JP6142766B2 - α-Olefin Polymerization Catalyst and Method for Producing α-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, and more particularly, 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 polymerization activity per transition metal than a Ziegler-Natta catalyst, and is a homogeneous active species. It is possible to produce polyolefins having a narrow molecular weight distribution, and therefore, it is possible to produce differentiated polyolefins compared to polymers obtained with Ziegler-Natta catalysts.

  The metallocene complex was originally 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 polymerization activity, the conjugated 5-membered ring has electrons. By arranging a donating substituent and connecting the conjugated 5-membered ring with a bridging group, the regularity is controlled, and by introducing a substituent at a specific position, the regiospecificity at the time of α-olefin insertion is improved. In addition, a number of improved catalysts have been disclosed, such as improving the molecular weight of the polymer produced by using an indenyl ring or a fluorenyl ring in which another conjugated ring is condensed to a conjugated 5-membered ring.

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. Thus, 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 of 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 polymerization activity is improved. Polypropylene with high regularity is 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, and a polypropylene having improved regularity, melting point and molecular weight is obtained. Patent Document 6 proposes a catalyst complex in which the substituent at the 4-position of the azulenyl skeleton is a phenyl group, and another carbocyclic ring is condensed to this phenyl group, and the regularity, melting point and molecular weight are increased. Polypropylene has been obtained. Further, Patent Document 7 discloses a catalyst complex in which the substituent at the 4-position of the azulenyl skeleton is a phenyl group, and a silyl group is further substituted on this phenyl group, and polypropylene having improved regularity, melting point and molecular weight. Is obtained.

  In addition, the metallocene catalyst using a metallocene complex as described above has high polymerization activity, and the resulting polypropylene is excellent in regularity. However, the molecular weight distribution is narrow and the molding processability is poor. 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.

Furthermore, Patent Document 11 discloses that a polymer having excellent operational stability and high molecular weight and wide 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.

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 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. Moreover, only the ethylene polymerization is disclosed by the said patent document 12, 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.

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. An object of the present invention is to provide an α-olefin polymerization catalyst capable of producing an α-olefin polymer and a method for producing an α-olefin polymer having a wide molecular weight distribution and excellent molding processability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use a diamine derivative in a specific metallocene catalyst system to broaden the molecular weight distribution of a polymer obtained by polymerizing an α-olefin. Further, the inventors have found that the melting point is further increased and have completed the present invention.

That is, according to the first invention of the present invention, there is provided an α-olefin polymerization catalyst characterized by contacting at least the following components [A] to [D] in the absence of an olefin. The
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 each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, each of which may have a substituent, and Q ¹¹ May have a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. Represents a germylene group, M ¹¹ represents zirconium or hafnium, X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. A silyl group having a hydrogen group, 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. ]
Component [B]: An aluminum oxy compound [B-1] supported on solid fine particles and the transition metal compound [A] supported on solid fine particles may react to convert [A] into a cation. At least one selected from the group consisting of possible ionic compounds or Lewis acids [B-2] and ion-exchange layered silicates [B-3].
Component [C]: an organoaluminum compound.
Component [D]: a diamine derivative.

Further, according to the second invention of the present invention, in the first invention, the component [B] and the component [D] are contacted in advance before the component [A] and the component [D] are contacted. An α-olefin polymerization catalyst is provided.
Furthermore, according to the third invention of the present invention, in the first or second invention, the component [D] is a diamine derivative represented by the following general formula (D1). A catalyst is provided.

［一般式（Ｄ１）中、Ｒは、炭素数１〜２０の炭化水素基を表し、Ｘは、水素原子、炭素数１〜１０の炭化水素基またはジアルキルアミノ基を表し、複数のＲ及びＸは、それぞれ同一でも異なっていてもよく、任意のＲ、Ｘが連結された環状構造を有してもよく、ｎは、０≦ｎ≦４を表す。］

[In General Formula (D1), R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a dialkylamino group, and a plurality of R and X Each may be the same or different, and may have a cyclic structure in which arbitrary R and X are connected, and n represents 0 ≦ n ≦ 4. ]

According to a fourth invention of the present invention, in any one of the first to third inventions, the component [B] is an ion-exchange layered silicate [B-3]. A catalyst is provided.
According to a fifth aspect of the present invention, there is provided an α-olefin polymerization catalyst according to the fourth aspect, wherein the ion-exchange layered silicate [B-3] is a smectite group. .
Furthermore, according to the sixth aspect of the present invention, the α-olefin polymerization catalyst of any one of the first to fifth aspects is preliminarily polymerized in the range of 0.01 to 100 by weight. A prepolymerization catalyst for olefin polymerization is provided.

  According to the seventh invention of the present invention, the α-olefin polymerization catalyst according to any one of the first to fifth inventions or the α-olefin polymerization prepolymerization catalyst according to the sixth invention is used, and α -The manufacturing method of the alpha olefin polymer characterized by performing olefin polymerization 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, 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, thus having a high melting point and high heat resistance. it can.

It is a figure of the description of the base line 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 absence.

