JP2016050189A - Metallocene compound, olefin polymerization catalyst prepared therefrom and method for producing olefin polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization catalyst prepared from a metallocene compound that allows an olefin polymer of high molecular weight such as ethylene to be produced and is easy to synthesize.SOLUTION: A metallocene compound is represented by general formula [I] [M is Ti, Zr, or Hf; R-Rand R-Rare H, a halogen atom, an alkyl group, a halogenated alkyl group, an aryl group or the like; at least one of R-Rand R-Ris other than H; Q is Si or Ge; n is a natural number of 1-3].SELECTED DRAWING: None

Description

  The present invention relates to a metallocene compound, an olefin polymerization catalyst using the same, and a method for producing an olefin polymer. More specifically, the present invention relates to a novel metallocene compound that is easy to synthesize and can produce a high molecular weight polymer when used as an olefin polymerization catalyst. It is related.

  Olefin copolymers represented by ethylene / α-olefin copolymers and propylene / α-olefin copolymers are excellent in various properties such as mechanical properties, are relatively easy to manufacture, and are compatible with environmental problems. Because it is highly resource-reusable, it has a wide range of physical properties, from hard to soft, and is used for films, sheets, fibers and nonwovens, various containers and molded products, automotive parts and electrical equipment. As materials and modifiers, it is widely used from industrial use to daily life materials.

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

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

Here, a crosslinked bisindenyl complex having a phenyl group at the 4-position of the indenyl ring is known as a metallocene having excellent copolymerizability and capable of producing a high molecular weight olefin polymer. In particular, it has been reported that introduction of a methyl group substituent at the 2-position of the indenyl ring is effective in improving the molecular weight (see Non-Patent Documents 2 and 3), so that the 4-position should be produced in order to produce a higher molecular weight polymer. The search for the 2-position substituent of the bridged bisindenyl complex having a phenyl group at the same position continues.
Non-Patent Document 4 reports that a complex having an i-propyl group at the 2-position can produce a higher molecular weight polyethylene than a complex having a methyl group at the 2-position substituent in ethylene polymerization under high pressure conditions. Has been. Patent Documents 1 and 2 include a complex having an α-position branched alkyl substituent at the 2-position, Patent Document 3 includes a complex having a heteroaromatic ring substituent at the 2-position, and Patent Documents 4-7 include two bisindenyls. It has been reported that complexes having different ring 2-position substituents can each produce a high molecular weight olefin polymer and olefin copolymer.

However, investigations by the present inventors have revealed that when these catalysts are polymerized at a high temperature preferable from the viewpoint of production efficiency, the molecular weight of the resulting polymer is still insufficient.
In addition, as the 2-position substituent has a complex structure, when these complexes are produced on a large scale industrially necessary for organic synthesis, a complicated synthesis route or a multi-step synthesis route is required. This causes a problem that the cost of manufacturing the complex increases. Therefore, at present, it is desired to develop a new complex which can produce a high molecular weight olefin copolymer and has a simpler complex structure and can be easily synthesized than the conventional one. That is, under such circumstances, a novel metallocene compound that is easy to synthesize and can produce a high-molecular-weight olefin copolymer at an industrially advantageous polymerization temperature and polymerization conditions, as well as a metallocene catalyst and an olefin system using the same. A method for producing a polymer is desired.

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

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

  In view of the problems of the background art, the problem to be solved by the present invention is to provide a high molecular weight olefin polymer, particularly an ethylene-based polymer, at an industrially advantageous polymerization temperature and polymerization conditions when polymerizing an olefin such as ethylene. An object of the present invention is to provide a metallocene compound that is easy to synthesize, used as a catalyst for producing a copolymer, an olefin polymerization catalyst using the compound, and a method for producing an olefin polymer using the catalyst.

  In order to solve the above-mentioned problems, the inventors of the present invention have developed a metallocene catalyst as a polymerization catalyst for an olefin-based copolymer. In order to obtain a copolymer and to synthesize a metallocene compound that is easy to synthesize, a multifaceted study and an experimental search were conducted. In the process, a metallocene compound having a specific structure and easy to synthesize was obtained. By using an olefin polymerization catalyst, it is found that an olefin polymer having a high molecular weight can be produced at an industrially advantageous polymerization temperature and polymerization conditions when an olefin such as ethylene is polymerized. It came to be completed.

  That is, the inventors have, as a technical technique for solving the above problems, a novel metallocene compound having a specific substituent at a specific position, having a hydrogen atom as a substituent at the 2-position of the indenyl ring. It was also found that a bridged metallocene compound having a phenyl group having a substituent other than at least one hydrogen atom at the 4-position of the indenyl ring can solve the above-mentioned problems.

  Thus, a novel specific transition metal compound is used for the catalyst component for olefin polymerization including the metallocene compound that is easily synthesized and represented by the chemical structure represented by the following formula [I], which forms the basic structure of the present invention. The complex is characterized by the structure of the chemical and steric and electronic environment of the ligand of the catalyst structure in the metallocene catalyst, thereby providing a high molecular weight olefinic system under industrially advantageous conditions. Copolymers can be produced.

  The easily synthesized metallocene compound that constitutes the basic constitution of the present invention is represented by the chemical structure represented by the following formula [I].

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, or —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, carbon number be 6-20 aryl group), provided ^that at least one of R 5 to R ⁹ and ^R 15 ^{to R 19} may be other than hydrogen ^atom, adjacent R 5 to R ⁹ and ^R 15 ^{to R 19} is The substituent does not form an aromatic ring and R ² ˜R ⁴ and R ¹² ˜R ¹⁴ adjacent groups together with the atoms connecting them form one or more aromatic or aliphatic rings, or R ⁴ and R ⁵ , R ⁴ and R ⁹ , R ¹⁴ and R ¹⁵ or R ¹⁴ and R ¹⁹ together with the atoms connecting them may form one aromatic or aliphatic ring;
Q is a silicon atom or a germanium atom, n is a natural number of 1 to 3, R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, a C 1-10 alkyl group, a C 1 10 fluoroalkyl groups, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and 2 to 10 carbon atoms An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ together with the atoms connecting them. May form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from an alkyl group having 1 to 20 carbon atoms, a substituted amino group having 1 to 10 carbon atoms, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair. Each may be the same or different, and X ¹ and X ² may be combined with atoms connecting them to form one ring. ]

The invention of the embodiment or supplementary manufacturing method following the above basic invention (first invention) of the present invention includes the second to eleventh inventions. And the third invention specifies R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ in the general formula (I), and the fourth invention relates to R ^{1 to} R ⁴ and R ¹¹ in the general formula (I). identify to R ^14, the invention of the fifth and sixth, in the general formula (I), to identify n and M, the invention of sixth to eighth is used a metallocene compound of general formula (I) polymerization The ninth to eleventh inventions are catalysts that embody a method for producing a polymer.

And, as demonstrated by the comparison of Examples and Comparative Examples described later, the metallocene compound of the present invention is easy to synthesize, particularly easy to produce a racemate, and uses the compound as a catalyst component for olefin polymerization. Thus, an olefin polymer having a high molecular weight can be produced under industrially advantageous conditions.
The metallocene compound represented by the general formula ([I]) in the present invention has a hydrogen atom as a substituent at the 2-position of the indenyl ring, and has at least one substituent other than a hydrogen atom at the 4-position of the indenyl ring. The basic feature is that it has a unique structure in terms of chemical, steric and electronic environment, which has one phenyl group and two indenyl rings connected by an atomic group. Can be presumed to provide specificity due to the metallocene complex of the present invention.

The reason why the olefin polymerization catalyst of the present invention exerts the above-described effects of the present invention will be more specifically examined. In the structure in which a hydrogen atom is arranged at the 2-position substituent of the indenyl ring, Although there is no arrangement in which the polymer elimination reaction, which causes a decrease in the molecular weight of the growing polymer chain, is sterically suppressed at the polymerization temperature often reported, at a high polymerization temperature as in the examples of the present invention, In the structure in which the molecular motion of the growing polymer chain is activated and the hydrogen atom having the smallest atomic radius is arranged at the 2-position, the steric repulsion between the polymer chain and the 2-position substituent is minimized. It is thought that it was suppressed as compared with a compound having a structure having a substituent other than hydrogen at the 2-position.
As demonstrated by comparison between Examples and Comparative Examples described later, the structure in which a methyl group or an isopropyl group is arranged at the 2-position of the indenyl ring is not an arrangement environment in which the polymer elimination reaction can be sufficiently suppressed at a high polymerization temperature.
On the other hand, it is considered that the structure having a hydrogen atom at the 2-position of the indenyl ring found in the present invention can provide an appropriate steric environment capable of suppressing the polymer elimination reaction at a high polymerization temperature.

