alkenyl group having 2 to 8 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, and a trialkyl having 1 to 3 carbon atoms. A C1-C3 alkyl group having an alkylsilyl group, a silyl group having a C1-C6 hydrocarbon group, or an oxygen-containing heterocyclic group or a sulfur-containing heterocyclic group, and R ³² and R ³⁴ are: Each independently represents halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. . X ³¹ and Y ³¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms, and Q ³¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. Represents a silylene group or a germylene group, and M ³¹ represents zirconium or hafnium. ]

The above ^{R 31} and ^{R 33} are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, methoxy, ethoxy, phenoxy, butenyl , Fluoromethyl, phenyl, 5-methyl-2-furyl, 4,5-dimethylfuryl, etc., preferably methyl, ethyl, n-propyl, i-propyl, 5-methyl-2-furyl, 4,5 -Dimethylfuryl.

R ³² and R ³⁴ are halogen, silicon, or an aryl group having 6 to 30 carbon atoms that may contain a plurality of heteroelements selected from these. As the aryl group, In the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton You may have a hydrocarbon group as a substituent.
R ³² and R ³⁴ are preferably at least one of phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di- t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group. 4-chlorophenyl group. R ³² and R ³⁴ are preferably the same as each other.

Further, X ³¹ and Y ³¹ are auxiliary ligands, and react with the component [B] to generate an active metallocene having olefin polymerization ability. In order to achieve this object, X ³¹ and Y ³¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, carbon A halogenated hydrocarbon group having 1 to 20 amino acids, an amino group or an alkylamino group having 1 to 20 carbon atoms is represented.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, or triarylsilyl group having 1 to 20 carbon atoms.

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

Non-limiting examples of the metallocene compound represented by the general formula (a4) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound in which the central metal is hafnium has been described, it is obvious that the same zirconium compound can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used.
(1) dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenylindenyl)} hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) indenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) indenyl}] hafnium,
(4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) indenyl}] hafnium,
(5) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-tert-butylphenyl) indenyl}] hafnium,
(6) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-tert-butylphenyl) indenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) indenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (1-naphthyl) indenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) indenyl}] hafnium,
(11) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] hafnium,
(12) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenyl) indenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) indenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) indenyl}] hafnium,
(15) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) indenyl}] hafnium,
(16) Dichloro [1,1′-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] hafnium,
(17) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) indenyl}] hafnium,
(18) dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] hafnium,
(19) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) indenyl}] hafnium,
(20) Dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) indenyl}] hafnium,
(21) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4--4-phenylindenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) indenyl}] hafnium,
(23) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium,
Etc.

In addition, when E ¹¹ and E ¹² are substituted azulenyl groups, the following structures can be exemplified.

[In General Formula (a5), R ⁴¹ and R ⁴² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. R ⁴³ and R ⁴⁴ each independently represent halogen, silicon, or an aryl group having 6 to 30 carbon atoms that may contain a plurality of hetero elements selected from these. Q ⁴¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁴¹ represents zirconium or hafnium. X ⁴¹ and Y ⁴¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

R ⁴¹ and R ⁴² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ⁴³ and R ⁴⁴ each independently contain halogen, silicon, or a plurality of heteroelements selected from these, having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms. Of the aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ⁴¹ and Y ⁴¹ are auxiliary ligands, which react with the component [B] as a cocatalyst to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ⁵¹ and Y ⁵¹ are not limited to the type of ligand, and are independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Show.

Q ⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁴¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc .; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁴¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a5) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound in which the central metal is hafnium has been described, it is obvious that the same zirconium compound can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used.
(1) dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(5) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(6) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium,
(11) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(12) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium,
(15) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(16) dichloro [1,1′-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(17) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(18) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(19) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(20) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(21) Dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(23) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(24) dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
Etc.

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

[In General Formula (a6), R ⁵¹ represents a hydrocarbon group having 1 to 6 carbon atoms. R ⁵² is halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Q ⁵¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁵¹ represents zirconium or hafnium. , X ⁵¹ and Y ⁵¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

In the general formula (a6), R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ⁵² is an aryl group having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.
R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, Examples include i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like, preferably methyl, ethyl, n-propyl, i- Propyl, t-butyl, phenyl.
However, any two or more of R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are substituents other than a hydrogen atom, and any one or more of R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are hydrogen. Is an atom.

X ⁵¹ and Y ⁵¹ are auxiliary ligands that react with the component [B] as a co-catalyst to generate an active metallocene having olefin polymerization ability. In order to achieve this object, X ⁵¹ and Y ⁵¹ are each independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkylamide group, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.
Q ⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene, diethylsilylene, diethylene. Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁵¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a6) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound in which the central metal is hafnium has been described, it is obvious that the same zirconium compound can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used.
(1) dichloro {1,1′-dimethylsilylene (2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(2) dichloro {1,1′-dimethylsilylene (3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(3) dichloro {1,1′-dimethylsilylene (2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(4) dichloro {1,1′-dimethylsilylene (2,3-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(5) dichloro {1,1′-dimethylsilylene (3,4-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(6) dichloro {1,1′-dimethylsilylene (2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(7) dichloro {1,1′-dimethylsilylene (2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(8) dichloro {1,1′-dimethylsilylene (3,4-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(9) dichloro {1,1′-dimethylsilylene (2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(10) dichloro {1,1′-dimethylsilylene (2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(11) dichloro {1,1′-dimethylsilylene (2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(12) dichloro {1,1′-dimethylsilylene (2-methyl-4-tert-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(13) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(14) dichloro {1,1′-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(15) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(16) dichloro {1,1′-dimethylsilylene (2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(17) dichloro {1,1′-dimethylsilylene (2,3-dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium,
(18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} hafnium,
(19) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} hafnium,
(20) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (4-phenyl-2-i-propyl-4H-azurenyl)} hafnium,

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

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

(61) Dichloro [dimethylsilylene {2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(62) Dichloro [dimethylsilylene {2-ethyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(63) Dichloro [dimethylsilylene {2-ethyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(64) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(65) Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(66) Dichloro [dimethylsilylene {2-ethyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(67) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(68) Dichloro [dimethylsilylene {2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(69) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(70) dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(71) Dichloro [dimethylsilylene {2-ethyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(72) Dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(73) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(74) Dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(75) Dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(76) Dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(77) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(78) Dichloro [dimethylsilylene {2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(79) Dichloro [dimethylsilylene {3- (cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(80) Dichloro [dimethylsilylene {3- (2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,

(81) Dichloro [dimethylsilylene {2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(82) Dichloro [dimethylsilylene {3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(83) Dichloro [dimethylsilylene {2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(84) Dichloro [dimethylsilylene {3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(85) Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(86) Dichloro [dimethylsilylene {2-n-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(87) Dichloro [dimethylsilylene {3- (1-cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(88) Dichloro [dimethylsilylene {2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(89) Dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(90) Dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(91) Dichloro [dimethylsilylene {2-n-propyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(92) Dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(93) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(94) Dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(95) Dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(96) Dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(97) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
Etc.

Further, when E ¹¹ and E ¹² are a cyclopentadienyl group and a fluorenyl group, the following structures can be exemplified.