(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 each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, each of which may have a substituent, and Q ¹¹ May have a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. Represents a germylene group, M ¹¹ represents zirconium or hafnium, X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. A silyl group having a hydrogen group, 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. ]

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.
Preferably, it is a substituted cyclopentadienyl group, a substituted indenyl group or a substituted azulenyl group. More preferably, E ¹¹ and E ¹² are substituted azulenyl groups.

The ^{Q 11 couples} the ^{E 11} and ^{E 12,} divalent hydrocarbon group having 1 to 20 carbon atoms bridging the ^{E 11} and ^{E 12} through the carbon of 1 or 2 carbon atoms, silylene group, A germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ¹¹ is zirconium or hafnium, preferably hafnium.

X ¹¹ and Y ¹¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ¹¹ and / or Y ¹¹ is eliminated to become an active metallocene having olefin polymerization ability. As this object is achieved, 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, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

In the case where E ¹¹ and E ¹² are substituted cyclopentadienyl groups, the following structures can be exemplified.

[In General Formula (A2), R ²¹ and R ²⁴ each independently represent 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, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, or Represents a germylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, M ²¹ represents zirconium or hafnium, X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, carbon It represents 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. ]

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 group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, i-pentyl group, n- A hexyl group etc. are mentioned, Preferably they are a methyl group, an ethyl group, n-propyl group, n-butyl group, More preferably, it is 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 having 1 to 6 carbon atoms, more preferably 1 carbon atom. ˜4 alkyl groups.
Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i- A pentyl group, an n-hexyl group, a phenyl group and the like can be mentioned, preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, an n- A hexyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or a t-butyl group.

Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which links two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which connects two five-membered rings, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

The M ²¹ is zirconium or hafnium, preferably hafnium.

X ²¹ and Y ²¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ²¹ and / or Y ²¹ is eliminated to become 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.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

Non-limiting examples of the metallocene compound represented by the general formula (A2) 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 (A3), 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. Represents an alkyl group having 1 to 3 carbon atoms having an alkylsilyl group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an oxygen-containing heterocyclic group or a sulfur-containing heterocyclic group, and R ³² and R ³⁴ are respectively independently, halogen, represents silicon or an aryl group having 6 to 30 carbon atoms which may contain hetero elements selected from these, Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms , 1-20 carbons It represents an germylene group which may have a hydrocarbon group which has silylene group or a carbon atoms, which may 20 have a hydrogen group, M ³¹ represents zirconium or hafnium, X ³¹ and Y ³¹ are, Each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or An alkylamino group having 1 to 20 carbon atoms is represented. ]

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, or an alkenyl having 2 to 8 carbon atoms. Group, 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 carbon number in which the alkyl group has a trialkylsilyl group having 1 to 3 carbon atoms. A silyl group having 1 to 3 alkyl groups, a hydrocarbon group having 1 to 6 carbon atoms, an oxygen-containing heterocyclic group or a sulfur-containing heterocyclic group, preferably an alkyl group having 1 to 4 carbon atoms or an oxygen-containing heterocyclic ring It is a group.
Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, i-pentyl group, n- Hexyl group, methoxy group, ethoxy group, phenoxy group, butenyl group, fluoromethyl group, phenyl group, 5-methyl-2-furyl group, 4,5-dimethylfuryl group, etc. are preferable, preferably methyl group, ethyl group N-propyl group, i-propyl group, 5-methyl-2-furyl group, and 4,5-dimethyl-2-furyl group.

R ³² and R ³⁴ 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. As the aryl group, in the range of 6 to 30 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, and 1 carbon atom on the aryl cyclic skeleton. May have a halogen-containing hydrocarbon group of -6 as a substituent.
At least one of R ³² and R ³⁴ is preferably a 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, It is a 4-chlorophenyl group, and more preferably, R ³² and R ³⁴ are the same as each other.

Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings and bridges two conjugated five-membered ring ligands through carbon having 1 or 2 carbon atoms, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ³¹ is zirconium or hafnium, preferably hafnium.

X ³¹ and Y ³¹ are auxiliary ligands. Component [A] reacts with component [B], and X ³¹ and / or Y ³¹ is eliminated to form 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, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

The following can be mentioned as a non-limiting example of the metallocene compound represented by the general formula (A3).
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-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 (A4), R ⁴¹ and R ⁴² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁴³ and R ⁴⁴ each independently represent halogen, silicon, or a combination thereof. Represents an aryl group having 6 to 30 carbon atoms which may contain a plurality of selected hetero elements, and Q ⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms Represents a silylene group which may have a hydrocarbon group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, M ⁴¹ represents zirconium or hafnium, and 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, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a carbon number 1-20 a It represents a Kiruamino group. ]

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

R ⁴³ and R ⁴⁴ 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, preferably 6 to 24 carbon atoms. Of the aryl group.
Preferred examples include phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-methylphenyl group, 4-i-propylphenyl group, 4-t-butylphenyl. Group, 4-trimethylsilylphenyl group, 4- (2-fluoro-4-biphenylyl) group, 4- (2-chloro-4-biphenylyl) group, 1-naphthyl group, 2-naphthyl group, 4-chloro-2- Naphthyl group, 3-methyl-4-trimethylsilylphenyl group, 3,5-dimethyl-4-tert-butylphenyl group, 3,5-dimethyl-4-trimethylsilylphenyl group, 3,5-dichloro-4-trimethylsilylphenyl group Etc.