On the other hand, a structure in which a hydrogen atom is arranged at the 2-position substituent of the indenyl ring and an unsubstituted phenyl group is arranged at the 4-position is not sufficient from the viewpoint of production of a complex, although the catalyst performance is excellent. When synthesizing a complex, a meso form with low performance is produced as a by-product at the same time as a racemic form with excellent performance, and the solubility of the meso form is lower than that of the racemic form. This is because it is difficult to remove the meso form by washing using a recrystallization or a solvent used.
On the other hand, in the present invention, as demonstrated by the comparison of Examples and Comparative Examples described later, a hydrogen atom is substituted on the 2-position substituent of the indenyl ring, and a substituent other than a hydrogen atom is placed on the 4-position of the indenyl ring. In addition to the lower solubility of the racemic form than the meso form, the complex of the structure with a phenyl group having at least one of the above can be converted into the racemic form by a known technique called isomerization. A complex useful as a polymerization catalyst can be obtained easily and with high yield.
At the same time, since the complex in which the 2-position of the indenyl ring is a hydrogen atom has less steric hindrance around the central metal than the complex in which the 2-position is a methyl group or an isopropyl group, alkylation with an alkylating agent of X ¹ and X ² Easily proceeds, and a racemic rich dialkyl complex can be obtained easily and in high yield.

  By the way, the present invention is significantly different from the conventional invention according to each of the documents listed above as patent documents and non-patent documents in terms of constituent requirements (specific matters of the invention) and effects of the invention. Unlike the results of the present invention that a compound in which the substituent at the 2-position of the indenyl ring is a hydrogen atom gives a higher molecular weight olefin polymer than a compound having a substituent at the 2-position, and a specific substitution at the 4-position of the indenyl ring It can be said that the result of the present invention that the synthesis of the complex is greatly simplified by the simple method of introducing a group may be insignificant from those conventional documents.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general, and here, the overall configuration of the present invention is reviewed and summarized. [11] The invention unit group.
Here, the metallocene compound represented by the general formula [I] is configured as the basic invention [1], and [2] each of the following inventions adds an additional requirement to the basic invention or indicates an embodiment thereof. Is. The inventions of the polymerization catalysts [7] and [8] and the inventions of the production methods [9] to [11] specify additional requirements for solving the problems of the present invention. All invention units are collectively referred to as an invention group.

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

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, or —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, carbon number be 6-20 aryl group), provided ^that at least one of R 5 to R ⁹ and ^R 15 ^{to R 19} may be other than hydrogen ^atom, adjacent R 5 to R ⁹ and ^R 15 ^{to R 19} is The substituent does not form an aromatic ring and R ² ˜R ⁴ and R ¹² ˜R ¹⁴ adjacent groups together with the atoms connecting them form one or more aromatic or aliphatic rings, or R ⁴ and R ⁵ , R ⁴ and R ⁹ , R ¹⁴ and R ¹⁵ or R ¹⁴ and R ¹⁹ together with the atoms connecting them may form one aromatic or aliphatic ring;
Q is a silicon atom or a germanium atom, n is a natural number of 1 to 3, R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, a C 1-10 alkyl group, a C 1 10 fluoroalkyl groups, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and 2 to 10 carbon atoms An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ together with the atoms connecting them. May form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from an alkyl group having 1 to 20 carbon atoms, a substituted amino group having 1 to 10 carbon atoms, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair. Each may be the same or different, and X ¹ and X ² may be combined with atoms connecting them to form one ring. ]

[2] In the general formula (I), R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. The metallocene compound according to [1], wherein the metallocene compound is an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having 1 to 6 carbon atoms or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms.
[3] In the general formula (I), R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different and are a hydrogen atom, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a carbon number of 1 to 1 The metallocene compound according to [1] or [2], which is an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having 6 hydrocarbon groups.
[4] In the general formula (I), any one of [1] to [3], wherein R ^{1 to} R ⁴ and R ^{11 to} R ¹⁴ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Metallocene compounds in

[5] The metallocene compound according to any one of [1] to [4], wherein in the general formula (I), n is 1.
[6] The metallocene compound according to any one of [1] to [5], wherein in the general formula (I), M is Hf.

[7] An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metallocene compound in any one of [1] to [6] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchange layered silicate component (C): Organic Aluminum compound [8] The olefin polymerization catalyst according to [7], wherein the component (B) is a boron compound.

[9] A method for producing an olefin polymer, characterized in that olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst according to [7] or [8].
[10] The method for producing an olefin polymer according to [9], wherein the olefin contains ethylene.
[11] The method for producing an olefin polymer according to [9] or [10], wherein the polymerization temperature is 120 ° C. or higher.

  The metallocene compound of the present invention is (i) easy to synthesize, (ii) particularly easy to produce a racemate useful as a polymerization catalyst in the synthesis, and (iii) used as a polymerization catalyst, Compared to metallocene compounds, a high molecular weight olefin polymer can be obtained at an industrially advantageous polymerization temperature and polymerization conditions, and (iv) the comonomer content can be increased under appropriate polymerization conditions. The metallocene compound and olefin polymerization catalyst of the invention and the method for producing an olefin polymer using the olefin polymerization catalyst are very useful from an industrial viewpoint.

It is a graph which shows the relationship between the molecular weight (Mn) and the density in the Example and comparative example of this invention.

  In the following, the metallocene compound and the olefin polymerization catalyst constituting the invention group ([1] to [11]) of the present invention, and the production method of the olefin polymer using the same will be described in detail for each item. To do.

1. Metallocene Compound (1) Specificity of Metallocene Compound The metallocene compound of the present invention is a novel metallocene compound having a specific substituent represented by the general formula [I], and hydrogen as a substituent at the 2-position of the indenyl ring. It is a bridged metallocene compound having a phenyl group having an atom and having at least one substituent other than a hydrogen atom at the 4-position of the indenyl ring. And it is easy to synthesize, and in particular, it is easy to produce a racemate useful as a polymerization catalyst in the synthesis.
The complex is characterized by the chemical and steric and electronic environmental structure of the ligand in the catalyst structure in the metallocene catalyst, thereby providing a high molecular weight olefinic copolymer in industrially favorable conditions. Coalescence can be produced.
The metallocene compound has a structural isomer due to its chemical structure, but a racemic form is preferred over a meso form for use as a catalyst for olefin polymerization.

(2) Chemical structure A metallocene compound represented by the following general formula [I]:

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, or —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, carbon number be 6-20 aryl group), provided ^that at least one of R 5 to R ⁹ and ^R 15 ^{to R 19} may be other than hydrogen ^atom, adjacent R 5 to R ⁹ and ^R 15 ^{to R 19} is The substituent does not form an aromatic ring and R ² ˜R ⁴ and R ¹² ˜R ¹⁴ adjacent groups together with the atoms connecting them form one or more aromatic or aliphatic rings, or R ⁴ and R ⁵ , R ⁴ and R ⁹ , R ¹⁴ and R ¹⁵ or R ¹⁴ and R ¹⁹ together with the atoms connecting them may form one aromatic or aliphatic ring;
Q is a silicon atom or a germanium atom, n is a natural number of 1 to 3, R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, a C 1-10 alkyl group, a C 1 10 fluoroalkyl groups, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and 2 to 10 carbon atoms An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ together with the atoms connecting them. May form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from an alkyl group having 1 to 20 carbon atoms, a substituted amino group having 1 to 10 carbon atoms, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair. Each may be the same or different, and X ¹ and X ² may be combined with atoms connecting them to form one ring. ]

(3) Details of chemical structure In general formula [I], M is a titanium atom, a zirconium atom, or a hafnium atom, preferably zirconium or hafnium, and particularly preferably hafnium.

X ¹ and X ² are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or 2 carbon atoms. A silyl group having a C-10 alkenyl group, a C7-40 arylalkyl group, a C7-40 alkylaryl group, a C8-40 arylalkenyl group, a C1-6 hydrocarbon group. Selected from the group consisting of a substituted alkyl group having 1 to 20 carbon atoms, a substituted amino group having 1 to 10 carbon atoms, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone electron pair, and the same However, they may be different, and X ¹ and X ² may be combined with atoms connecting them to form one ring.

Specifically, chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, phenyl group, benzyl group, dimethylamino group, diethylamino group or trimethylsilyl A methyl group etc. can be mentioned.
Further, as an atomic group in which X ¹ and X ² form a ring together with atoms connecting them, specifically, 1,3-butadiene, 1,4-diphenyl-1,3- Butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,3-pentadiene, 1,4-ditolyl-1,3-butadiene, 1, 4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.
Here, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, and a trimethylsilylmethyl group are particularly preferable. Most preferred are a chlorine atom, a methyl group, an i-butyl group, a benzyl group, and a trimethylsilylmethyl group.

R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group Group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, or —PR ²¹ ₂ group (wherein R ²¹ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 carbon atoms). ~ 20 aryl groups).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

R ¹ , R ² , R ³ , R ⁴ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, Preferably, they are a hydrogen atom and a C1-C10 alkyl group.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. More preferably, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a carbon number 1 substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. An alkyl group having ˜20, most preferably a hydrogen atom, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms.