[In General Formula (a7), R ⁶² represents a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. R ⁶¹ , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon having 1 to 20 carbon atoms. Each may be the same or different, and adjacent substituents from R ^{65 to} R ⁶⁸ may be bonded to each other to form a ring. Q ⁶¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁶¹ represents zirconium or hafnium. , X ⁶¹ and Y ⁶¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

In the general formula (a7), R ⁶² is selected from a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and R ⁶¹ , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different, and R ^{65 to} R ⁶⁸ Up to adjacent substituents may be bonded to each other to form a ring.
Further, the X ⁶¹ and Y ⁶¹ are auxiliary ligands to generate an active metallocene having olefin polymerizability reacts with the component [B] as a cocatalyst. In order to achieve this purpose, X ⁶¹ and Y ⁶¹ are each independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. An alkylamide group, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

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

Non-limiting examples of the metallocene compound represented by the general formula (a7) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Further, although a compound in which the central metal is zirconium has been described, it is obvious that the same hafnium compound can be used, and various ligands, cross-linking groups or auxiliary ligands can be arbitrarily used.
(1) dichlorodimethylmethylene (3-i-propylcyclopentadienyl) fluorenyl) zirconium,
(2) dichlorodimethylmethylene (3-tert-butylcyclopentadienyl) fluorenyl) zirconium,
(3) dichlorodimethylmethylene (3-trimethylsilylcyclopentadienyl) fluorenyl) zirconium,
(4) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) cyclopentadienyl) fluorenyl) zirconium,
(5) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) fluorenyl) zirconium,
(6) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenyl) zirconium,
(7) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) fluorenyl) zirconium,
(8) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) fluorenyl) zirconium,
(9) dichlorodimethylmethylene (3-i-propyl-5-ethylcyclopentadienyl) fluorenyl) zirconium,
(10) dichlorodimethylmethylene (3-t-butyl-5-ethylcyclopentadienyl) fluorenyl) zirconium,
(11) dichlorodimethylmethylene (3-trimethylsilyl-5-ethylcyclopentadienyl) fluorenyl) zirconium,
(12) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-ethylcyclopentadienyl) fluorenyl) zirconium,
(13) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(14) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium,
(15) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(16) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(17) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium,
(18) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium,
(19) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium,
(20) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium,

(21) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl) zirconium,
(22) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl) zirconium,
(23) Dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7, 8,9,10-octahydrodibenzofluorenyl) zirconium,
(24) Dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8, 9,10-octahydrodibenzo [b, h] fluorenyl) zirconium,
(25) dichlorodiphenylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(26) dichlorodiphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(27) dichlorodiphenylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(28) dichlorodiphenylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(29) dichlorodimethylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(30) dichlorodimethylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(31) dichlorodimethylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(32) dichlorodimethylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(33) dichlorodiphenylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(34) dichlorodiphenylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(35) dichlorodiphenylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
(36) dichlorodiphenylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium,
Etc.

Also, E ¹¹ and E ¹² are, in the case of an indenyl group and azulenyl group, can be exemplified by the following structures.

[In General Formula (a8), R ⁷¹ and R ⁷² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ⁷³ and R ⁷⁴ are each independently an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. Q ⁷¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁷¹ represents zirconium or hafnium. X ⁷¹ and Y ⁷¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

In the general formula ^{(a8), R 71} and ^{R 72} are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms It is. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
In addition, R ⁷³ and R ⁷⁴ each independently contain halogen, silicon, or a plurality of heteroelements selected from these, having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms. Of the aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Moreover, said ^X71 and ^Y71 are auxiliary ligands, and react with component [B] as a cocatalyst to produce an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ⁷¹ and Y ⁷¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Show.
Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁷¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ⁷¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the general formula (a8) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Further, although a compound in which the central metal is zirconium has been described, it is obvious that the same hafnium compound can be used, and various ligands, cross-linking groups or auxiliary ligands can be arbitrarily used.
(1) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(2) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(3) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(4) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(5) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] hafnium,
(6) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] hafnium,
(7) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-t-butylphenyl) -4H-1-azulenyl)] hafnium,
(8) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-t-butylphenyl) -4H-1-azurenyl)] hafnium,
(9) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] hafnium,
(10) Dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] hafnium,
(11) dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] hafnium,
(12) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] hafnium,
(13) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] hafnium,
(14) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] hafnium,
(15) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium,
(16) Dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium,
(17) Dichloro [dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(18) dichloro [dimethylsilylene (2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,
(19) Dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium,
(20) dichloro [dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] hafnium,

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

(2) Component [B]
As the component [B], an ionic property capable of reacting with the transition metal compound [A] carried on the solid fine particles and the above-mentioned transition metal compound [A] carried on the solid fine particles can be converted into a cation. At least one selected from the group consisting of a compound or a Lewis acid [B-2] and an ion-exchange layered silicate [B-3] is used.

(2-1) Component [B-1]
Specific examples of the aluminum oxy compound [B-1] include compounds represented by the following general formula (9), (10) or (11).

In each of the above general formulas, R ⁸¹ , R ⁹¹ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Indicates a group. A plurality of R ⁸¹ , R ⁹¹ and R ¹⁰¹ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (9) and (10) are also called alumoxanes. Among these, methylalumoxane or methylisobutylalumoxane is preferable.
The above-mentioned alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.
The compound represented by the general formula (11) is 10: 1 to 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (12). : 1 (molar ratio) reaction.
In the general formulas (11) and (12), R ¹⁰² and R ¹¹¹ represent a hydrocarbon residue or a halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

  Component [B-1] is used by being supported on a solid particulate carrier. The solid fine particles will be described later.

(2-2) Component [B-2]
Component [B-2] is an ionic compound or Lewis acid that can be converted into a cation by reacting with the above-described transition metal compound [A] supported on solid fine particles.
Specifically, as the ionic compound, a cation such as a carbonium cation or an ammonium cation, and an organic boron compound such as tetraphenylboron, tetrakis (3,5-difluorophenyl) boron or tetrakis (pentafluorophenyl) boron And a complex with an anion.
Examples of the Lewis acid that can convert the component [A] into a cation include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with component [A] and can convert component [A] into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one.
The solid fine particles will be described below.

(2-3) Solid Fine Particles Here, the solid fine particle carriers in the components [B-1] and [B-2] will be described.
In the present invention, the solid fine particles are not particularly limited in terms of their elemental composition and compound composition. For example, solid fine particles made of an inorganic or organic compound can be exemplified.
Examples of the inorganic carrier include silica, alumina, silica / alumina magnesium chloride, activated carbon, inorganic silicate, and the like. Alternatively, a mixture thereof may be used.
Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated carbonization such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer of hydrogen. Alternatively, a mixture thereof may be used.
These solid particulate carriers usually have an average particle size of 1 μm to 5 mm, preferably 5 μm to 1 mm, and more preferably 10 μm to 200 μm.

(2-4) Component [B-3]
Component [B-3] is an ion-exchange layered silicate (hereinafter simply referred to as silicate).
In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other and having exchangeable ions. Say. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can. Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

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

(A) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid. Two or more salts and acids may be used in the treatment. The treatment conditions with salts and acids are not particularly limited, but usually the salt and acid concentrations are selected from 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchanged layered silicate is eluted. In addition, salts and acids are generally used in an aqueous solution.

(B) Salt treatment In the present invention, 40% or more, preferably 60% or more, of the exchangeable Group 1 metal cation contained in the ion-exchangeable layered silicate before treatment with salts is described below. It is preferable to exchange ions with cations dissociated from the salts shown.

The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O ₄ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , Zr F ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , _{HF (SO 4) 2, HFOCl} 2, HFF 4, HFCl 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, VCl 4, VBr 3 , etc. _{and, Cr (CH 3 COCHCOCH 3)} 3 Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI _{3 , Mn (OOCCH 3) 2,} Mn (CH 3 COCHCOCH 3) 2, MnCO 3, Mn (NO 3) 2, MnO, Mn _{ClO 4) 2, MnF 2,} MnCl 2, Fe (OOCCH 3) 2, Fe (CH 3 COCHCOCH 3) 3, FeCO 3, Fe (NO 3) 3, Fe (ClO 4) 3, FePO 4, FeSO 4, Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O ₇ , Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _2, etc., Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Z n (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

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

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

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

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

The component [B] is preferably spherical particles having an average particle diameter of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.