Q ⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that links two 5-membered rings and bridges two conjugated 5-membered ring ligands via carbon having 1 or 2 carbon atoms, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ⁴¹ is zirconium or hafnium, preferably hafnium.

X ⁴¹ and Y ⁴¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ⁴¹ and / or Y ⁴¹ is eliminated to become 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.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

The following can be mentioned as a non-limiting example of the metallocene compound represented by the general formula (A4).
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 (A5), R ⁵¹ represents a hydrocarbon group having 1 to 6 carbon atoms, and R ⁵² may contain halogen, silicon, or a plurality of heteroelements selected therefrom. represents 30 aryl ^{group, R 53, R 54, R} 55 and ^{R 56} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon ^{atoms,, Q 51} is 1 to carbon atoms 20 represents a divalent hydrocarbon group having 20 carbon atoms, a silylene group optionally having 1 to 20 carbon atoms, or a germylene group optionally having 1 to 20 carbon atoms, M ⁵¹ represents zirconium or hafnium, and X ⁵¹ and Y ⁵¹ each independently represents a silyl group having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. , Halogen having 1 to 20 carbon atoms Hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, i-pentyl group, n- A hexyl group etc. are mentioned, Preferably they are a methyl group, an ethyl group, and n-propyl group.
R ⁵² is an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Preferred examples include phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-methylphenyl group, 4-i-propylphenyl group, 4-t-butylphenyl. Group, 4-trimethylsilylphenyl group, 2-fluoro-4-biphenylyl group, 2-chloro-4-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 4-chloro-2-naphthyl group, 3-methyl-4 -Trimethylsilylphenyl group, 3,5-dimethyl-4-t-butylphenyl group, 3,5-dimethyl-4-trimethylsilylphenyl group, 3,5-dichloro-4-trimethylsilylphenyl group 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 group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i- Examples thereof include a pentyl group, an n-hexyl group, and a phenyl group, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, and a phenyl group are preferable.
Preferably, 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.

Q ⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings and bridges two conjugated five-membered ring ligands through one or two carbon atoms, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ⁵¹ is zirconium or hafnium, preferably hafnium.

X ⁵¹ and Y ⁵¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ⁵¹ and / or Y ⁵¹ is eliminated to become 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 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.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

The following can be mentioned as a non-limiting example of the metallocene compound represented by the general formula (A5).
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) (2-i-propyl-4-phenyl-4H-azurenyl)} hafnium,

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

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

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

(81) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(82) Dichloro [1,1′-dimethylsilylene {3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(83) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(84) Dichloro [1,1′-dimethylsilylene {3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(85) Dichloro [1,1′-dimethylsilylene {3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(86) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(87) Dichloro [1,1′-dimethylsilylene {3- (1-cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(88) dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(89) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(90) Dichloro [1,1′-dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium ,
(91) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(92) Dichloro [1,1′-dimethylsilylene {2-n-propyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(93) Dichloro [1,1′-dimethylsilylene {3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(94) Dichloro [1,1′-dimethylsilylene {3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(95) Dichloro [1,1′-dimethylsilylene {3- (1-s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(96) Dichloro [1,1′-dimethylsilylene {3- (1-t-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(97) Dichloro [1,1′-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 (A6), R ⁶² represents 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 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, Adjacent substituents from ^{65 to} R ⁶⁸ may be bonded to each other to form a ring, and Q ⁶¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms. Represents a silylene group which may have an alkyl group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, M ⁶¹ represents zirconium or hafnium, and X ⁶¹ and Y ⁶¹ each independently represent Hydrogen atom, halogen A silyl group having a hydrocarbon group having 1 to 20 carbon atoms, 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 Represents. ]

R ⁶² is 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 a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group 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 is a divalent hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings and bridges two conjugated five-membered ring ligands through one or two carbon atoms, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ⁶¹ is zirconium or hafnium, preferably hafnium.

X ⁶¹ and Y ⁶¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ⁶¹ and / or Y ⁶¹ is eliminated to become an active metallocene having olefin polymerization ability. In order to achieve this object, X ⁶¹ and Y ⁶¹ are each independently a hydrogen atom, a halogen 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.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

The following can be mentioned as a non-limiting example of the metallocene compound represented by the general formula (A6).
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) dichlorodimethylmethylene (3-i-propylcyclopentadienyl) (fluorenyl) hafnium,
(2) dichlorodimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) hafnium,
(3) dichlorodimethylmethylene (3-trimethylsilylcyclopentadienyl) (fluorenyl) hafnium,
(4) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium,
(5) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (fluorenyl) hafnium,
(6) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) hafnium,
(7) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (fluorenyl) hafnium,
(8) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (fluorenyl) hafnium,
(9) dichlorodimethylmethylene (3-i-propyl-5-ethylcyclopentadienyl) (fluorenyl) hafnium,
(10) dichlorodimethylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (fluorenyl) hafnium,
(11) dichlorodimethylmethylene (3-trimethylsilyl-5-ethylcyclopentadienyl) (fluorenyl) hafnium,
(12) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-ethylcyclopentadienyl) (fluorenyl) hafnium,
(13) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(14) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium,
(15) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(16) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(17) dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium,
(18) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium,
(19) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium,
(20) dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium,