R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Aryl group, C6-C10 fluoroaryl group, C6-C10 aryloxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C7-C40 alkyl An aryl group or an arylalkenyl group having 8 to 40 carbon atoms.
R ¹⁰ and R ²⁰ are preferably each an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or 7 carbon atoms. An alkylaryl group having -40 carbon atoms, an arylalkenyl group having 8-40 carbon atoms, more preferably an alkyl group having 1-10 carbon atoms, an aryl group having 6-20 carbon atoms, an alkenyl group having 2-10 carbon atoms, An arylalkyl group having 7 to 40 carbon atoms and an alkylaryl group having 7 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and most preferably carbon. It is a number 1-10 alkyl group.

  Q is preferably a silicon atom, and n is preferably 1.

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

(Indenyl metallocene compounds)
Dimethylsilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3-ethylphenyl) -1-indenyl) dimethylhafniumdimethyldimethylsilylenebis (4- (3- Isopropylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-trimethylsilylphenyl) -1-indenyl) Dimethylhafnium / dimethylsilylenebis (4- (3-triethylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (3-triisopropylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsi Renbisu (4- (3-triphenylsilyl) -1-indenyl) dimethyl hafnium dimethylsilylenebis (4- (3-tri-methylphenyl) -1-indenyl) dimethyl hafnium

Dimethylsilylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafniumDimethylsilylenebis (4- (4-ethylphenyl) -1-indenyl) dimethylhafniumdimethyldimethylsilenebis (4- (4- Isopropylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) Dimethylhafnium / dimethylsilylenebis (4- (4-triethylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (4-triisopropylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsi Renbisu (4- (4-triphenylsilyl) -1-indenyl) dimethyl hafnium dimethylsilylenebis (4- (4-trimethylsilyl-methylphenyl) -1-indenyl) dimethyl hafnium

Dimethylsilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafniumdimethyldimethylsilylenebis (4- (2- Isopropylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-tert-butylphenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-trimethylsilylphenyl) -1-indenyl) Dimethylhafnium / dimethylsilylenebis (4- (2-triethylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (2-triisopropylsilylphenyl) -1-indenyl) dimethylhafnium / dimethylsi Renbisu (4- (2-triphenylsilyl-phenyl) -1-indenyl) dimethyl hafnium dimethyl silylene-bis (4- (2-trimethylsilyl-methylphenyl) -1-indenyl) dimethyl hafnium

Dimethylsilylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3,5-diethylphenyl) -1-indenyl) dimethylhafniumdimethyldimethylylenebis (4 -(3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium-dimethylsilylenebis (4- ( 3,5-di (trimethylsilyl) phenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di (triethylsilyl) phenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di (triisopropylsilyl) fur Nyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di (2-triphenylsilyl) phenyl) -1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5- Di (2-trimethylsilylmethyl) phenyl) -1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafniumdimethyldimethylylenebis (4 -(2,6-Dimethylphenyl) -1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium Dimethylsilylenebis (4-biphenylyl-1-indenyl) dimethylha Um-dimethylsilylene-bis (4- (2,6-dimethyl-biphenylyl) -1-indenyl) dimethyl hafnium dimethyl silylene-bis (4- (2 ', 6'-dimethyl biphenylyl) -1-indenyl) dimethyl hafnium

(5-methylindenyl metallocene compound)
Dimethylsilylenebis (4- (3-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3-ethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdimethyl Silylenebis (4- (3-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (3-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethyl Silylenebis (4- (3-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (3-triethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylene Bis (4- (3-triiso (Lopylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (3-triphenylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- ( 3-trimethylsilylmethylphenyl) -5-methyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (4-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (4-ethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdimethyl Silylenebis (4- (4-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (4-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethyl Silylenebis (4- (4-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (4-triethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylene Bis (4- (4-triiso (Lopylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (4-triphenylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- ( 4-trimethylsilylmethylphenyl) -5-methyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2-methylphenyl) -5-methyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2-ethylphenyl) -5-methyl-1-indenyl) dimethylhafniumdimethyl Silylenebis (4- (2-isopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (2-tert-butylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethyl Silylenebis (4- (2-trimethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (2-triethylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium / dimethylsilylene Bis (4- (2-triiso (Lopylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-triphenylsilylphenyl) -5-methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- ( 2-trimethylsilylmethylphenyl) -5-methyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (3,5-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3,5-diethylphenyl) -5-methyl-1-indenyl) Dimethylhafnium · dimethylsilylenebis (4- (3,5-diisopropylphenyl) -5-methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5 Methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di (trimethylsilyl) phenyl) -5-methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di) (Triethylsilyl) phenyl) -5-methyl-1-indenyl) dimethylhafni Dimethylsilylenebis (4- (3,5-di (triisopropylsilyl) phenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-triphenyl) Silyl) phenyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-trimethylsilylmethyl) phenyl) -5-methyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2,3-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2,5-dimethylphenyl) -5-methyl-1-indenyl) Dimethylhafnium · dimethylsilylenebis (4- (2,6-dimethylphenyl) -5-methyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2,3,5,6-tetramethylphenyl) -5 -Methyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (2,3,4,5,6-pentamethylphenyl) -5-methyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- ( 4-tert-butyl-2-methyl-phenyl) -5-methyl-1-indenyl) dimethylhafni Dimethylsilylenebis (4-biphenylyl-5-methyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (2 ′, 6′-dimethylbiphenylyl) -5-methyl-1-indenyl) dimethylhafnium

(5,6-dimethylindenyl metallocene compound)
Dimethylsilylenebis (4- (3-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3-ethylphenyl) -5,6-dimethyl-1-indenyl) Dimethylhafnium · dimethylsilylenebis (4- (3-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-tert-butylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-triethylsilylphenyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium dimethyl Lucylylenebis (4- (3-triisopropylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (3-triphenylsilylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium / dimethylsilylenebis (4- (3-trimethylsilylmethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (4-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (4-ethylphenyl) -5,6-dimethyl-1-indenyl) Dimethylhafnium · dimethylsilylenebis (4- (4-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-tert-butylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-triethylsilylphenyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium dimethyl Lucylylenebis (4- (4-triisopropylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (4-triphenylsilylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium / dimethylsilylenebis (4- (4-trimethylsilylmethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2-methylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2-ethylphenyl) -5,6-dimethyl-1-indenyl) Dimethyl hafnium dimethylsilylene bis (4- (2-isopropylphenyl) -5,6-dimethyl-1-indenyl) dimethyl hafnium dimethylsilylene bis (4- (2-tert-butylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-trimethylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-triethylsilylphenyl) -5,6 -Dimethyl-1-indenyl) dimethylhafnium dimethyl Lucylylenebis (4- (2-triisopropylsilylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium / dimethylsilylenebis (4- (2-triphenylsilylphenyl) -5,6-dimethyl-1-indenyl ) Dimethylhafnium / dimethylsilylenebis (4- (2-trimethylsilylmethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (3,5-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3,5-diethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-diisopropylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di-tert- Butylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-di (trimethylsilyl) phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene Bis (4- (3,5-di (triethylsilyl) phenyl) -5,6-dimethyl 1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3,5-di (triisopropylsilyl) phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3 , 5-Di (2-triphenylsilyl) phenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-trimethylsilylmethyl) phenyl) -5 6-Dimethyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2,3-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2,5-dimethylphenyl) -5,6-dimethyl- 1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,3,5,6- Tetramethylphenyl) -5,6-dimethyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2,3,4,5,6-pentamethylphenyl) -5,6-dimethyl-1-indenyl) Dimethyl hafnium dimethylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -5,6-dimethyl Ru-1-indenyl) dimethylhafnium · dimethylsilylenebis (4-biphenylyl-5,6-dimethyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -5,6- Dimethyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -5,6-dimethyl-1-indenyl) dimethylhafnium

(5-methoxyindenyl metallocene compound)
Dimethylsilylenebis (4- (3-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (3-ethylphenyl) -5-methoxy-6 tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (3-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (3- tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethyl hafnium dimethylsilylene bis (4- ( -Triethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3-triisopropylsilylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-triphenylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (3-trimethylsilylmethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (4-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (4-ethylphenyl) -5-methoxy-6 tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (4-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (4- tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethyl hafnium dimethylsilylene bis (4- ( -Triethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (4-triisopropylsilylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-triphenylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (4-trimethylsilylmethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium

Dimethylsilylenebis (4- (2-methylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2-ethylphenyl) -5-methoxy-6 tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (2-isopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium-dimethylsilylenebis (4- (2- tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-trimethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) Dimethyl hafnium dimethylsilylene bis (4- ( -Triethylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2-triisopropylsilylphenyl) -5-methoxy-6-tert-butyl-1- Indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-triphenylsilylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium · dimethylsilylenebis (4- (2-trimethylsilylmethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium

Dimethylsilylene bis (4- (3,5-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-diethylphenyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-diisopropylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (trimethylsilyl) phenyl) -5-Methoxy-6-tert-butyl-1-indenyl) dimethyl huff Um.dimethylsilylenebis (4- (3,5-di (triethylsilyl) phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (Triisopropylsilyl) phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-triphenylsilyl) phenyl) -5-methoxy -6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-trimethylsilylmethyl) phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethyl hafnium

Dimethylsilylenebis (4- (2,3-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniumDimethylsilylenebis (4- (2,5-dimethylphenyl) -5 Methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,6-dimethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,3,5,6-tetramethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylenebis (4- (2,3,4,5,6 -Pentamethylphenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafniu Dimethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium Dimethylsilylenebis (4-biphenylyl-5-methoxy- 6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis (4- (2,6-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium dimethylsilylene bis ( 4- (2 ′, 6′-dimethylbiphenylyl) -5-methoxy-6-tert-butyl-1-indenyl) dimethylhafnium

(Tetrahydroindacenyl metallocene compound)
Dimethylsilylene bis (4- (3-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (3-ethylphenyl) -1,5,6 7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3- tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) Dimethylhafnium ・ dimethylsilylenebis (4- (3-triethylsilyl Enyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3-triisopropylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium dimethylsilylene bis (4- (3-triphenylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (3-trimethylsilylmethylphenyl) -1, 5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

Dimethylsilylene bis (4- (4-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (4-ethylphenyl) -1,5,6 7-tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- (4-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- (4- tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) Dimethylhafnium ・ dimethylsilylenebis (4- (4-triethylsilyl Enyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (4-triisopropylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium dimethylsilylene bis (4- (4-triphenylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (4-trimethylsilylmethylphenyl) -1, 5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

Dimethylsilylene bis (4- (2-methylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (2-ethylphenyl) -1,5,6 7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2-isopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2- tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2-trimethylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) Dimethylhafnium ・ dimethylsilylenebis (4- (2-triethylsilyl Enyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2-triisopropylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethyl Hafnium dimethylsilylene bis (4- (2-triphenylsilylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (2-trimethylsilylmethylphenyl) -1, 5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

Dimethylsilylene bis (4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (3,5-diethylphenyl) -1, 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-diisopropylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (trimethylsilyl) phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilyl Bis (4- (3,5-di (triethylsilyl) phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (triisopropylsilyl) ) Phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-triphenylsilyl) phenyl) -1,5,6,7 -Tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (3,5-di (2-trimethylsilylmethyl) phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

Dimethylsilylene bis (4- (2,3-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene bis (4- (2,5-dimethylphenyl) -1, 5,6,7-Tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- (2,6-dimethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- (2,3,5,6-tetramethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4- (2,3,4,5,6 -Pentamethylphenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylene (4- (4-tert-butyl-2-methyl-phenyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium dimethylsilylenebis (4-biphenylyl-1,5,6,7 -Tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium-dimethylsilylenebis (4- ( 2 ', 6'-dimethylbiphenylyl) -1,5,6,7-tetrahydro-s-indacenyl) dimethylhafnium

  In addition to the compounds listed above, the crosslinking group may be a diethylsilylene group, di-n-propylsilylene group, di-n-pentylsilylene group, di-n-hexylsilylene group, dicyclopentylsilylene group, diphenylsilylene group, Methylenesilylene group, tetramethylenesilylene group, pentamethylenesilylene group, methyl (ethyl) silylene group, methyl (n-propyl) silylene group, methyl (n-butyl) silylene group, methyl (n-hexyl) silylene group, methyl ( Cyclohexyl) silylene group, methyl (vinyl) silylene group, methyl (allyl) silylene group, dimethylgermylene group and other compounds changed to germanium atom bridges, compounds in which the central metal is replaced with zirconium or titanium, and bonded to the central metal The methyl group is chlorine, bromine, iodine or Substituted compound in Le group can be exemplified similarly.

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

  In the above synthetic route, Compound 2 is obtained by conducting a coupling reaction between Compound 1 and 4-trimethylsilylphenylboronic acid in the presence of a palladium catalyst. A crosslinked product of compound 3 is obtained by anionizing compound 2 with butyllithium or the like and then reacting with dimethyldichlorosilane. After compound 3 is dianionized with 2 equivalents of n-butyllithium or the like, metallocene compound 4 can be obtained by reaction with hafnium tetrachloride.

In general, the metallocene compound 4 is a mixture of a racemate and a meso isomer, and the racemate having excellent catalytic performance is concentrated by purification. At this time, in the recrystallization solvent, when the racemic form is less soluble than the meso form and the solubility difference is large, the recrystallization is facilitated and the yield is easily improved. The metallocene compound of the present invention corresponds to this case.
Further, the meso form can be isomerized into a racemate by the method described in the literature (WO2000 / 017213), and the yield of the racemate can be improved.
As in the examples of the present invention, by using lithium chloride by-produced in the reaction, isomerization can be continuously carried out without taking out the complex once.
The dimethyl body 5 can be obtained by treating the metallocene compound 4 with 2 equivalents or more of MeMgBr or the like.

The synthesis of the metallocene compound into which a substituent is introduced can be synthesized by using a corresponding substitution raw material. Instead of 4-trimethylsilylphenylboronic acid, a corresponding boronic acid such as 4-isopropylphenylboronic acid, 3 By using 1,5-dimethylphenylboronic acid or the like, a substituent can be introduced on the 4-position phenyl group (R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ ) of the indenyl ring.
The synthesis of metallocene compounds having different substituents on the bridging group can be synthesized by using corresponding substitution raw materials, and corresponding R ¹⁰ (R ²⁰ ) SiCl ₂ or R ¹⁰ (R) instead of dimethyldichlorosilane. ²⁰ ) By using Si (OSO ₂ CF ₃ ) ₂ , substituents (R ¹⁰ and R ²⁰ ) can be introduced onto the bridging group.

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

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

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

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

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

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

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

  Examples of the organoaluminum oxy compound include those represented by the following general formula [III].

(In the formula [III], R ^b represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, alkenyl group, aryl group or aralkyl group, and R ^c represents 1 to 1 carbon atoms. 10 represents a hydrocarbon group, wherein a plurality of R ^b in the formula [III] may be the same or different.
The compound represented by the general formula [III] is 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the general formula: R ^c B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

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

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

In formula [IV], R ^d and R ^e are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and depending on the bridging group The substituents of the substituted aromatic hydrocarbon group may be linked to each other, and examples of the substituent include alkyl groups represented by methyl group, ethyl group, propyl group, isopropyl group, and halogens such as fluorine, chlorine, bromine and iodine. preferable.
Furthermore, ^Xb and ^Xc are each independently a hydride group, a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1 to 20 hydrogen atoms substituted with one or more hydrogen atoms. A substituted hydrocarbon group containing a carbon atom.

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

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

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

  Specific examples of the compound represented by the general formula [IV] include trityltetraphenylborate, trityltetra (o-tolyl) borate, trityltetra (p-tolyl) borate, trityltetra (m-tolyl) borate, and trityl. Tetra (o-fluorophenyl) borate, trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, Trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropini Mutetra (o-tolyl) borate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, Tropinium tetra (m-fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropi Nitrotetra (3,5-ditrifluoromethylphenyl) borate, tropiniumtetra (perfluoronaphthyl) borate, sodiumtetraphenylborate, sodiumtetra (o-tolyl) borate, sodiumtetra (p-to ) Borate, sodium tetra (m-tolyl) borate, sodium tetra (o-fluorophenyl) borate, sodium tetra (p-fluorophenyl) borate, sodium tetra (m-fluorophenyl) borate, sodium tetra (3,5-difluorophenyl) borate, Sodium tetra (pentafluorophenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodium tetra (3,5-ditrifluoromethylphenyl) borate, sodium tetra (perfluoronaphthyl) borate, hydrogen tetraphenylborate-2diethyl ether , Hydrogen tetra (3,5-difluorophenyl) borate-2 diethyl ether, hydrogen tetra (pentafluorophenyl) borate-2 Diethyl ether, hydrogen tetra (2,6-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogen tetra (3,5-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogen tetra (perfluoronaphthyl) borate · 2 diethyl An ether etc. can be illustrated.

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

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

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

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

  Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferred examples include agitation granulation method, spray granulation method, rolling granulation method, and fluidization granulation method, and particularly preferred are agitation granulation method and spray granulation method.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (B) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . Although the inlet temperature of the hot air of spray granulation from which spherical particles are obtained varies depending on the dispersion medium, taking water as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

  In granulation, in order to obtain a carrier having high particle strength and to improve the olefin polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a forced stirring method using polytron or the like, a dyno mill, a pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use an organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder to be used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol and the like.