  The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization step. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

Among the above-mentioned component [B], [B-3] ion exchange layered silicate is particularly preferable.
In the propylene polymerization catalyst according to the present invention, [B-1] an aluminum oxy compound supported on solid fine particles, and [B-2] a component [A] reacted with component [A] supported on solid fine particles. The ionic compound or Lewis acid that can be converted into a cation, or [B-3] ion-exchange layered silicate fine particles are each used alone as the component [B], and these three components are appropriately added. Even in combination, it can be used.

(3) Component [C]
As the component [C], an organoaluminum compound is used. In the present invention, the following general formula:
AlR ⁷¹ _q Z _3-q (13)
An organoaluminum compound represented by the formula is preferred.
In the present invention, it goes without saying that the compounds represented by this formula can be used singly or in combination of two or more. In this formula, R ⁷¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q is a number greater than 0 and up to 3. R ⁷¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and a carbon atom number 1 when it is an amino group. An amino group of ˜8 is preferred.

Specific examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, trialkylaluminum and dialkylaluminum hydrides with q = 3 are preferred. More ^preferably trialkylaluminum ^{R 71} is 1 to 8 carbon atoms.

(4) Component [D]
In the α-olefin polymerization catalyst of the present invention, a cyclopentadiene derivative is used as component [D]. The cyclopentadiene derivative does not contain a metal complex.

The cyclopentadiene derivative is cyclopentadiene, indene, fluorene, or azulene, and each may have a substituent. Examples of the substituent include an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur, halogen, silicon, or a plurality of hetero elements selected from these The aryl group may contain 6 to 30 carbon atoms, and the aryl group may have one or more carbon atoms of 1 to 6 on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. A hydrocarbon group of 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, and a halogen-containing hydrocarbon group having 1 to 6 carbon atoms as a substituent.
Specific examples of the substituent include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2- Methylfuryl, phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di-t-butylphenyl group, 4-phenyl -Phenyl group, chlorophenyl group, naphthyl group, phenanthryl group, etc. are mentioned, preferably methyl, ethyl, furyl, 2-methylfuryl, phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4- t-Butylphenyl group.

  Specific examples of the cyclopentadiene derivative include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, isobutylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclo Pentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, methylethylcyclopentadiene, methylpropylcyclopentadiene, methylbutylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4 -Tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, methylindene, ethylindene, propyl 7 carbon atoms such as Ndene, Butylindene, 4-Methyl-1-indene, 4,7-Dimethylindene, 4,5,6,7-Tetrahydroindene, Azulene, Methylazulene, Ethylazulene, Fluorene, Methylfluorene To 24 cyclopolyenes or substituted cyclopolyenes.

  The cyclopentadiene derivative may have two or more cyclopentadienyl rings cross-linked by a cross-linking group, and examples thereof include compounds having the following structure.

[In General Formula (2), E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Of these, a substituted cyclopentadienyl group and a substituted indenyl group are preferable, and a substituted indenyl group is particularly preferable.
Moreover, the said cyclopentadiene derivative may be bridge | crosslinked, and the following structure 1 can be illustrated.

[In the structure 1, R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ and R ¹²⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or It is a C4-C16 heterocyclic group containing nitrogen, oxygen or sulfur. Q ¹²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl group can be considered, and only one of them is illustrated, but only the position of the double bond in the cyclopentadienyl group May be other isomers different from each other or a mixture thereof. ]

In the structure 1, R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ^127, and R ¹²⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or nitrogen , A heterocyclic group having 4 to 16 carbon atoms containing oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. And preferably a methyl group.

Q ¹²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings and bridges two conjugated five-membered ring ligands via one or two carbon atoms; It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹²¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 1 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] silane,
(2) Dimethyl [bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] methane,
(3) [Bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] methane,
(4) [Bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] ethane,
(5) Dimethyl [bis (2,4-cyclopentadien-1-yl)] silane,
(6) Dimethyl [bis (2,4-cyclopentadien-1-yl)] methane,
(7) [Bis (2,4-cyclopentadien-1-yl)] methane,
(8) [2,4-cyclopentadien-1-yl)] ethane,
(9) Dimethyl [bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] silane,
(10) Dimethyl [bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] methane,
(11) [Bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] methane,
(12) [Bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] ethane,
(13) Dimethyl [bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] silane,
(14) Dimethyl [bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] methane,
(15) [Bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] methane,
(16) [Bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] ethane,
(17) Dimethyl [bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] silane,
(18) Dimethyl [bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] methane,
(19) [Bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] methane,
(20) [Bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] ethane,

(21) Dimethyl [bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] silane,
(22) Dimethyl [bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] methane,
(23) [Bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] methane,
(24) [Bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] ethane,
(25) Dimethyl [bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] silane,
(26) Dimethyl [bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] methane,
(27) [Bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] methane,
(28) [Bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] ethane,
(29) Dimethyl [bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] silane,
(30) Dimethyl [bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] methane,
(31) [Bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] methane,
(32) [Bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] ethane,
(33) Dimethyl [bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] silane,
(34) Dimethyl [bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] methane,
(35) [Bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] methane,
(36) [Bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] ethane,
Etc.

  Moreover, the following structure 2 can be illustrated.

[In the structure 2, each of R ¹³¹ and R ¹³³ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic ring having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Indicates a group. R ¹³² and R ¹³⁴ are each independently a hydrogen atom, a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ¹³¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the indenyl group can be considered, and only one of them is illustrated, but the double in the 5-membered ring in the indenyl group is exemplified. Other isomers that differ only in the position of the bond may be used, or a mixture thereof. ]

R ¹³¹ and R ¹³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Preferably methyl, ethyl, furyl, 2-methylfuryl.
R ¹³² and R ¹³⁴ are a hydrogen atom, halogen, silicon, or an aryl group having 6 to 30 carbon atoms that may contain a plurality of hetero elements selected from these. As the group, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, 1 to 1 carbon atoms on the aryl cyclic skeleton. 6 halogen-containing hydrocarbon groups may be substituted.
Specific examples include a phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-dit-butylphenyl group, 4 -Phenyl-phenyl group, chlorophenyl group, naphthyl group, phenanthryl group and the like can be mentioned, preferably. A phenyl group, a 4-i-propylphenyl group, a 4-trimethylsilylphenyl group, and a 4-t-butylphenyl group.

Q ¹³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹³¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 2 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [bis {2- (2-furyl) -4-phenyl-indenyl}] silane,
(2) Dimethyl [bis {2- (2-thienyl) -4-phenyl-indenyl}] silane,
(3) Dimethyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] silane,
(4) diphenyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] silane,
(5) Dimethyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] germanium,
(6) Dimethyl [bis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] germanium,
(7) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] silane,
(8) Dimethyl [bis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] silane,
(9) Dimethyl [bis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] silane,
(10) Dimethyl [bis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] silane,
(11) Dimethyl [bis {2- (2-benzofuryl) -4-phenyl-indenyl}] silane,
(12) Dimethyl [bis {2- (2-furfuryl) -4-phenyl-indenyl}] silane,
(13) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] silane,
(14) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] silane,
(15) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] silane,
(16) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] silane,
(17) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] silane,
(18) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] silane,
(19) Dimethyl [bis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(20) Dimethyl [bis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] silane,

(21) Dimethyl [bis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(22) Dimethyl [bis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(23) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(24) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] silane,
(25) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(26) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(27) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(28dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] silane,
(29) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(30) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(31) Dimethyl {bis (2-methyl-4-phenylindenyl)} silane,
(32) Dimethyl [bis {2-methyl-4- (4-chlorophenyl) indenyl}] silane,
(33) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) indenyl}] silane,
(34) Dimethyl [bis {2-methyl-4- (4-trimethylsilylphenyl) indenyl}] silane,
(35) Dimethyl [bis {2-methyl-4- (3-chloro-4-t-butylphenyl) indenyl}] silane,
(36) Dimethyl [bis {2-methyl-4- (3-methyl-4-t-butylphenyl) indenyl}] silane,
(37) Dimethyl [bis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] silane,
(38) Dimethyl [bis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) indenyl}] silane,
(39) Dimethyl [bis {2-methyl-4- (1-naphthyl) indenyl}] silane,
(40) Dimethyl [bis {2-methyl-4- (2-naphthyl) indenyl}] silane,

(41) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] silane,
(42) Dimethyl [bis {2-methyl-4- (2-chloro-4-biphenyl) indenyl}] silane,
(43) Dimethyl [bis {2-methyl-4- (9-phenanthryl) indenyl}] silane,
(44) Dimethyl [bis {2-methyl-4- (4-chloro-2-naphthyl) indenyl}] silane,
(45) Dimethyl [bis {2-ethyl-4- (3-chloro-4-t-butylphenyl) indenyl}] silane,
(46) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] germanium,
(47) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) indenyl}] germanium,
Etc.