(21) dichlorodimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl) hafnium,
(22) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (dibenzo [b, h] fluorenyl) hafnium,
(23) Dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7, 8,9,10-octahydrodibenzo [b, h] fluorenyl) hafnium,
(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) hafnium,
(25) dichlorodiphenylmethylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(26) dichlorodiphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium,
(27) dichlorodiphenylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(28) dichlorodiphenylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(29) dichlorodimethylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(30) dichlorodimethylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(31) dichlorodimethylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(32) dichlorodimethylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(33) dichlorodiphenylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(34) dichlorodiphenylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(35) dichlorodiphenylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
(36) dichlorodiphenylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium,
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 (A7), R ⁷¹ and R ⁷² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁷³ and R ⁷⁴ each independently represent halogen, silicon, or Represents an aryl group having 6 to 30 carbon atoms which may contain a plurality of selected hetero elements, and Q ⁷¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms Represents a silylene group which may have an alkyl group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, M ⁷¹ represents zirconium or hafnium, and X ⁷¹ and Y ⁷¹ 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 a carbon number 1-20 a It represents a Kiruamino group. ]

R ⁷¹ and R ⁷² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. is there. 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 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, 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.

Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which links two conjugated five-membered ligands via carbon having 1 or 2 carbon atoms, which connects two five-membered rings, silylene. Group, a germylene group, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms. When the silylene group or the germylene group has two hydrocarbon groups, they may be bonded to each other to form a ring structure.
Examples of the divalent hydrocarbon group include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene, and arylalkylene groups such as diphenylmethylene. Examples of the silylene group having a hydrocarbon group include alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and methyl (phenyl). Examples thereof include (alkyl) (aryl) silylene groups such as silylene, arylsilylene groups such as diphenylsilylene, and alkyl oligosilylene groups such as tetramethyldisilylene. As the silylene group having a hydrocarbon group, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, an alkyl oligogermylene, in which silicon in the above-mentioned silylene group having a hydrocarbon group is replaced with germanium Groups and the like.
A silylene group having a hydrocarbon group or a germylene group having a hydrocarbon group is preferable, and an alkylsilylene group or an alkylgermylene group is more preferable.

M ⁷¹ is zirconium or hafnium, preferably hafnium.

X ⁷¹ and Y ⁷¹ are auxiliary ligands. The component [A] reacts with the component [B], and X ⁷¹ and / or Y ⁷¹ are eliminated to become an active metallocene having olefin polymerization ability. In order to achieve this object, X ⁷¹ and Y ⁷¹ are each independently a hydrogen atom, a halogen 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.
Here, examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group having 1 to 20 carbon atoms.

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. 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-methyl-4-phenylindenyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(2) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(3) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] hafnium,
(4) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] hafnium,
(5) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (4-fluorophenyl) -4H-azurenyl)] hafnium,
(6) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (4-fluorophenyl) -4H-azurenyl)] hafnium,
(7) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-azulenyl)] hafnium,
(8) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-azulenyl)] hafnium,
(9) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-azurenyl)] hafnium,
(10) Dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-azurenyl)] hafnium,
(11) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (1-naphthyl) -4H-azulenyl)] hafnium,
(12) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (1-naphthyl) -4H-azulenyl)] hafnium,
(13) Dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-methyl-4- (2-naphthyl) -4H-azulenyl)] hafnium,
(14) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-methyl-4- (2-naphthyl) -4H-azulenyl)] hafnium,
(15) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-ethyl-4-phenyl-4H-azurenyl)] hafnium,
(16) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-ethyl-4-phenyl-4H-azurenyl)] hafnium,
(17) dichloro [1,1′-dimethylsilylene (2-methyl-4-phenylindenyl) (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] hafnium,
(18) dichloro [1,1′-dimethylsilylene (2-ethyl-4-phenylindenyl) (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] hafnium,
(19) Dichloro [1,1′-dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium,
(20) dichloro [1,1′-dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] hafnium,

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

(2) Component [B]
As the component [B], the aluminum oxy compound [B-1] supported on the solid fine particles and the transition metal compound [A] supported on the solid fine particles react to convert [A] into a cation. At least one selected from the group consisting of an ionic compound or Lewis acid [B-2] and an ion-exchange layered silicate [B-3].

(2-1) Component [B-1]
Specific examples of the aluminum oxy compound [B-1] include compounds represented by the following general formula (B1), (B2), or (B3).

In 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, more preferably 1 to 1 carbon atom. 6 hydrocarbon residues are shown. A plurality of R ⁸¹ , R ⁹¹ and R ¹⁰¹ may be the same or different. R ¹⁰² represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (B1) and (B2) are also called alumoxanes, and 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.
In addition, the compound represented by the general formula (B3) 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 (B4). : 1 (molar ratio) reaction.