  The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1,000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

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

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

A salt used for ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of Group 1 to 14 atoms of a long-period periodic table (hereinafter simply referred to as “periodic table”) Preferably, at least one 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 atom, an inorganic acid and an organic acid. A cation comprising at least one atom selected from the group consisting of Group 2-14 atoms of the periodic table, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) At least one selected from the group consisting of ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ It is a compound consisting of Two or more of these salts may be used simultaneously.

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

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

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

(3) Preparation method of catalyst In the preparation method of the olefin polymerization catalyst according to the present invention, the contact method of component (A), component (B) and component (C) is not particularly limited, but the following method is used. It can be illustrated.
(I) A component (A) and a component (B) are made to contact.
(Ii) After contacting the component (A) and the component (B), the component (C) is added.
(Iii) Component (A) and component (C) are contacted, and then component (B) is added.
(Iv) Component (B) and component (C) are contacted, and then component (A) is added.
(V) The components (A), (B), and (C) are contacted simultaneously.

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

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

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

(3-3) Catalyst preparation method when a fine particle carrier other than silicate is used as component (B) When component (B) is other than silicate, component (A), component (B) and / or Component (C) can be supported on a fine particle carrier other than silicate and used for polymerization. Examples of the fine particle carrier to be used include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel, and the like.

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

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

These inorganic carriers are usually baked in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl group is 0.8 to 1.5 mmol / g. It is preferable to adjust to use.
The properties of these inorganic carriers are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1,000 mm, preferably 50 to 500 mm, and the specific surface area is 150. ˜1,000 m ² / g, preferably 200 to 700 m ² / g, pore volume is 0.3 to 2.5 cm ³ / g, preferably 0.5 to 2.0 cm ³ / g, and apparent specific gravity is 0 It is preferable to use an inorganic carrier having 20 to 0.50 g / cm ³ , preferably 0.25 to 0.45 g / cm ³ .

  Of course, the above-mentioned inorganic carriers can be used as they are, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after contacting an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

  The contact method of each component when obtaining a catalyst for olefin polymerization comprising a component (A), a compound that reacts with the component (A) to form an ion pair (component B), and a fine particle carrier is not particularly limited, For example, the following method can be arbitrarily adopted.

(I) After contacting the component (A) and the component (B), the fine particle carrier is contacted.
(II) After contacting the component (A) and the fine particle carrier, the component (B) is contacted.
(III) The component (B) and the fine particle carrier are contacted, and then the component (A) is contacted.
Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane or dodecane is usually used in an inert atmosphere such as nitrogen or argon. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.
This contact is usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  Further, when the component (A), the component (B) and the fine particle carrier are brought into contact with each other, as described above, a certain component is soluble or hardly soluble in an aromatic hydrocarbon solvent, and a certain component is insoluble or hardly soluble. Any aliphatic or alicyclic hydrocarbon solvent can be used.

  When the contact reaction between the components is carried out stepwise, it may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid, or part or all of the soluble solvent is once removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

In the present invention, the use ratio of the component (A), the component (B), and the fine particle carrier is not particularly limited, but the following ranges are preferable.
When an organoaluminum oxy compound is used as the component (B), the atomic ratio (Al / M) of the aluminum of the organoaluminum oxy compound to the transition metal (M) in the component (A) is usually 1 to 100,000, The range is preferably 5 to 1,000, more preferably 50 to 400. When a borane compound or a borate compound is used, the atomic ratio of boron to the transition metal (M) in the component (A) (B / M) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as a compound (component (B)) that forms an ion pair, the transition metal (M) is used for each compound in the mixture. On the other hand, it is desirable to select at a use ratio similar to the above.

  The amount of the fine particle carrier used is 1 g per 0.0001 to 5 mmol of transition metal in component (A), preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol. .

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

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

(4) Prepolymerization Before using the catalyst containing component (A), component (B) and optionally component (C) as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, Even if a prepolymerization treatment for preliminarily polymerizing small amounts of olefins such as 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene is performed. Good. As the prepolymerization method, a known method can be used.

3. Olefin Polymerization Method (1) Polymerization Form In the present invention, the polymerization form allows the polymerization catalyst containing the metallocene compound represented by the general formula [I] and the monomer to efficiently come into contact with each other to perform olefin polymerization or copolymerization. Any style can be adopted.
Specifically, a slurry method and a solution method using an inert solvent, a bulk polymerization method using a olefin monomer as a solvent without using an inert solvent, and a high-pressure ion polymerization, or each monomer using substantially no liquid solvent. For example, a gas phase polymerization method for keeping the gas in a gaseous state can be employed. Preferably, solution polymerization and high pressure ionic polymerization can be mentioned.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. The combination of polymerization modes is not particularly limited, and may be a solution polymerization 2-stage, bulk polymerization 2-stage, gas phase polymerization after bulk polymerization, gas-phase polymerization 2-stage, and more polymerization stages. It is also possible to manufacture with.

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

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

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

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

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

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

(1) Melt flow rate (MFR)
According to JIS K7210 (2004 edition), Annex A Table 1-Condition D, the measured value at a test temperature of 190 ° C. and a nominal load of 2.16 kg is shown as MFR.
(2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The generated ethylene polymer was subjected to gel permeation chromatography (GPC) under the following conditions to determine the number average molecular weight (Mn) and the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) was calculated.
[Gel permeation chromatographic measurement conditions]:
Apparatus: Alliance GPC2000 type manufactured by Waters, column: Shodex-HT806M, solvent: 1,2-dichlorobenzene, flow rate: 1 ml / min, temperature: 145
Universal rating was performed using a monodisperse polystyrene fraction at ° C.
Measurement was performed under the above-mentioned conditions, and a chromatogram was recorded at a sampling interval of 1 second. Based on this chromatogram, Sadao Mori “Size Exclusion Chromatography” (Kyoritsu Shuppan), Chapter 4, p. The differential molecular weight distribution curve and the average molecular weight value (Mn, Mw) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram was corrected by the following equation. H ′ = [1.032 + 189.2 / M (PE)] × H
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

(3) Density Density was measured according to Method A (underwater substitution method) among the test methods described in JIS K7112 (2004 edition).
(4) Comonomer content The monomer composition of the ethylene / 1-hexene copolymer is described in the literature (Anal. Chem. 20
04, 5734-5747) and calculated by NMR analysis.
[NMR measurement conditions]
As the solvent, a 1,2-dichlorobenzene / heavy bromobenzene (4/1) mixed solvent was used. The sample concentration was 150 mg / 2.4 mL. After introducing the sample into the NMR sample tube, the sample was sufficiently purged with nitrogen, and then dissolved in a 130 ° C. heat block to obtain a uniform solution. Bruker Avance III Cryo-NMR, using a 10 mmφ cryoprobe, 13
Measurements were taken at 0 ° C.
The measurement conditions are as follows: ¹ H-NMR: solvent presaturation method, 18 ° pulse, accumulated 256 times, ¹³ C-NMR: proton complete decouple condition, 90 ° pulse, accumulated 512 times.
(5) Melting point (Tm)
Using an EXSTAR6000 DSC differential scanning calorimeter manufactured by Seiko Denshi Co., Ltd., a sample (about 5 mg) was melted at 180 ° C. for 5 minutes, cooled to −20 ° C. at a rate of 10 ° C./min, and then at −20 ° C. for 5 minutes. After being held, the melting curve was obtained by raising the temperature to 180 ° C. at a rate of 10 ° C./min. The peak top temperature of the main endothermic peak in the final temperature increase stage performed to obtain the melting curve was defined as the melting point Tm.

The molecular weight of the polymer obtained by carrying out the above measurements (1) and (2) can be evaluated. That is, it can be said that the smaller the MFR value obtained from the measurement (1), and the higher the number average molecular weight obtained in the measurement (2), the higher the molecular weight.
In addition, by carrying out the above measurements (3) and (4), it is possible to evaluate the amount of 1-hexene, which is an α-olefin, in the comonomer in the copolymer, and in this example and the comparative example. It can be said that the smaller the density value obtained from measurement (3), the higher the comonomer content.
That is, when the polymers obtained under the same temperature using different catalysts are compared at the same density, the higher the number average molecular weight, the better the catalyst performance.

[1] Synthesis of metallocene compound Metallocene compound A (Example): Synthesis of dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] dimethylhafnium

（メタロセン化合物Ａ）

(Metalocene Compound A)

(A-1) Synthesis of 4- (4-trimethylsilylphenyl) indene In a 200 mL glass reaction vessel, 16 g (75.4 mmol) of tripotassium phosphate, 42 mL of distilled water, 42 mL of 1,2-dimethoxyethane (DME), 4-trimethylsilylphenylboronic acid 5.0 g (25.8 mmol), 7-bromo-1H-indene 4.19 g (21.5 mmol), dichlorobis (triphenylphosphine) palladium 420 mg (0.60 mmol), triphenylphosphine 313 mg ( 1.19 mmol) was added in order, and the mixture was heated to reflux at 90 ° C. for 4 hours. After leaving to room temperature, the reaction solution was poured into 50 mL of distilled water, transferred to a separatory funnel, and extracted three times with hexane. The hexane solution was washed three times with saturated brine and distilled water, dried over sodium sulfate, filtered through sodium sulfate, the solvent was distilled off under reduced pressure, and silica gel column chromatography (developing solvent, hexane / diisopropyl ether = 20: 1) to obtain 5.69 g of 4- (4-trimethylsilylphenyl) indene as a colorless oil (yield 100%).