  Moreover, the following structure 3 can be illustrated.

[In the structure 3, R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ and R ¹⁴⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon atom. Each represents a silicon-containing hydrocarbon group of 1 to 20, which may be the same or different, and adjacent substituents R ^{141 to} R ¹⁴⁴ and R ^{145 to} R ¹⁴⁸ are bonded to each other to form a ring; Also good. Q ¹⁴¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

Q ¹⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, carbon Either a silylene group or a germylene group which may have a hydrocarbon group of 1 to 20 is shown. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁴¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 3 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 1,2-di (9H-fluoren-9-yl) ethane,
(2) Di (9H-fluoren-9-yl) (dimethyl) silane,
(3) di (9H-fluoren-9-yl) (diphenyl) silane,
(4) 1- {2,7-di-t-butyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(5) {2,7-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(6) {2,7-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(7) 1- {3,6-di-t-butyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(8) {3,6-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(9) {3,6-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(10) 1- {2,7-diphenyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(11) {2,7-diphenyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(12) {2,7-diphenyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(13) 1-((12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h Fluoren-12-yl) -2- (9H-fluoren-9-yl) ethane,
(14) (12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h] fluorene- 12-yl (9H-fluoren-9-yl) (dimethyl) silane,
(15) (12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h] fluorene- 12-yl) (9H-fluoren-9-yl) (diphenyl) silane,
Etc.

  Moreover, the following structure 4 can be illustrated.

[In the structure 4, R ¹⁵¹ and R ¹⁵² are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹⁵³ and R ¹⁵⁴ are each independently an aryl group having 6 to 30 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these. Q ¹⁵¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Further, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the azulenyl group can be considered, and only one of them is illustrated, but the double in the 5-membered ring in the azulenyl group is exemplified. Other isomers that differ only in the position of the bond may be used, or a mixture thereof. ]

R ¹⁵¹ and R ¹⁵² are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
Specific examples include methyl, ethyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like. Preferably, methyl, ethyl and n-propyl are used.

R ¹⁵³ and R ¹⁵⁴ are each independently an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Q ¹⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ¹⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 4 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl {bis (2-methyl-4-phenyl-4-hydroazurenyl)} silane,
(2) Dimethyl [bis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] silane,
(3) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] silane,
(4) Dimethyl [bis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(5) Dimethyl [bis {2-methyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(6) Dimethyl [bis {2-methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(7) Dimethyl [bis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(8) Dimethyl [bis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(9) Dimethyl [bis {2-methyl-4- (1-naphthyl) -4-hydroazulenyl}] silane,
(10) Dimethyl [bis {2-methyl-4- (2-naphthyl) -4-hydroazulenyl}] silane,
(11) Dimethyl [bis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] silane,
(12) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] silane,
(13) Dimethyl [bis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] silane,
(14) Dimethyl [bis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] silane,
(15) Dimethyl [bis-2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] silane,
(16-dimethyl [bis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] silane,
(17) Dimethyl [bis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(18) Dimethyl [bis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(19) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] germanium,
(20) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] germanium,

(21) 9,9-bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}]-9-silafluorene,
(22) Dimethyl [bis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] silane,
(23) Dimethyl [bis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] silane,
(24) 9,9-bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}]-9-silafluorene,
Etc.

  Moreover, the following structure 5 can be illustrated.

[In the structure 5, R ¹⁶¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹⁶² is an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ and R ¹⁶⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Q ¹⁶¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the cyclopentadienyl group and the azulenyl group can be considered, and only one of them is illustrated, but cyclopentadienyl Other isomers that differ only in the position of the double bond in the 5-membered ring in the group and the azulenyl group may be used, or a mixture thereof. ]

In the structure 5, R ¹⁶¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably Methyl, ethyl, n-propyl.
R ¹⁶² is an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl. 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like can be mentioned.
R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ and R ¹⁶⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n- Examples include propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, and phenyl, and a methyl group is preferable.

Q ¹⁶¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Q ¹⁶¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via 1 or 2 carbon atoms, which bonds two five-membered rings; It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁶¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 5 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl {(2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(2) Dimethyl {(3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(3) Dimethyl {(2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(4) Dimethyl {(2,3-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(5) Dimethyl {(3,4-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(6) Dimethyl {(2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(7) Dimethyl {(2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(8) Dimethyl {(3,4-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(9) Dimethyl {(2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(10) Dimethyl {(2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(11) Dimethyl {(2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(12) Dimethyl {(2-methyl-4-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(13) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(14) Dimethyl {(2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(15) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(16) Dimethyl {(2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(17) Dimethyl {(2,3-dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(18) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} silane,
(19) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} silane,
(20) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (4-phenyl-2-i-propyl-4H-azurenyl)} silane,

(21) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-i-propyl-4-t-phenyl-2-i-propyl-4H-azurenyl)} silane,
(22) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azulenyl)} silane,
(23) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azurenyl)} silane,
(24) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azulenyl)} silane,
(25) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azurenyl)} silane,
(26) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -2-methyl-4H-azurenyl)} silane,
(27) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -2-methyl-4H-azurenyl)} silane,
(28) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azurenyl)} silane,
(29) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azurenyl)} silane,
(30) methylphenyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(31) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} silacyclobutane,
(32) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} silacyclopentane,
(33) 9- (2,4,5-trimethylcyclopentadienyl) -9- (2-methyl-4-phenyl-4H-azurenyl)} silafluorene,
(34) methylphenyl (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} germanium,
(35) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} germacyclobutane,
(36) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} germacyclopentane,
(37) 9- (2,4,5-trimethylcyclopentadienyl) -9- (2-methyl-4-phenyl-4H-azurenyl)} germafluorene,
(38) Dimethyl [{2-methyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(39) Dimethyl [{2-methyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(40) Dimethyl [{3- (2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(41) Dimethyl [{2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(42) Dimethyl [{2-methyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(43) Dimethyl [{2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(44) Dimethyl [{3- (1-cyclopropylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(45) Dimethyl [{3- (1,2-dimethylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(46) Dimethyl [{2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(47) Dimethyl [{3- (1-cyclohexylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(48) Dimethyl [{2-methyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(49) Dimethyl [{2-methyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(50) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(51) Dimethyl [{2-methyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(52) Dimethyl [{2-methyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(53) Dimethyl [{3- (1-i-propylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(54) Dimethyl [{3- (1-cyclopropylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(55) Dimethyl [{3- (1-s-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azuler)] silane,
(56) Dimethyl [{3- (1-t-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azuler)] silane,
(57) Dimethyl [{3- (1-cyclohexylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(58) Dimethyl [{2-ethyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(59) Dimethyl [{2-ethyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(60) Dimethyl [{3- (2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(61) Dimethyl [{2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(62) Dimethyl [{2-ethyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(63) Dimethyl [{2-ethyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(64) Dimethyl [{2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(65) Dimethyl [{3- (1,2-dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(66) Dimethyl [{2-ethyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(67) Dimethyl [{2-ethyl-4- (1-cyclohexylethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(68) Dimethyl [{2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(69) Dimethyl [{2-ethyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(70) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(71) Dimethyl [{2-ethyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(72) Dimethyl [{2-ethyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(73) Dimethyl [{3- (1-i-propylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(74) Dimethyl [{3- (1-cyclopropylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(75) Dimethyl [{3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(76) Dimethyl [{3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(77) Dimethyl [{3- (1-cyclohexylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(78) Dimethyl [{2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(79) Dimethyl [{3- (cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(80) Dimethyl [{3- (2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(81) Dimethyl [{2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(82) Dimethyl [{3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(83) Dimethyl [{2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(84) Dimethyl [{3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(85) Dimethyl [{3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(86) Dimethyl [{2-n-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(87) Dimethyl [{3- (1-cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(88) Dimethyl [{2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(89) Dimethyl [{2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(90) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(91) Dimethyl [{2-n-propyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(92) Dimethyl [{2-n-propyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(93) Dimethyl [{3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(94) Dimethyl [{3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(95) Dimethyl [{3- (1-s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(96) Dimethyl [{3- (1-t-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(97) Dimethyl [{3- (1-cyclohexylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
Etc.