In General Formula (B4), R ¹¹¹ represents a hydrocarbon residue or 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 is supported on the solid fine particles and can react with the above-described transition metal compound [A] to convert [A] into a cation.
Specific examples of the ionic compound include a cation such as a carbonium cation and an ammonium cation, and an organic boron compound such as tetraphenylboron, tetrakis (3,5-difluorophenyl) boron, and tetrakis (pentafluorophenyl) boron. And a complex with an anion.
Examples of the Lewis acid include organic boron compounds such as tris (pentafluorophenyl) boron, and metal halide compounds such as aluminum chloride and magnesium chloride.
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, a finely divided solid inorganic compound or organic compound can be used.
Examples of inorganic compounds 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 compound 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 hydrocarbons such as styrene and divinylbenzene. Examples thereof include porous polymers made of polymers. Alternatively, a mixture thereof may be used.
The solid fine particles usually have an average particle diameter of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.

(2-4) Component [B-3]
Component [B-3] is an ion-exchange layered silicate (hereinafter sometimes simply referred to as “silicate”).
In the present invention, the silicate 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 (interlayer cations). 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 of 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 further 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 silicate. Specific examples of the chemical treatment in the present invention include (a) acid treatment, (b) salt treatment, (c) alkali treatment, and (d) organic matter treatment.

(A) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute part 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 acids may be used for the treatment. The treatment conditions with the acid are not particularly limited. Usually, the acid concentration is 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition of eluting at least a part of the substance constituting at least one compound selected from the group consisting of exchangeable layered silicates. The acid is generally used as an aqueous solution.

(B) Salt treatment
Ion-exchange 40% or more, preferably 60% or more of the exchangeable metal cations contained in the ion-exchange layered silicate before being treated with salts with cations dissociated from the salts shown below. Is preferred.
Salts used in such salt treatment for ion exchange are composed of at least one cation selected from the group consisting of an organic cation, an inorganic cation and a metal ion, and an organic anion and an inorganic anion. Examples thereof include salts composed of at least one anion selected from the group. For example, at least selected from the group consisting of a cation containing at least one atom selected from the group consisting of Group 1 to 14 atoms of the periodic table, a halogen anion, and an anion derived from an inorganic acid and an organic acid A preferred example is a compound composed of a kind of anion. Here, the anion derived from an acid is an anion in which at least one hydrogen cation is eliminated from the acid. For example, in the case of a monovalent inorganic acid such as HNO ₃ , the anion derived from the acid is NO ₃ ^— , and in the case of a trivalent inorganic acid such as H ₃ PO ₄ , the acid There are three types of anions derived from H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ and PO ₄ ³⁻ . The same applies to anions derived from organic acids. More preferred is a compound in which the cation is a metal ion and the anion is an anion derived from an inorganic acid or a halogen anion.

Specific examples of such salts are LiF, LiCl, LiBr, LiI, Li ₂ SO ₄ , Li (CH ₃ COO), Li ₂ CO ₃ , LiHCO ₂ , Li ₂ C ₂ O ₄ , LiClO ₄ , Li _3. PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg ₃ (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , _{mg (NO 3) 2, mg} (CH 3 COO) 2 and the like.

_{Further, Ti (CH 3 COO) 4} , Ti (CO 3) 2, Ti (NO 3) 4, Ti (SO 4) 2, TiF 4, TiCl 4, Zr (CH 3 COO) 4, Zr (CO 3) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , Hf (CH ₃ COO) ₄ , Hf (CO ₃ ) ₂ , Hf (NO ₃ ) ₄ , Hf (SO ₄ ) _{2 , HfF 4, HfCl 4, V} (CH 3 COCHCOCH 3) 3, VOCl 3, VCl 3, VCl 4, VBr 3 , and the like.

Furthermore, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn ( CH ₃ COO) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (CH ₃ COO) 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 and the} like.

In addition, Co (CH ₃ COO) 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 and the} like.
Furthermore, Zn (CH ₃ COO) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

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

(D) Organic matter treatment Examples of the organic matter used for the organic matter treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Furthermore, examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, tetraphenylborate, and the like other than the anions 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%.

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.
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, it is 20 mmol or less, Preferably it is 0.5 mmol-10 mmol. 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 α-olefin polymerization catalyst according to the present invention, [B-1] an aluminum oxy compound supported on solid fine particles, and [B-2] a component reacting with component [A] supported on solid fine particles. An ionic compound or Lewis acid capable of converting [A] to a cation, or [B-3] ion-exchanged layered silicate is used alone as component [B]. Even if the components are appropriately combined, they can be used.

(3) Component [C]
As the component [C], an organoaluminum compound is used. In the present invention, the following general formula:
AlR ¹²¹ _q Z _3-q (13)
An organoaluminum compound represented by the formula is preferred.
In the present invention, it is needless to say that the organoaluminum compound can be used alone, in combination of plural kinds or in combination. In this formula, R ¹²¹ represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents a halogen, hydrogen, an alkoxy group or an amino group, and q is a number greater than 0 and up to 3. R ¹²¹ 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, R ¹²¹ is trialkylaluminum having 1 to 8 carbon atoms.