(A-2) Synthesis of dimethylbis (4- (4-trimethylsilylphenyl) inden-1-yl) silane In a 200 ml glass reaction vessel, 5.69 g (21.5 mmol) of 4- (4-trimethylsilylphenyl) indene , 50 ml of THF was added, and the mixture was cooled to −78 ° C. in a dry ice-methanol bath. To this, 14.0 ml (22.4 mmol) of a 1.60 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 4 hours. The mixture was cooled to −78 ° C., 0.050 mL (0.63 mmol) of 1-methylimidazole and 1.30 mL (10.9 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 100 mL of distilled water, transferred to a separatory funnel, and extracted three times with diisopropyl ether. The diisopropyl ether solution was washed three times with saturated saline and distilled water, dried over sodium sulfate, filtered through sodium sulfate, the solvent was distilled off under reduced pressure, and silica gel column chromatography (developing solvent, hexane / diisopropyl ether). = 1: 0, 30: 1, 20: 1, 10: 1 stepwise) to obtain 5.11 g of dimethylbis (4- (4-trimethylsilylphenyl) inden-1-yl) silane as a white solid. (Yield 81%).

(A-3) Synthesis of racemic-dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] hafnium dichloride In a 200 mL glass reaction vessel, dimethylbis (4- (4-trimethylsilylphenyl) indene -1-yl) silane (5.09 g, 8.70 mmol) and diethyl ether (87 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. To the solution, 11.1 ml (17.8 mmol) of a 1.60 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 85 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-heptane bath. Thereto was added 2.79 g (8.71 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 18 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 63:37. In addition, the racemic body had lower solubility in toluene than the meso body.
The solvent of the reaction solution was distilled off under reduced pressure, 40 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. The reaction solution is cooled to room temperature, filtered through a glass frit, and the solid is collected by filtration, whereby a racemic dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] hafnium dichloride containing lithium chloride is collected. Was obtained as a yellow solid. This solid was extracted with 1.2 L of dichloromethane, filtered through celite, and then the solvent was distilled off under reduced pressure to obtain racemic-dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] hafnium dichloride as a yellow solid. 5.24 g was obtained (yield 72%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.63 (d, 4H), 7.57 (d, 4H), 7.53 (d, 2H), 7.37 (d, 2H), 7 .16 (t, 2H), 7.03 (d, 2H), 6.08 (d, 2H), 1.18 (s, 6H), 0.27 (s, 18H).

(A-4) Racemic-dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] dimethylhafnium Racemic-dimethylsilylenebis [4 containing 15 wt% lithium chloride in a 100 ml glass reaction vessel. -(4-Trimethylsilylmethylphenyl) -1-indenyl)] hafnium dichloride (1.00 g (containing 1.02 mmol of dichloride complex)) and toluene (35 mL) were added. To this, 3.6 mL (10.8 mmol) of a 3.0 mol / L methylmagnesium bromide-diethyl ether solution was added dropwise at room temperature, followed by stirring at 80 ° C. for 2 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 1.06 mL (8.39 mmol) of chlorotrimethylsilane was added and stirred at room temperature for 15 minutes, followed by 2.15 mL (25.1 mmol) of 1,4-dioxane. The mixture was further stirred at room temperature for 50 minutes. The suspension was filtered through celite, and the solvent was evaporated under reduced pressure. The obtained yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed three times with 5 mL of hexane, whereby dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl) 721 mg of a racemic dimethylhafnium was obtained as a yellow solid (89% yield).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ = 7.80 (d, 4H), 7.56 (d, 4H), 7.33 (d, 2H), 7.26 (d, 2H) , 7.21 (d, 2H), 6.93 (dd, 2H), 5.63 (d, 2H), 0.61 (s, 6H), 0.20 (s, 18H), -0.99 (S, 6H). 7.63 (d, 2H), 7.42 (d, 2H), 7.30-7.06 (m, 6H), 6.91 (dd, 2H), 6.48 (d, 2H), 5 .71 (d, 2H), 2.21 (s, 6H), 2.15 (s, 6H), 1.88 (s, 6H), -0.87 (s, 6H).

Metallocene compound B (comparative example): Synthesis of dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium

（メタロセン化合物Ｂ）

(Metallocene compound B)

(B-1) Synthesis of dimethylbis (4-phenylinden-1-yl) silane The compound was synthesized according to the method described in the literature (Oraganometallics 1994, Vol. 13, pages 954-963).
(B-2) Synthesis of racemic dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, 4.90 g of dimethylbis (4-phenylinden-1-yl) silane (11. 1 mmol) and 110 ml of diethyl ether were added and cooled to -70 ° C. in a dry ice-heptane bath. A 1.62 mol / L n-butyllithium-n-hexane solution (14.0 ml, 22.7 mmol) was added dropwise thereto, and the mixture was stirred at room temperature for 3.5 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. Thereto was added 3.56 g (11.1 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 17 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 55:45. The meso form was less soluble in toluene than the racemic form.
After adding 200 mL of dichloromethane and filtering through celite, recrystallization in toluene at room temperature results in primary crystals of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride having a racemic: meso ratio of 5:95. As a result, 1.37 g was obtained. Next, the mother liquor was concentrated and recrystallized at −20 ° C. to precipitate yellow microcrystals and orange crystals having a size of several mm. The mother liquor and yellow microcrystals were removed with a 2 mm diameter pipe to obtain 2.23 g of a racemic dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride as an orange solid (yield 29%). It was difficult to isolate racemates with good reproducibility by this method.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.63 (d, 4H), 7.53 (d, 2H), 7.42 (t, 4H), 7.38-7.31 (m, 4H) 7.16 (dd, 2H), 7.01 (d, 2H), 6.10 (d, 2H), 1.18 (s, 6H).

(B-2 ′) Synthesis of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride 5.73 g of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride having a racemic: meso ratio of 9:91 To (8.33 mmol), 169 mg (3.99 mmol) of lithium chloride and 42 mL of 1,2-dimethoxyethane were added and stirred at 60 ° C. for 5.5 hours. The reaction solution is cooled to room temperature, filtered through a glass frit, and the solid is collected by filtration to obtain a meso form of dimethylsilylenebis [4- (4-trimethylsilylmethylphenyl) -1-indenyl)] hafnium dichloride containing lithium chloride. Was obtained as a yellow solid.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.66-7.50 (m, 6H), 7.
42 (t, 4H), 7.34 (t, 2H), 7.20 (d, 2H), 7.06-6.94 (m, 4H), 6.13 (d, 2H), 1.42 (S, H), 1.01 (s, 3H).

(B-3) Synthesis of racemic-dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, 1.20 g of racemic-dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride. (1.56 mmol) and 50 mL of toluene were added. To this, 3.6 mL (10.8 mmol) of a 3.0 mol / L methylmagnesium bromide-diethyl ether solution was added dropwise at room temperature, followed by stirring at 80 ° C. for 1 hour. After cooling the reaction solution to 0 ° C. in an ice bath, 0.98 mL (7.76 mmol) of chlorotrimethylsilane was added and stirred at room temperature for 30 minutes, followed by 2.0 mL (23.4 mmol) of 1,4-dioxane. The mixture was further stirred at room temperature for 30 minutes. The suspension was filtered through celite, and the solvent was evaporated under reduced pressure. The obtained yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed with 5 mL of hexane three times to obtain a racemic dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium. 837 mg was obtained as a yellow solid (yield 85%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.70 (dd, 4H), 7.27-7.18 (m, 8H), 7.15-7.07 (m, 4H), 6. 90 (dd, 2H), 5.63 (d, 2H), 0.60 (s, 6H), -1.07 (s, 6H).

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

（メタロセン化合物Ｃ）

(Metalocene Compound C)

(C-1) Synthesis of dimethylbis (2-methyl-4-phenylinden-1-yl) silane The compound was synthesized according to the method described in the literature (Oraganometallics 1994, 13, 954-963).
(C-2) Synthesis of racemic-methylsilylenebis (2-methyl-4-phenyl-1-indenyl) hafnium dichloride In a 200 mL glass reaction vessel, dimethylbis (2-methyl-4-phenylinden-1-yl) ) 8.00 g (17.1 mmol) of silane and 130 ml of diethyl ether were added and cooled to -70 ° C. in a dry ice-heptane bath. To this, 22.0 ml (35.0 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 130 ml of toluene was added, and the solution was cooled to −70 ° C. in a dry ice-heptane bath. There, 5.47 g of hafnium tetrachloride (8.
71 mmol) was added. Thereafter, the mixture was stirred for 18 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 70:30. In addition, the racemic body had lower solubility in toluene than the meso body.
The solvent of the reaction solution was distilled off under reduced pressure, 40 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, filtered through a glass frit, and the resulting solid was extracted with dichloromethane. After filtration through celite, the solvent was distilled off under reduced pressure to remove dimethylsilylene bis (2-methyl-4-phenyl-1). -Indenyl) Hafnium dichloride racemate was obtained as a yellow solid, 8.97g (yield 73%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.71 (d, 2H), 7.62 (d, 4H), 7.43 (t, 4H), 7.40-7.30 (m, 4H), 7.10 (dd, 2H), 6.88 (s, 2H), 2.35 (s, 6H), 1.34 (s, 6H).