  Moreover, the following structure 6 can be illustrated.

[In the structure 6, R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ , R ¹⁷⁵ , R ¹⁷⁶ , R ¹⁷⁷ and R ¹⁷⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon number 1 to 20 silicon-containing hydrocarbon groups, which may be the same or different, and adjacent substituents from R ^{175 to} R ¹⁷⁸ may be bonded to each other to form a ring. Q ¹⁷¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl group can be considered, and only one of them is illustrated, but only the position of the double bond in the cyclopentadienyl group May be other isomers different from each other or a mixture thereof. ]

In the above structure 6, Q ¹⁷¹ is a divalent carbon atom having 1 to 20 carbon atoms that bridges two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. It represents either a hydrogen group, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁷¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 6 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 2- (3-i-propylcyclopentadienyl) -2′-fluorenylpropane,
(2) 2- (3-tert-butylcyclopentadienyl) -2′-fluorenylpropane,
(3) 2- (3-trimethylsilylcyclopentadienyl) -2′-fluorenylpropane,
(4) 2- {3- (t-butyldimethylsilyl) cyclopentadienyl} -2′-fluorenylpropane,
(5) 2- (3-i-propyl-5-methylcyclopentadienyl) -2'-fluorenylpropane,
(6) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2′-fluorenylpropane,
(7) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2′-fluorenylpropane,
(8) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2′-fluorenylpropane,
(9) 2- (3-i-propyl-5-ethylcyclopentadienyl) -2'-fluorenylpropane,
(10) 2- (3-tert-butyl-5-ethylcyclopentadienyl) -2′-fluorenylpropane,
(11) 2- (3-trimethylsilyl-5-ethylcyclopentadienyl) -2′-fluorenylpropane,
(12) 2- {3- (t-butyldimethylsilyl) -5-ethylcyclopentadienyl} -2′-fluorenylpropane,
(13) 2- (3-i-propyl-5-methylcyclopentadienyl) -2 '-(3,6-di-t-butylfluorenyl) propane,
(14) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 ′-(3,6-ditert-butylfluorenyl) propane,
(15) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 '-(3,6-di-t-butylfluorenyl) propane,
(16) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2 ′-(3,6-di-t-butylfluorenyl) propane,
(17) 2- (3-i-propyl-5-methylcyclopentadienyl) -2 '-(2,7-di-t-butylfluorenyl) propane,
(18) 2- (3-t-butyl-5-methylcyclopentadienyl) -2 ′-(2,7-di-t-butylfluorenyl) propane,
(19) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 '-(2,7-di-t-butylfluorenyl) propane,
(20) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2 ′-(2,7-di-t-butylfluorenyl) propane,

(21) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 '-(dibenzo [b, e] fluorenyl) propane,
(22) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 ′-(dibenzo [b, e] fluorenyl) propane,
(23) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 '-(2,2,5,5,8,8,11,11-octamethyl-2,3,4,5 , 8,9,10,11-octahydrodibenzo [b, e] fluorenyl) propane,
(24) 2- (3-Trimethylsilyl-5-methylcyclopentadienyl) -2 '-(2,2,5,5,8,8,11,11-octamethyl-2,3,4,5,8 , 9,10,11-octahydrodibenzo [b, e] fluorenyl) propane,
(25) Diphenyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) propane,
(26) Diphenyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) methane,
(27) Diphenyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) methane,
(28) Diphenyl {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} (3,6-di-t-butylfluorenyl) methane,
(29) Dimethyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(30) Dimethyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(31) Dimethyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(32) methyl (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(33) diphenyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(34) diphenyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(35) diphenyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(36) Diphenyl {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} (3,6-di-t-butylfluorenyl) silane,
Etc.

  Moreover, the following structure 7 can be illustrated.

[In the structure 7, R ¹⁸¹ and R ¹⁸² are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Each of R ¹⁸³ and R ¹⁸⁴ is independently a hydrogen atom, or an aryl group having 6 to 30 carbon atoms, which may contain a halogen, silicon, or a plurality of hetero elements selected from these. Q ¹⁸¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the indenyl group and the azulenyl group can be considered, and only one of them is illustrated, but in the indenyl group and the azulenyl group It may be another isomer that differs only in the position of the double bond in the 5-membered ring, or a mixture thereof. ]

R ¹⁸¹ and R ¹⁸² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Of these, methyl, ethyl, furyl, and 2-methylfuryl are preferable.
R ¹⁸³ and R ¹⁸⁴ are each independently a hydrogen atom or an aryl group having 6 to 30 carbon atoms which may contain a halogen, silicon, or a plurality of hetero elements selected from these. In addition, as the aryl group, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms and trialkylsilyl groups having 1 to 6 carbon atoms on the aryl cyclic skeleton The halogen-containing hydrocarbon group having 1 to 6 carbon atoms may be substituted.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Q ¹⁸¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁸¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 7 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] silane,
(2) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] silane,
(3) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] silane,
(4) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azulenyl)] silane,
(5) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] silane,
(6) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] silane,
(7) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-1-azurenyl)] silane,
(8) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-1-azulenyl)] silane,
(9) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] silane,
(10) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] silane,
(11) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] silane,
(12) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] silane,
(13) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] silane,
(14) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] silane,
(15) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] silane,
(16) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] silane,
(17) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azulenyl)] silane,
(18) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] silane,
(19) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] silane,
(20) Dimethyl [(2-ethyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] silane,
Etc.

  Moreover, the following structure 8 can be illustrated.

[In the structure 8, R ¹⁹¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. R ¹⁹² is halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. R ¹⁹³ , R ¹⁹⁴ , R ¹⁹⁵ and R ¹⁹⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Q ¹⁹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, it is possible to consider the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the cyclopentadienyl group and indenyl group, and only one of them is illustrated, but cyclopentadienyl It may be another isomer that differs only in the position of the double bond in the 5-membered ring in the group and the indenyl group, or a mixture thereof. ]

R ¹⁹¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Of these, methyl, ethyl, furyl, and 2-methylfuryl are preferable.
R ¹⁹² is an aryl group having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl. 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like can be mentioned.

R ¹⁹³ , R ¹⁹⁴ , R ¹⁹⁵ and R ¹⁹⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, Examples include i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like, preferably methyl, ethyl and n-propyl. .