(4) Component [D]
In the α-olefin polymerization catalyst of the present invention, a diamine derivative is used as component [D]. The diamine derivative shall not contain a metal complex.
Preferably, the diamine derivative is a diamine derivative represented by the following general formula (D1).

［一般式（Ｄ１）中、Ｒは、炭素数１〜２０の炭化水素基を表し、Ｘは、水素原子、炭素数１〜１０の炭化水素基またはジアルキルアミノ基を表し、複数のＲ及びＸは、それぞれ同一でも異なっていてもよく、任意のＲ、Ｘが連結された環状構造を有してもよく、ｎは、０≦ｎ≦４を表す。］

[In General Formula (D1), R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a dialkylamino group, and a plurality of R and X Each may be the same or different, and may have a cyclic structure in which arbitrary R and X are connected, and n represents 0 ≦ n ≦ 4. ]

Said R is a C1-C20 hydrocarbon group, Preferably it is a C1-C10 hydrocarbon group. Specific examples of R include linear aliphatic hydrocarbon groups such as methyl group, ethyl group and n-propyl group, branched aliphatic hydrocarbon groups such as i-propyl group and t-butyl group, and cyclopentyl. Group, an alicyclic hydrocarbon group such as cyclohexyl group, and an aromatic hydrocarbon group such as phenyl group. A linear aliphatic hydrocarbon group is preferable, and a methyl group, an ethyl group, an i-propyl group, and an i-butyl group are more preferable.
X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a dialkylamino group, preferably having a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms or a hydrocarbon group having 1 to 3 carbon atoms. A dialkylamino group; Specific examples of X are hydrogen, methyl group, ethyl group, n-propyl group, dimethylamino group, diethylamino group and the like. A plurality of R and X may be the same or different. Moreover, you may have the cyclic structure to which arbitrary R and X were connected. n represents an integer of 0 ≦ n ≦ 4, particularly preferably 1 ≦ n ≦ 3.

Specific examples of the diamine derivative include the following diamine compounds.
(1) Tetramethylhydrazine (2) Tris (dimethylamino) methane
(3) N, N, N ′, N′-tetramethyldiaminomethane,
(4) N, N, N ′, N′-tetraethyldiaminomethane,
(5) N, N, N ′, N′-tetramethylethylenediamine,
(6) N, N, N ′, N′-tetraethylethylenediamine,
(7) N, N, N ′, N′-tetramethyl-1,2-diaminopropane,
(8) N, N′-dimethylpiperazine,
(9) 1,4-diazabicyclo [2,2,2] octane,
(10) N, N, N ′, N′-tetramethyl-1,3-diaminopropane,
(11) N, N, N ′, N′-tetraethyl-1,3-diaminopropane,
(12) N, N, N ′, N′-tetramethyl-1,4-diaminobutane,
(13) N, N, N ′, N′-tetraethyl-1,4-diaminobutane,
Etc. Two or more of these diamine compounds can be used.

Preferably,
N, N, N ′, N′-tetramethyldiaminomethane,
N, N, N ′, N′-tetraethyldiaminomethane,
N, N, N ′, N′-tetramethylethylenediamine,
N, N, N ′, N′-tetraethylethylenediamine,
N, N, N ′, N′-tetramethyl-1,3-diaminopropane,
N, N, N ′, N′-tetraethyl-1,3-diaminopropane,
It is.

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. It can form by making it contact. The contact between the components can be performed simultaneously, stepwise or continuously, and can be performed once or divided into a plurality of times.
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 in which the component [B] is contacted with the component [D] that has been previously contacted with the component [C], and the contact product that has been previously contacted with the component [C] is brought into contact with the contact product.
(4) A method in which a component [D] previously contacted with the component [C] is brought into contact with a contact product obtained by contacting the component [B] with the component [A] 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, usually the metallocene compound is activated by a promoter component, and in some cases an organoaluminum component, to form a polymerization active site. At this time, the metallocene compound becomes a cation species and forms a stable active site by forming an ion pair with the promoter.
By the way, in the present invention, the presence of a diamine derivative between the cation species of the metallocene and the cocatalyst changes the vicinity of the active site sterically and electronically, thereby generating a new active site. Further, such active sites are considered to have a feature of high regularity by being sterically modified. Further, it is considered that the molecular weight distribution is widened because the diamine derivative is present non-uniformly.
Therefore, in the present invention, before the metallocene compound of component [A] and the co-catalyst compound of component [B] are in contact, it is preferable that the diamine derivative of component [D] is in contact with either of them. B], when the component [B] is contacted with the diamine derivative of the component [D] before the component [B] is contacted with the component [A]. It is thought to be effective.
Therefore, as a method for contacting the above components, the component [B] that has been previously contacted with the organoaluminum compound of the component [C] is preferably contacted with the contact product obtained by bringing the component [D] into contact with the component [C]. Is then contacted with component [A].