(C-3) Synthesis of racemic-dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) was added. ) Hafnium dichloride 1.48 g (2.07 mmol) and toluene 60 mL were added. A 0.99 mol / L methylmagnesium bromide-tetrahydrofuran solution (14.0 mL, 13.9 mmol) was added dropwise at room temperature, and the mixture was stirred at 80 ° C. for 3.5 hours. After cooling the reaction solution to 0 ° C. with an ice bath, 1.0 mL (7.9 mmol) of chlorotrimethylsilane was added, and the mixture was stirred at room temperature for 30 minutes, followed by addition of 2.7 mL (32 mmol) of 1,4-dioxane, The mixture was further stirred at room temperature for 30 minutes. The suspension was filtered through Celite, and the filtrate was concentrated under reduced pressure, and then allowed to stand at -20 ° C. and recrystallized, whereby a racemic dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) dimethylhafnium was obtained. Was obtained as yellow crystals (yield 23%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.75 (dd, 4H), 7.49 (d, 2H), 7.27 (d, 2H) 7.23 (t, 4H), 7. 12 (t, 2H), 7.03 (s, 2H), 6.85 (dd, 2H), 2.00 (s, 6H), 0.80 (s, 6H), -0.83 (s, 6H).

  Metallocene compound D (comparative example): Synthesis of dimethylsilylenebis (2-methyl-4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium

（メタロセン化合物Ｄ）

(Metalocene Compound D)

(D-1) Synthesis of 4- (4-trimethylsilylphenyl) indene Synthesized according to the method described in JP-A-2014-070029.
(D-2) Synthesis of dimethylbis (2-methyl-4- (4-trimethylsilylphenyl) inden-1-yl) silane In a 50 ml glass reaction vessel, 1.20 g of 4- (4-trimethylsilylphenyl) indene ( 4.30 mmol) and 10 ml of THF were added and cooled to -78 ° C. in a dry ice-methanol bath. To this, 2.0 ml (5.0 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at 15 ° C. for 3 hours. The mixture was cooled to −40 ° C., 0.270 mL (2.15 mmol) of dimethyldichlorosilane was sequentially added, and the mixture was stirred at −40 ° C. for 30 minutes. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent, petroleum ether / dichloromethane = 20: 1) and dimethylbis (2-methyl-4- (4-trimethylsilylphenyl) inden-1-yl). 0.70 g of silane was obtained as a yellow solid (yield 56%).

(D-3) Synthesis of racemic-dimethylsilylenebis (2-methyl-4- (4-trimethylsilylphenyl) -1-indenyl) hafnium dichloride In a 200 mL glass reaction vessel, dimethylbis (2-methyl-4- ( 4-Trimethylsilylphenyl) inden-1-yl) silane (2.01 g, 3.26 mmol) and diethyl ether (50 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. To this, 4.1 ml (6.52 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred at room temperature for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-heptane bath. Thereto was added 1.00 g (3.26 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 18 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 71:29. The reaction solution was filtered, and the resulting solid was extracted with dichloromethane and filtered through celite. Dichloromethane was distilled off under reduced pressure, and the resulting solid was washed with toluene to obtain 286 mg of a racemic dimethylsilylene bis (2-methyl-4- (4-trimethylsilylphenyl) -1-indenyl) hafnium dichloride as a yellow solid. (Yield 10%).

(D-4) Synthesis of dimethylsilylenebis (2-methyl-4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium The dimethylation reaction was carried out under the same conditions as in (C-3). It was not completed.

  Metallocene compound E (comparative example): Synthesis of dimethylsilylene bis (2-isopropyl-4-phenyl-1-indenyl) dimethylhafnium

（メタロセン化合物Ｅ）

(Metallocene compound E)

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

(E-2) Synthesis of racemic-dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, dimethylbis (2-isopropyl-4-phenylinden-1-yl) was synthesized. ) 3.34 g (6.36 mmol) of silane and 50 ml of diethyl ether were added and cooled to -70 ° C. in a dry ice-heptane bath. To this, 8.0 ml (12.8 mmol) of 1.62 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred for 2.5 hours. The solvent of the reaction solution was distilled off under reduced pressure, 65 ml of toluene was added, and the solution was cooled to −70 ° C. in a dry ice-heptane bath. Thereto was added 2.04 g (6.37 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 17 hours while gradually returning to room temperature.
The reaction solution was filtered through Celite, and the filtrate was concentrated and then allowed to stand at −20 ° C. to obtain 0.85 g of a meso form of dimethylsilylenebis (2-isopropyl-4-phenyl-indenyl) hafnium dichloride as a yellow solid. . The filtrate was repeatedly concentrated and recrystallized to precipitate a complex mixture containing a large amount of meso form. Finally, the racemic form of dimethylsilylenebis (2-isopropyl-4-phenyl-indenyl) hafnium dichloride: meso form ratio 77 : 1.20 g of a mixture of 23 was obtained.
To this mixture, 60 mg of anhydrous lithium chloride and 6 mL of DME were added and stirred at 60 ° C. for 5 hours. The reaction solution was cooled to room temperature, filtered through a glass frit, and washed twice with 5 mL of DME to obtain 464 mg of a racemic dimethylsilylenebis (2-isopropyl-4-phenyl-1-indenyl) hafnium dichloride as an orange solid. (Yield 10%). In addition, this synthesis method has poor reproducibility, and meso form was sometimes obtained.
Racemate: ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.74-7.70 (m, 6H), 7.44 (t, 4H), 7.40-7.28 (m, 4H), 7 .07 (dd, 2H), 6.89 (s, 2H), 3.31 (sep, 2H), 1.36 (s, 6H), 1.14 (d, 6H), 1.11 (d, 6H).
Meso form: ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.69 (d, 2H), 7.60 (d, 4H), 7.43 (t, 4H), 7.34 (t, 2H), 7.12 (d, 2H), 6.96-6.80 (m, 4H), 3.31 (sep, 2H), 1.50 (s, 3H), 1.42 (d, 6H), 1 .29 (s, 3H), 1.20 (d, 6H).

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

[2] Batch solution polymerization: ethylene / 1-hexene copolymerization (Example 1) Ethylene / 1-hexene copolymerization using metallocene compound A 2.3L stainless steel autoclave thoroughly dried and substituted with nitrogen (stirring) Toluene 1,000 mL, 1-hexene 58 mL was added to a temperature controller, and the temperature was raised to 150 ° C. After the temperature in the reactor was stabilized, the pressure was increased to 0.7 MPaG with nitrogen and further to 2.7 MPaG with ethylene. Thereafter, 0.1 mmol of tri (n-octyl) aluminum was injected with nitrogen, and a metallocene compound A 0.30 μmol-toluene 1 mL solution and a cocatalyst [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] A 0.60 μmol-toluene 1 mL solution was contacted at room temperature under nitrogen and then a solution stirred for 10 minutes at room temperature was injected with nitrogen to initiate polymerization. Then, after stirring for 5 minutes while controlling the internal pressure to be 2.7 MPa, the reaction was stopped by injecting ethanol with nitrogen, and the polymer was obtained by drying after cooling. Polymer yield 6.4g.
Polymer index: density = 0.8991 g / cm ³ , MFR = 2.34 g / 10 min, weight average molecular weight Mw = 82,000, number average molecular weight Mn = 37,300, Mw / Mn = 2.20, 1-hexene content 9.6 mol%.

(Example 2)
The same polymerization operation as in Example 1 was carried out except that 96 mL of 1-hexene was used. Polymer yield 6.2g.
Polymer index: density = 0.719 g / cm ³ , MFR = 10.2 g / 10 min, weight average molecular weight Mw = 59,400, number average molecular weight Mn = 28,300, Mw / Mn = 2.10, 1-hexene content 14.3 mol%.

(Comparative Example 1)
The same polymerization operation as in Example 1 was carried out except that 0.10 μmol of metallocene compound B, 0.05 μmol of promoter and 33 mL of 1-hexene were used instead of metallocene compound A. Polymer yield 7.4g.
Polymer index: Density = 0.020 g / cm ³ , MFR = 1.10 g / 10 min, Weight average molecular weight Mw = 102,700, Number average molecular weight Mn = 54,300, Mw / Mn = 1.89, Tm = 91. 7 ° C., 1-hexene content 5.8 mol%.