Q ¹⁹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Q ¹⁹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 8 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane,
(2) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-tert-butylphenyl) -indenyl} ethane,
(3) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(4) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,
(5) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane,
(6) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(7) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(8) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(9) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane,
(10) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(11) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(12) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(13) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(14) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(15) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(16) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(17) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(18) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(19) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(20) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,

(21) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(22) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(23) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(24) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(25) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(26) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(27) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(28) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(29) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(30) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(31) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(32) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(33) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(34) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(35) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(36) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(37) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane;
(38) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-tert-butylphenyl) -indenyl} ethane;
(39) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(40) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,

(41) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane,
(42) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-tert-butylphenyl) -indenyl} ethane,
(43) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(44) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(45) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane,
(46) 1- (2-Methyl-4-t-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane ,
(47) 1- (2-Methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane ,
(48) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(49) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(50) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4- (4-tert-butylphenyl) -indenyl} (dimethyl) silane,
(51) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(52) (2-methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(53) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(54) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(55) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(56) (2-methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(57) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(58) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(59) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(60) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,

(61) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(62) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(63) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(64) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(65) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(66) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(67) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(68) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(69) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(70) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(71) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(72) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(73) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane,
(74) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-t-butylphenyl) -indenyl} ethane,
(75) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(76) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,
(77) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane;
(78) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(79) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(80) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,

(81) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane;
(82) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(83) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(84) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(85) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(86) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(87) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(88) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(89) (2-methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(90) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(91) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(92) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(93) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(94) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(95) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(96) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(97) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(98) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(99) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(100) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,

(101) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(102) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(103) (2-methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(104) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(105) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(106) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(107) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(108) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
Etc.

2. Method for Producing α-Olefin Polymerization Catalyst The α-olefin polymerization catalyst of the present invention comprises the above component [A], component [B], component [C] and component [D] in the absence of an olefin. Or it can form by making it contact continuously or several times at once.
In addition, when the component [A] or the component [D] is contacted with the component [B], the component [C] may be contacted simultaneously or continuously, or once or a plurality of times.
In addition, each of the component [A], the component [B], the component [C], and the component [D] may be used alone or in combination of two or more.

As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
(1) The component [B] previously contacted with the component [C] is further contacted with the component [C] after contacting the component [D] with the contact product obtained by contacting the component [D]. Method,
(2) The component [B] previously contacted with the component [C] is further contacted with the component [C] after contacting the component [A] with the contact product obtained by contacting the component [A]. Method,
(3) A method of contacting a component [A] previously contacted with the component [C] with a contact product obtained by contacting the component [B] with the component [D] previously contacted with the component [C].
(4) A method of contacting a component [D] that has been previously contacted with the component [C] with a contact product that has been previously contacted with the component [B] with the component [A] that has been previously contacted with the component [C].
(5) A method of bringing the component [A] into contact with the contact product obtained by bringing the component [D] into contact with the component [B] which has been brought into contact with the component [C] in advance.
(6) A method of bringing the component [D] into contact with the contact product obtained by bringing the component [A] into contact with the component [B] that has been brought into contact with the component [C] in advance.
(7) A method in which the component [A] and the component [D] are simultaneously brought into contact with the component [B] that has been previously brought into contact with the component [C].
It is.

The regularity improving effect according to the present invention is considered to be due to the following reaction mechanism.
That is, the metallocene compound is usually activated by a promoter component and, if necessary, an organoaluminum component to form a polymerization active site. At the same time, the metallocene compound has become a stable active site by forming an ion pair with the cocatalyst as a cation species.
By the way, in the present invention, the presence of cyclopentadiene between such a metallocene cation species and the co-catalyst ion pair changes the vicinity of the active site sterically and electronically, and a new active site is formed. to be born. Further, such active sites are considered to have a feature of high regularity by being sterically modified.
Therefore, in the present invention, before the metallocene compound of component [A] and the co-catalyst compound of component [B] come into contact, it is necessary that the cyclopentadiene compounds of component [D] come into contact with either of them. In particular, it is considered that the effect is most exhibited when the cyclopentadiene compound of the component [D] is brought into contact in advance by utilizing the adsorption action of the solid of the component [B].
Therefore, the contact method of the above component is preferably (1) the contact product obtained by bringing the component [D] into contact with the component [B] previously contacted with the organoaluminum compound of the component [C], In this method, after contacting [C], component [A] is contacted.

  The contacting of each component is usually performed in an aliphatic hydrocarbon or an aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It carries out between -20 degreeC-150 degreeC, Preferably it carries out between 0 degreeC-60 degreeC, More preferably, it is between 10 degreeC-30 degreeC.

The amount of the components [A], [B], [C] and [D] used in the present invention is arbitrary. For example, the amount of component [A] used relative to component [B] is preferably in the range of 0.1 to 100 μmol, particularly preferably 0.5 to 50 μmol, relative to 1 g of component [B]. In addition, the amount of component [D] used relative to component [B] is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component [B]. However, the molar ratio [D] / [A] of [D] to component [A] is 0.1 to 99.0, preferably 1.0 to 10.0.
The amount of component [C] relative to component [A] or component [D] is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ in terms of molar ratio. It is.

Moreover, the catalyst which concerns on this invention can implement prepolymerization which consists of making this contact an olefin and polymerizing a small amount.
Therefore, the amount of the polymer to be prepolymerized is preferably 0.01 or more, more preferably 0.1 or more by weight ratio with respect to the component [B], and the upper limit is 100 or less for economy and handling. Preferably it is 50 or less. Here, the weight ratio of the polymer to the component [B] may be expressed as the prepolymerization magnification.

The olefin used for the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkane and styrene, and propylene is preferable.
The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. Moreover, component [C] can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.
The catalyst used in the present invention includes, in addition to the components [A], [B], [C], and [D], polyethylene, polypropylene, and the like that are usually used as long as the object of the present invention is not impaired. Polymers, solids of inorganic oxides such as silica and titania may be added.

3. Use of Catalyst / Propylene Polymerization As long as the monomer efficiently contacts the α-olefin polymerization catalyst including the component [A], the component [B], the component [C] and the component [D], any polymerization method can be used. Can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas without using a liquid solvent substantially. For example, a vapor phase method that maintains the shape can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.
The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.0 MPa or more is preferable, and 1.5 MPa or more is more preferable. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Furthermore, as a molecular weight regulator and for activity improvement effect, hydrogen is supplementarily used in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene. be able to.

  Moreover, when using propylene as a monomer, you may perform the copolymerization which uses a C2-C20 olefin or alpha olefin as a comonomer other than propylene. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and a plurality of the above-mentioned comonomers can be used. Specifically, they are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Among these, a preferable comonomer is ethylene. At this time, in order to obtain a polymer having high rigidity, it is preferable to use 5 mol% or less of ethylene contained in the polymer. More preferably, ethylene is used so that the amount is 1 mol% or less, and propylene homopolymerization is more preferable.

4). Analysis / property evaluation of propylene-based polymer Propylene-based polymer that can be produced using the catalyst for α-olefin polymerization of the present invention depends on the characteristics of the production method (or preparation method) of the catalyst. It is considered that the active site is sterically modified by interposing a cyclopentadiene between the ion pair and the feature is that the regularity is high.
The propylene-based polymer obtained by the production method of the present invention is considered to have higher stereoselectivity as the value of mm is higher. Therefore, the propylene-based polymer according to the present invention preferably has this mm of 99% or more.
In addition, it is considered that the position selectivity becomes higher as the value of the heterogeneous bond represented by 2,1 bond is smaller. Therefore, the propylene-based polymer according to the present invention preferably has an amount of 2,1 bonds of 0.5% or less.
The amount of these mm, 2,1 bonds can be controlled by the amount of cyclopentadiene used in the present invention, in addition to the polymerization temperature and MFR.
In the present invention, high regularity means that the stereoselectivity and position selectivity are high.
Examples of regularity include the following ¹³ CNMR measurement methods, and in the present invention, regularity was also evaluated from ¹³ CNMR measurement.