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

The amount of the components [A], [B], [C] and [D] used in the present invention is not particularly limited, but can be determined in consideration of the expression of polymerization activity. For example, the usage-amount of component [A] with respect to component [B] becomes like this. Preferably it is 0.1 micromol-100 micromol with respect to 1 g of component [B], More preferably, it is 0.5 micromol-50 micromol. Moreover, the usage-amount of component [D] with respect to component [B] becomes like this. Preferably it is 0.1 micromol-1000 micromol with respect to 1 g of component [B], More preferably, it is 0.5 micromol-500 micromol. However, the molar ratio [D] / [A] of [D] to component [A] is 0.1 to 99.0, preferably 1.0 to 10.0.
Moreover, the amount of the component [C] relative to the component [A] or the component [D] is preferably 0.01 to 5 × 10 ⁶ , more preferably 0.1 to 1 × 10 ⁴ in terms of molar ratio.

Moreover, the catalyst which concerns on this invention is formed by making component [A]-[D] contact as above-mentioned. In addition, when adjusting the catalyst for α-olefin polymerization in the present invention, in addition to the components [A], [B], [C], and [D], they are usually used within a range not impairing the object of the present invention. Polymers such as polyethylene and polypropylene, and inorganic oxide solids such as silica and titania may be added. You may use this as it is, and can also use the prepolymerization catalyst which implemented the prepolymerization which contacts this with an olefin and polymerizes in small quantities.
Therefore, the amount of polymer to be prepolymerized is preferably 0.01 or more, more preferably 0.1 or more by weight ratio with respect to the catalyst, and the upper limit is 100 or less, more preferably 50 for economy and handling. It is as follows. Here, the weight ratio of the polymer to the catalyst may be expressed as the prepolymerization ratio.

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, vinylcycloalkane. , Styrene and the like, and propylene is preferable.
The olefin feed method may be any method such as a feed method in which the olefin is maintained in the prepolymerization reaction tank at a constant speed or a constant pressure, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. Moreover, an organoaluminum compound can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.

3. Use of Catalyst / Polymerization of α-Olefin As for the polymerization mode, any mode can be adopted as long as the catalyst for α-olefin polymerization (including a prepolymerization catalyst for α-olefin polymerization, the same applies hereinafter) and the monomer are in efficient contact. obtain.
Specifically, it is applied to a slurry polymerization method using an inert solvent, a liquid phase solvent-free polymerization or a gas phase polymerization substantially using no solvent. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, multistage polymerization of two or more stages is also possible.

In the case of the slurry polymerization method, a saturated aliphatic hydrocarbon 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. When using a bulk polymerization method, it is preferably 40 ° C or higher, more preferably 50 ° C or higher. Moreover, an upper limit becomes like this. Preferably it is 80 degrees C or less, More preferably, it is 75 degrees C or less. Moreover, when using a vapor phase polymerization method, it is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. Moreover, an upper limit becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 90 degrees C or less.

  The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. When using a bulk polymerization method, it 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. Moreover, when using a gas phase polymerization method, it is preferably 1.0 MPa or more, more preferably 1.5 MPa or more. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Further, as a molecular weight regulator and for the purpose of improving the polymerization activity, hydrogen is supplementally added to propylene in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less. Can be used.

The α-olefin polymerized in the catalyst system of the present invention has the general formula R—CH═CH 2 (where R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branched group). )).
Specifically, α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. In addition to homopolymerization of these α-olefins, random copolymerization with monomers (for example, ethylene, α-olefins, dienes, styrenes, etc.) copolymerizable with α-olefins can also be performed. Further, block copolymerization in which homopolymerization in the first stage and random copolymerization in the second stage can be performed. The copolymerizable monomer can be used up to, for example, about 15% by weight in random copolymerization and up to, for example, about 50% by weight in block copolymerization.

4). Analysis / property evaluation of propylene-based polymer The propylene-based polymer that can be produced using the catalyst for α-olefin polymerization of the present invention has a characteristic between the metallocene cation species and the co-catalyst ion pair depending on the characteristics of the catalyst. The active site is considered to be sterically modified through the diamine derivative, and the effect of improving the regularity can be expected.
In the present invention, the high regularity of the propylene-based polymer means that the stereoselectivity and the regioselectivity are high. In order to quantitatively show the stereoselectivity, the mm fraction can be increased. It is considered that the higher the mm fraction value, the higher the stereoselectivity. Therefore, the propylene-based polymer according to the present invention preferably has this mm of 99% or more. In addition, in order to quantitatively indicate the position selection system, the value of heterogeneous bond represented by 2,1 bond can be raised. It is considered that the position selectivity increases as the value of the heterogeneous bond decreases. Therefore, the propylene-based polymer according to the present invention preferably has an amount of 2,1 bonds of 0.5% or less.
In addition to the polymerization temperature and MFR, the mm fraction and the amount of 2,1 bonds can be controlled by the amount of the diamine derivative used in the present invention.
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 carbon peak intensities 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.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to an Example. 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.

[Synthesis Example of Catalyst Component [A]]
According to the method described in Example 1 of JP-A-11-240909, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is synthesized. did.

[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 400 g 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 added to 4000 g of distilled water and then filtered 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 cake-like solid 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, and further washing with distilled water to pH 5-6, followed by filtration to obtain 760 g of a cake-like solid.
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 and further dried at 200 ° C. for 2 hours under reduced pressure to obtain 220 g of chemically treated montmorillonite.
The composition of this chemically treated montmorillonite 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].