(Comparative Example 2)
Instead of metallocene compound A, 0.10 μmol of metallocene compound B and 0.
The same polymerization operation as in Example 1 was performed except that 05 μmol was used and 58 mL of 1-hexene was used. Polymer yield 5.6 g.
Polymer index: density = 0.8887 g / cm ³ , MFR = 2.9 g / 10 min, Mw = 81,200, Mn = 42,700, Mw / Mn = 1.90, Tm = 74.1
° C., 1-hexene content 9.6 mol%.

(Comparative Example 3)
A polymerization operation was carried out in the same manner as in Example 1 except that 0.10 μmol of metallocene compound B, 0.20 μmol of promoter and 96 mL of 1-hexene were used instead of metallocene compound A. Polymer yield 7.9g.
Polymer index: density = 0.8729 g / cm ³ , MFR = 11 g / 10 min, Mw = 53,200, Mn = 24,700, Mw / Mn = 2.15, Tm = 59.3 ° C.

(Comparative Example 4)
The same polymerization operation as in Example 1 was conducted except that 0.30 μmol of metallocene compound C was used instead of metallocene compound A, 0.15 μmol of cocatalyst was used, the amount of 1-hexene used was 33 mL, and the polymerization time was 5 minutes. Carried out. Polymer yield 19.1 g.
Polymer index: density = 0.8981 g / cm ³ , MFR = 5.3 g / 10 min, Mw = 84,400, Mn = 19,200, Mw / Mn = 4.40, Tm = 77.8
° C., 1-hexene content 7.8 mol%.

(Comparative Example 5)
A polymerization operation was carried out in the same manner as in Example 1 except that 0.48 μmol of metallocene compound C was used instead of metallocene compound A, 0.24 μmol of promoter was used, and the polymerization time was 5 minutes. Polymer yield 13.6 g.
Polymer index: Density = 0.8764 g / cm ³ , MFR = 51 g / 10 min, Mw = 41,800, Mn = 10,300, Mw / Mn = 4.04, Tm = 67.0
° C, 1-hexene content 12.3 mol%.

(Comparative Example 6)
The same polymerization operation as in Example 1 was conducted except that 0.80 μmol of metallocene compound E was used instead of metallocene compound A, 0.40 μmol of cocatalyst was used, the amount of 1-hexene used was 33 mL, and the polymerization time was 12 minutes. Carried out. Polymer yield 15.1 g.
Polymer index: MFR = 3600 g / 10 min, Mw = 8,200, Mn = 3,600, Mw / Mn = 2.25, Tm = 75.7 ° C., 1-hexene content 7.9 mol%.

(Comparative Example 7)
A polymerization operation was carried out in the same manner as in Example 1 except that 0.70 μmol of metallocene compound E was used instead of metallocene compound A, 0.35 μmol of promoter was used, and the polymerization time was 18 minutes. Polymer yield 6.0 g.
Polymer index: Mw = 6,800, Mn = 3,100, Mw / Mn = 2.1
7, Tm = 62.0 ° C.

  The performances of Examples 1 and 2 and Comparative Examples 1 to 7 are collectively shown in Table 1, and the relationship between the molecular weight (Mn) and the density in Examples 1 and 2 and Comparative Examples 1 to 5 is shown in FIG. Table 2 summarizes the results of the complexation reaction and dimethylation reaction of the synthesis example and the results of the polymerization examples. The criteria for determination in the catalyst performance column in Table 2 are shown in Table 1 and FIG. 1 as ◯ for those capable of producing high molecular weight copolymers and x for those not capable of being produced.

[Consideration of Comparison Results of Examples and Comparative Examples]
As is clear from Table 1, FIG. 1 and Table 2, the comparison between Examples 1 and 2, Comparative Examples 1 to 3 and Comparative Examples 4 to 7 in Table 1 and FIG. According to the comparison of the synthesis yield of the metallocene compound used in the comparative example, the indenyl ring has a hydrogen atom at the 2-position and the phenyl group having at least one substituent other than the hydrogen atom at the 4-position of the indenyl ring. It is apparent that the metallocene compound A of the present invention can be easily synthesized in the production of a racemate and can produce a high molecular weight copolymer.
More specifically, FIG. 1 shows that in the examples, the density and molecular weight are high in a balanced manner, and the comonomer content and molecular weight are both good. Tables 1 and 2 show that, in the Examples, high molecular weight copolymers can be produced, and the yield of the racemate is high, so that synthesis is easy from the viewpoint of production of the racemate. .

On the other hand, the metallocene compound B having a hydrogen atom at the 2-position of the indenyl ring and a phenyl group having no substituent at the 4-position of the indenyl ring can produce a high molecular weight copolymer, From the viewpoint of production of the body, it is difficult to produce the compound and the synthesis yield is low.
In the metallocene compounds C and E having a substituent other than a hydrogen atom at the 2-position of the indenyl ring, the molecular weight of the copolymer that can be produced is not sufficient, and in addition, the metallocene compound E has a low racemic yield. In addition, in the metallocene compound D having a substituent other than a hydrogen atom at the 2-position of the indenyl ring and introducing a substituent on the 4-position phenyl group, the synthesis yield of the racemate decreased.

  As described above, only a metallocene compound having a hydrogen atom at the 2-position of the indenyl ring and a phenyl group having at least one substituent other than a hydrogen atom at the 4-position of the indenyl ring can be synthesized. It is clear that it is easy and can produce high molecular weight copolymers.

  Although the invention has been described in detail above with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

As is apparent from the above, the metallocene compound of the present invention is easy to synthesize and is used as a polymerization catalyst to obtain a higher molecular weight olefin copolymer in olefin copolymer than in the conventional complex catalyst system. be able to. In particular, a low density and high molecular weight ethylene copolymer can be produced.
As a result, the olefin polymerization catalyst of the present invention and the method for producing an olefin polymer using the olefin polymerization catalyst can be polymerized at industrially advantageous polymerization temperatures and conditions, and the metallocene catalyst can be easily produced. It is possible and has extremely high industrial value.

Claims (11)

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

[Wherein M is Ti, Zr or Hf;
R ^{1 to} R ⁹ and R ^{11 to} R ¹⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a 6 to 20 carbon atom. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group A group, —NR ²¹ ₂ group, —SR ²¹ group, —OSiR ²¹ ₃ group, or —PR ²¹ ₂ group, wherein R ²¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, carbon number be 6-20 aryl group), provided ^that at least one of R 5 to R ⁹ and ^R 15 ^{to R 19} may be other than hydrogen ^atom, adjacent R 5 to R ⁹ and ^R 15 ^{to R 19} is The substituent does not form an aromatic ring and R ² ˜R ⁴ and R ¹² ˜R ¹⁴ adjacent groups together with the atoms connecting them form one or more aromatic or aliphatic rings, or R ⁴ and R ⁵ , R ⁴ and R ⁹ , R ¹⁴ and R ¹⁵ or R ¹⁴ and R ¹⁹ together with the atoms connecting them may form one aromatic or aliphatic ring;
Q is a silicon atom or a germanium atom, n is a natural number of 1 to 3, R ¹⁰ and R ²⁰ are the same or different and are a hydrogen atom, a halogen atom, a C 1-10 alkyl group, a C 1 10 fluoroalkyl groups, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, and 2 to 10 carbon atoms An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkenyl group having 8 to 40 carbon atoms, and R ¹⁰ and R ²⁰ together with the atoms connecting them. May form one or more rings;
X ¹ and X ² are the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms Selected from an alkyl group having 1 to 20 carbon atoms, a substituted amino group having 1 to 10 carbon atoms, an OH group, a halogen atom, and a neutral ligand capable of coordinating with a lone pair. Each may be the same or different, and X ¹ and X ² may be combined with atoms connecting them to form one ring. ] In the general formula (I), R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different and have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. Or a metallocene compound according to claim 1, which is an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. In the general formula (I), R ^{5 to} R ⁹ and R ^{15 to} R ¹⁹ are the same or different and are a hydrogen atom, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a carbon atom having 1 to 6 carbon atoms. The metallocene compound according to claim 1 or 2, which is an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrogen group. In the general formula ^(I), characterized in that R 1 to R ⁴ and ^R 11 ^{to R 14} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, according to any one of claims 1 to 3 Metallocene compounds. The metallocene compound according to claim 1, wherein n is 1 in the general formula (I).   The metallocene compound according to any one of claims 1 to 5, wherein in the general formula (I), M is Hf. An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metallocene compound component (B) according to any one of claims 1 to 6: Compound that reacts with component (A) to form an ion pair or ion-exchange layered silicate component (C) : Organoaluminum compound   The olefin polymerization catalyst according to claim 7, wherein the component (B) is a boron compound.   A method for producing an olefin polymer, wherein the olefin polymerization catalyst according to claim 7 or 8 is used to perform olefin polymerization or copolymerization.   The method for producing an olefin polymer according to claim 9, wherein the olefin contains ethylene. The method for producing an olefin polymer according to claim 9 or 10, wherein the polymerization temperature is 120 ° C or higher.

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