(1) Analysis of propylene-based polymer by ¹³ CNMR Measurement was performed using a Bruker BioSpin AV400M NMR apparatus equipped with a 10 mmφ cryoprobe.
Specifically, 200 mg of a sample was completely dissolved in 2.5 ml of a mixed solvent of o-dichlorobenzene / benzene bromide-d5 (volume ratio 4/1) in an NMR sample tube (10 mmφ), and then protonated at 130 ° C. It was measured by a complete decoupling method.
・ Flip angle: 90 degrees ・ Pulse interval: 15 seconds ・ Number of integrations: 512 times

A more specific method for determining the mm fraction will be described below. Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit occur in three regions depending on the configuration.
mm: about 23.3 to about 21.2 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.8 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight or the like, but the above three regions can be easily identified.
Here, mm, mr, and rr are represented by the following structural formulas (3-a) to (3-c), respectively.

The mm fraction is calculated from the following mathematical formula (I).
mm fraction = peak area of mm region / (peak area of mm region + peak area of mr region + peak area of rr region) × 100 [%] (I)

  The propylene-based polymer that can be produced using the α-olefin polymerization catalyst of the present invention may have the following structural formulas (4-a) and (4-b) as a partial structure including a position irregular unit.

Among these, the carbon A and A ′ peaks appear in the mr region. Carbon B and B ′ peaks appear at 16.8 to 17.8 ppm.
Therefore, when calculating the mm fraction according to the above formula (I), the peak area based on the carbons A and A ′ appearing in mr from the peak area of the mr region to the peak not based on the head-to-tail three-linked chain. Need to be reduced.

The peak areas based on carbon A are carbon C (resonance near 42.4 ppm), carbon D and G (both resonance near 36.0 ppm), carbon E of the position irregular partial structure [structural formula (4-a)]. It can be evaluated from 1/6 of the sum of the peak areas of (resonance around 38.7 ppm), carbon F (resonance around 30.7 ppm), and carbon H (resonance around 31.6 ppm).
The peak areas based on carbon A ′ are carbon I (resonance near 27.7 ppm), carbon J (resonance near 37.6 ppm), and carbon K (positional disorder partial structure [Structure (4-b)]). It can be evaluated by 1/3 of the sum of the peak areas of resonance at around 31.0 ppm.
Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
As described above, since the peak areas of mm, mr, and rr can be evaluated, it is possible to obtain the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center according to the above formula (I).

  The 2,1-bond content (the amount of heterogeneous bonds due to 2,1-insertion) is determined according to the following mathematical formula.

  However, among the symbols in the above formula, αα is a peak intensity derived from methylene carbon sandwiched between 1,2-bonded propylene chains, which occurs around 45.5 to 47.0 ppm, and C, D , E, F, G, H, I, J, and K are the peak intensities of carbon corresponding to the symbols shown in the structural formulas (4-a) and (4-b).

(2) Melting point (Tm)
As the stereoselectivity increases, the melting point (Tm) value increases. The propylene polymer according to the present invention preferably has a melting point (Tm) of 153 ° C. or higher, more preferably 154 ° C. or higher.
This melting point (Tm) can be controlled by the amount of cyclopentadiene used in the present invention, in addition to the polymerization temperature and MFR.

(3) Temperature (Tp) at the peak position of the TREF elution curve and 40 ° C. soluble content When the regularity is high, the value of the temperature (Tp) at the peak position of the TREF elution curve increases. The propylene polymer according to the present invention preferably has a Tp of 105 ° C. or higher, more preferably 106 ° C. or higher.
Moreover, when the active site with low regularity decreases, the amount of 40 ° C. solubles decreases. The propylene polymer according to the present invention preferably has a 40 ° C. soluble content of 0.3% by weight or less, more preferably 0.2% by weight or less.
The amount of Tp and 40 ° C. soluble component can be controlled by the amount of cyclopentadiene used in the present invention, in addition to the polymerization temperature and MFR.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, physical property measurement, analysis, and the like in the following examples are based on the analysis / physical property evaluation of the propylene polymer and the following method.

(1) Melt flow rate (MFR)
It was measured according to the melt flow rate (test condition: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.

(2) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(3) Melting point (Tm)
The melting point (Tm) was obtained by using a DSC6200 manufactured by Seiko Instruments Inc., filling a sheet-like sample piece into a 5 mg aluminum pan, raising the temperature from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and holding for 5 minutes. Thereafter, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the maximum melting temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min was obtained.

(4) Temperature (Tp) and 40 ° C. soluble content of peak position of TREF elution curve Measurement of temperature (Tp) and 40 ° C. soluble content of peak position of TREF elution curve is as follows.
A sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This was introduced into a temperature rising elution fractionation chromatograph (TREF) column at 140 ° C., cooled to 100 ° C. at a temperature decreasing rate of 8 ° C./min, and then cooled to 40 ° C. at a temperature decreasing rate of 4 ° C./min. Hold for a minute. Thereafter, orthodichlorobenzene, which is a solvent, is allowed to flow through the column at a flow rate of 1 mL / min, and components dissolved in orthodichlorobenzene at 40 ° C. are eluted in the TREF column for 10 minutes. The column is heated linearly to 140 ° C over time to obtain an elution curve. The temperature at the peak position of the elution curve was defined as Tp.
The apparatus configuration of TREF used is as follows.
Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inert treatment glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength infrared detector, manufactured by FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

[Synthesis Example of Catalyst Component [A]]
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium:
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. As well as.

[Synthesis Example of Catalyst Component [B]]
Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (668 g) was added to 2264 g of distilled water, and then 4 L of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated at 90 ° C. for 210 minutes. The reaction slurry was filtered after adding 4000 g of distilled water to obtain 810 g of a cake-like solid.
Next, 432 g of lithium sulfate and 1924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the solid on the cake was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, further washing with distilled water to pH 5-6, and filtration. As a result, 760 g of a cake-like solid was obtained.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

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

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

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

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

[Synthesis example 2 of catalyst component [D]]
Synthesis of dimethyl {bis (2-methyl-4-phenylindenyl)} silane:
The synthesis of dimethyl {bis (2-methyl-4-phenylindenyl)} silane was carried out in the same manner as described in “Synthesis of metallocene I used in polymerization examples” of JP-A No. 6-100579.

[Example 1]
Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (66 mL) was added to form a slurry. To this was added triisobutylaluminum (25 mmol; 0.0 mL) was added and the mixture was stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 30 mL.
In another flask (volume: 200 mL), the dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) prepared in Synthesis Example 1 of the catalyst component [D] was prepared. ) Indenyl}] silane (105 μmol) dissolved in toluene (21 mL) (solution 1), and further in a separate flask (volume 200 mL), rac-dichloro [1] prepared in the synthesis example of the catalyst component [A]. , 1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium (45 μmol) was dissolved in toluene (9 mL) (solution 2).

After adding triisobutylaluminum (0.42 mmol: 0.6 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, add the above solution 1 (21 mL) and stir at room temperature for 20 minutes. did.
Then, after further adding triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL), the above solution 2 was added, and the mixture was stirred at room temperature for 1 hour.
Thereafter, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 2 hours. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 23.9 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.39 (catalyst A-1).

[Example 2]
The catalyst was prepared in the same manner as in Example 1, except that the dimethyl {bis (2-methyl-4-phenylindenyl)} silane (105 μmol) prepared in Synthesis Example 2 was used as the catalyst component [D]. It was. The yield of the dried prepolymerized catalyst was 25.8 g, and the prepolymerization ratio was 1.58 (Catalyst A-2).