[Example 1]
Catalyst preparation In a three-necked flask (volume: 1 L), 10 g of the chemically treated montmorillonite obtained above as the catalyst component [B] was added, and heptane (66 mL) was added to form a slurry, to which triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (34.0 mL) was added and stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100, so that the total volume was 30 mL.
In another flask (volume: 200 mL), N, N, N ′, N′-tetramethylethylenediamine (105 μmol) as a catalyst component [D] was diluted with toluene (21 mL) (solution 1), and Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl} prepared in the synthesis example of the catalyst component [A] in a flask (volume: 200 mL) Hafnium (45 μmol) was dissolved in toluene (9 mL) (solution 2).

Triisobutylaluminum (0.42 mmol: 0.6 mL of a heptane solution having a concentration of 143 mg / mL) was added as a catalyst component [C] to a 1 L three-necked flask containing the chemically treated smectite, and then the above solution 1 (21 mL) ) Was added and stirred at room temperature for 20 minutes.
Thereafter, triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL) was further added as the catalyst component [C], and then the above solution 2 was added and stirred at room temperature for 1 hour. A slurry was obtained.

Prepolymerization 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 prepolymerized catalyst (Catalyst A). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.39.

[Comparative Example 1]
Catalyst preparation In a three-necked flask (volume: 1 L), 10 g of the chemically treated montmorillonite obtained above as the catalyst component [B] was added, and heptane (66 mL) was added to form a slurry, to which triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (34.0 mL) was added and stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100, so that the total volume was 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).

  Triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL) was added as a catalyst component [C] to a 1 L three-necked flask containing the chemically treated smectite, and then the above solution 1 (9 mL) ) And stirred at room temperature for 1 hour to obtain a catalyst slurry.

Prepolymerization 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 prepolymerized catalyst (Catalyst B). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.10.

[Example 2]
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), 39 Nml of hydrogen was introduced, 750 g of liquid propylene was further introduced, and the temperature was raised to 70 ° C.
Thereafter, 100 mg of the catalyst A synthesized in Example 1 in a 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, 180 g of a polymer was obtained. The MFR was 0.45 g / 10 min, and the polymerization activity was 1800 gPP / g catalyst · hour. The results are summarized in Table 1.

[Example 3]
In Example 2, the same polymerization was carried out except that hydrogen was introduced, the amount of hydrogen was 78 Nml, and 50 mg of catalyst A was used. As a result, 105 g of a polymer was obtained. The MFR was 0.91 g / 10 min, and the polymerization activity was 2100 gPP / g catalyst · hour. The results are summarized in Table 1.

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

[Comparative Example 3]
In Comparative Example 2, 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 polymerization activity was 3500 gPP / g catalyst · hour. The results are summarized in Table 1.

  As is apparent from Table 1, the α-olefin polymerization catalyst A of the present invention containing the component [D] has a molecular weight distribution (Q value: Q) as compared with the catalyst B not containing the component [D] of the conventional method. It can be seen that a propylene polymer having a wide (Mw / Mn) and a high melting point (Tm) can be produced.

  The α-olefin polymerization catalyst of the present invention has a wide molecular weight distribution, enables the production of α-olefin polymers having a high melting point, and has high industrial applicability. In addition, 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 (6)

An α-olefin polymerization catalyst, wherein at least the following components [A] to [D] are contacted 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 each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, each of which may have a substituent, and Q ¹¹ May have a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. Represents a germylene group, M ¹¹ represents zirconium or hafnium, X ¹¹ and Y ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. A silyl group having a hydrogen group, 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. ]
Component [B]: An aluminum oxy compound [B-1] supported on solid fine particles and the transition metal compound [A] supported on solid fine particles may react to convert [A] into a cation. At least one selected from the group consisting of possible ionic compounds or Lewis acids [B-2] and ion-exchange layered silicates [B-3].
Component [C]: an organoaluminum compound.
Component [D]: a diamine derivative represented by the following general formula (D1) .

[In General Formula (D1), R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a dialkylamino group, and a plurality of R and X May be the same as or different from each other, may have a cyclic structure in which arbitrary R and X are linked, and n represents 1 ≦ n ≦ 4. ]   2. The α-olefin polymerization catalyst according to claim 1, wherein the component [B] and the component [D] are contacted in advance before the component [A] and the component [D] are in contact with each other. The catalyst for α-olefin polymerization according to claim 1 or 2 , wherein the component [B] is an ion-exchange layered silicate [B-3]. The catalyst for α-olefin polymerization according to claim 3 , wherein the ion-exchange layered silicate [B-3] is a smectite group. The preliminary for olefin polymerization characterized by preliminarily polymerizing an olefin in the range of 0.01-100 by weight ratio with respect to the catalyst for alpha-olefin polymerization of any one of Claims 1-4. Polymerization catalyst. The α-olefin is polymerized using the α-olefin polymerization catalyst according to any one of claims 1 to 4 or the olefin polymerization prepolymerization catalyst according to claim 5. A method for producing an olefin polymer.

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