[Example 3]
The catalyst was prepared in the same manner as in Example 1, except that 1,4,6-trimethylcyclopentadiene (105 μmol) was used as the catalyst component [D]. The yield of the dry prepolymerized catalyst was 30.9 g, and the prepolymerization ratio was 2.09 (Catalyst A-3).

[Comparative Example 1]
Catalyst preparation and prepolymerization:
Into a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (66 mL) was added to form a slurry. To this was added triisobutylaluminum (25 mmol; 0.0 mL) was added and the mixture was stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 30 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4] prepared in the synthesis example of the catalyst component [A] was used. -Hydroazurenyl}] hafnium (45 μmol) was dissolved in toluene (9 mL) (solution 1).

After adding triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated smectite, add the above solution 1 (9 mL) and stir at room temperature for 1 hour. did.
Thereafter, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 31.0 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.10 (catalyst B).

[Polymerization Example 1]
Propylene polymerization:
After thoroughly drying in advance by flowing nitrogen through a 3 L autoclave, the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (144 mg / mL) and introducing 750 g of liquid propylene, the temperature was raised to 70 ° C.
Thereafter, 150 mg of the catalyst A-1 synthesized in Example 1 by weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° C. for 1 hour, ethanol was added to terminate the polymerization.
As a result, 235 g of a polymer was obtained. The MFR was 0.04 g / 10 min, and the activity was 1600 g PP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 2]
Polymerization was carried out in the same manner as in Polymerization Example 1, except that hydrogen was introduced, the amount of hydrogen was 54 Nml, and 120 mg of Catalyst A-1 was used.
As a result, 338 g of a polymer was obtained. The MFR was 0.35 g / 10 min, and the activity was 2800 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 3]
In the polymerization example 2, the same polymerization was carried out except that the amount of hydrogen was 80 Nml and the catalyst A-1 was used in an amount of 75 mg.
As a result, 159 g of a polymer was obtained. The MFR was 2.04 g / 10 min, and the activity was 2100 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 4]
In the polymerization example 2, the same polymerization was carried out except that the amount of hydrogen was 108 Nml and the catalyst A-1 was used in an amount of 50 mg.
As a result, 167 g of a polymer was obtained. The MFR was 11.6 g / 10 min, and the activity was 3300 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 5]
In the polymerization example 2, the same polymerization was performed except that 120 mg of the catalyst A-2 was used instead of the catalyst A-1.
As a result, 229 g of a polymer was obtained. The MFR was 0.30 g / 10 min, and the activity was 1900 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 6]
In Polymerization Example 2, the same polymerization was carried out except that the amount of hydrogen was 78 Nml and 50 mg of Catalyst A-3 was used instead of Catalyst A-1.
As a result, 107 g of a polymer was obtained. The MFR was 2.05 g / 10 min, and the activity was 2100 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 7]
In Polymerization Example 2, the same polymerization was carried out except that the amount of hydrogen was 39 Nml and 100 mg of catalyst A-3 was used instead of catalyst A-1.
As a result, 151 g of a polymer was obtained. The MFR was 0.25 g / 10 min, and the activity was 1500 gPP / g catalyst · hour. The results are summarized in Table 1.

[Polymerization Example 8]
In Polymerization Example 2, the same polymerization was carried out except that the amount of hydrogen was 18 Nml and 90 mg of Catalyst B synthesized in Comparative Example 1 was used instead of Catalyst A-1.
As a result, 235 g of a polymer was obtained. The MFR was 0.57 g / 10 min, and the activity was 2600 gPP / g catalyst · hour. The results are summarized in Table 2.

[Polymerization Example 9]
In the polymerization example 8, the same polymerization was carried out except that 54 Nml of hydrogen and 30 mg of catalyst B were used.
As a result, 104 g of a polymer was obtained. The MFR was 2.6 g / 10 min, and the activity was 3500 g PP / g catalyst · hour. The results are summarized in Table 2.

[Polymerization Example 10]
In Polymerization Example 9, the same polymerization was performed except that 100 Nml of hydrogen was used.
As a result, 124 g of a polymer was obtained. The MFR was 2.6 g / 10 min, and the activity was 4100 gPP / g catalyst · hour. The results are summarized in Table 2.

[Polymerization Example 11]
In Polymerization Example 9, the same polymerization was performed except that 130 Nml of hydrogen was used.
As a result, 152 g of a polymer was obtained. The MFR was 27.4 g / 10 min, and the activity was 5100 gPP / g catalyst · hour. The results are summarized in Table 2.

１：ｒａｃ−ジクロロ［１，１’−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４−ヒドロアズレニル｝］ハフニウム
２：ジメチル［ビス｛２−（２−メチル−５−フリル）−４−（４−ｉ−プロピルフェニル）インデニル｝］シラン
３：ジメチル｛ビス（２−メチル−４−フェニルインデニル）｝シラン
４：１，２，４−トリメチルシクロペンタジエン

1: rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium 2: dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] silane 3: dimethyl {bis (2-methyl-4-phenylindenyl)} silane 4: 1,2,4-trimethylcyclopentadiene

  As is clear from Tables 1 and 2, the α-olefin polymerization catalysts A-1, A-2 and A-3 of the present invention containing the component (D) do not contain the component (D) of the conventional method. Compared to catalyst B of the conventional method, the temperature at the peak position of the TREF elution curve (Tp) is high, 40 ° C. soluble component is small, molecular weight distribution (Q value: Mw / Mn) is wide, and melting point (Tm) It can be seen that a high propylene polymer can be efficiently produced.

  The α-olefin polymerization catalyst of the present invention enables the production of an α-olefin polymer having a high molecular weight and a high melting point, and has high industrial applicability. Further, the α-olefin polymer polymerized using the α-olefin polymerization catalyst of the present invention has a wide molecular weight distribution (Q value: Mw / Mn) and a high melting point. Moreover, it is highly available.

Claims (9)

An α-olefin polymerization catalyst prepared by contacting at least the following components [A] to [D] in the absence of an olefin.
Component [A]: a transition metal compound of Group 4 of the periodic table represented by formula (a1).

[In General Formula (a1), E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ¹¹ represents zirconium or hafnium. , X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: an ionicity capable of reacting with the transition metal compound [A] carried on the solid fine particles and converted into a cation by reacting with the aluminum oxy compound [B-1] carried on the solid fine particles At least 1 type chosen from the compound group which consists of a compound or Lewis acid [B-2], and an ion exchange layered silicate [B-3].
Component [C]: an organoaluminum compound.
Component [D]: cyclopentadiene derivative.   2. The α-olefin polymerization method according to claim 1, which is prepared by bringing the component [B] and the component [D] into contact with each other before the component [A] and the component [D] are in contact with each other. catalyst.   The α-olefin polymerization catalyst according to claim 1, wherein an α-olefin polymer having a melting point (Tm) of greater than 153 ° C. can be produced.   The temperature (Tp) at the peak position of the TREF elution curve is 105 ° C or higher, and an α-olefin polymer having a 40 ° C soluble component of less than 0.3% by weight can be produced. The α-olefin polymerization catalyst according to claim 1. Component [D] is the cyclopentadiene derivative represented by following General formula (2), The alpha-olefin polymerization catalyst of any one of Claims 1-4 characterized by the above-mentioned.

[In General Formula (2), E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]   The component [B] is an ion-exchange layered silicate [B-3], the α-olefin polymerization catalyst according to any one of claims 1 to 5.   The catalyst for α-olefin polymerization according to any one of claims 1 to 6, wherein the ion-exchange layered silicate [B-3] is a smectite group.   The olefin polymerization catalyst according to any one of claims 1 to 7, wherein the olefin is prepolymerized in a weight ratio of 0.01 to 100 with respect to the component [B].   The manufacturing method of the alpha olefin polymer characterized by superposing | polymerizing alpha olefin using the catalyst for alpha olefin polymerization of any one of Claims 1-8.

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