JP6729730B2 - Process for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer, and more particularly, to a method for producing an olefin polymer capable of suppressing a performance change of the obtained polymer even if a catalyst used for producing the olefin polymer is stored for a long period of time.

When an olefin polymer is produced by using a catalyst having a plurality of transition metal compounds as catalyst components, the olefin polymer is considered in terms of molecular weight distribution, composition distribution, macromer copolymerization involving the exchange of monomers between transition metal compounds, and the like. It is known that the structure of the coalesce can be controlled and give unique performance.
As such catalysts are used industrially, it is economically necessary to store them for a long period of time without deteriorating or deteriorating.

For a catalyst having a plurality of transition metal compounds as a catalyst component, one catalyst component forms a macromer by polymerizing a monomer, and the other catalyst component forms a macromer by copolymerizing the monomer with the macromer. It has been found that there are catalyst systems capable of producing polymers with chain branching, and various catalyst systems have been found. The method for producing a polymer having such a long chain branch is sometimes called a macromer method. For example, a macromer method for producing a long-chain branched propylene polymer is described in the following patent documents (for example, see Patent Documents 1 to 7).

As described above, in a catalyst system that forms a polymer having a long chain branch by the macromer method, the activity of the catalyst deteriorates due to deterioration and deterioration of the catalyst due to long-term storage of the catalyst. As described above, there is a problem that the performance of the obtained polymer changes.
Although it is not a catalyst system that forms a polymer having a long chain branch by the macromer method, for example, Patent Document 8 discloses a multimodal catalyst system including a bisamide catalyst system and a non-bisamide catalyst system at a controlled temperature. Disclosed is a method in which the polymer can be stored at a temperature (less than about 21° C., preferably less than about 1° C., more preferably less than about −9° C.) for a specific period of time without changing the multimodality of the polymer. ing. In this method, it is shown that a plurality of catalyst components are deteriorated at different speeds to change the multimodal property of the polymer, and a method for suppressing the change is suppressed.
However, the above suppression method is based on the premise of a multimodal catalyst system, and merely focuses on the change in the molecular weight distribution of the polymer, and when a catalyst system using a plurality of transition metal compounds as a catalyst component is used. The method for suppressing the performance change of the polymer obtained by the macromer method has not been found yet.

JP, 2009-040959, A JP, 2009-057542, A JP, 2009-108247, A JP, 2011-144356, A JP, 2010-196036, A Japanese Patent Publication No. 2001-525463 Special table 2001-527589 gazette Japanese Patent Publication No. 2010-509484

An object (problem) of the present invention is to provide a method for producing an olefin polymer capable of suppressing the performance change of the obtained polymer even when the catalyst is stored for a long time in view of the above-mentioned conventional circumstances and problems. is there.

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and in particular, in a catalyst system in which a polymer having a long chain branch is formed by a macromer method, the catalyst is stored for a long period of time, In order to solve the problem that the performance of the obtained polymer changes due to deterioration and deterioration, as a result of studying long-term storage of the catalyst, by adopting a specific long-term storage method, long-term (2 It has been found that the performance change of the obtained polymer can be suppressed even by using the stored catalyst for more than 1 year. The present invention has been completed based on these findings.

That is, according to the first aspect of the present invention, after producing an olefin polymerization catalyst containing the following components [A-1], [A-2] and [B], the olefin polymerization catalyst is heated to 1°C or higher. Provided is a method for producing an olefin polymer, which comprises storing at a controlled temperature of 20° C. or lower for 2 years or more, and polymerizing an olefin using the stored catalyst for olefin polymerization.
Component [A-1]: A metallocene compound represented by the following general formula (1).

[In the general formula ^{(1), Z 11 is, - (E 12) (R} 13) m '(R 14) p' -, - O -, - S -, - NR 15 - or ^{-PR 16} - a represents , E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and R ¹¹ and R ¹³ are each independently a halogen atom, a carbon number of 1 to 20. Hydrocarbon group or halogenated hydrocarbon group, silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group Represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or an amino group having a halogenated hydrocarbon group, and R ¹² and R ¹⁴ are each independently. Represents a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, wherein the heteroaromatic group is a halogen atom or a carbon number. 1-20 hydrocarbon groups or halogenated hydrocarbon groups, silyl groups having 1-20 carbon atoms hydrocarbon groups or halogenated hydrocarbon groups, 1-20 carbon atoms hydrocarbon groups or halogenated hydrocarbon groups It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a silyl group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Represents a silyl group having, m and m′ represent 0 or an integer of 1 to 8, and p and p′ are when Z ¹¹ is (E ¹² )(R ¹³ )m′(R ¹⁴ )p′. One or both are an integer of 1 to 8, and when Z ¹¹ is —O—, —S—, —NR ¹⁵ — or —PR ¹⁶ —, p is 0 or an integer of 1 to 8. , Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Optionally represents a germylene group, M ¹¹ represents titanium, zirconium or hafnium, X ¹¹ and X ¹² are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 20. Represents a hydrocarbon group or a halogenated hydrocarbon group, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [A-2]: a metallocene compound represented by the following general formula (2).

[In the general formula (2), E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent, The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, and Q ²¹ has 1 to 20 carbon atoms. Represents a divalent hydrocarbon group of, a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, M ²¹ Represents titanium, zirconium or hafnium, and X ²¹ and X ²² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and 1 to 20 carbon atoms. It represents a silyl group having a hydrocarbon group or a halogenated hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: At least one selected from the following compound group.
[B-1] Supported aluminum oxy compound,
[B-2] An ionic compound or Lewis acid capable of reacting with the supported metallocene compounds [A-1] and [A-2] and converted into a cation, and a [B-3] ion. Exchangeable layered silicate.

According to the second aspect of the present invention, an olefin polymerization catalyst containing the following components [A-1], [A-2] and [B] is produced, and the olefin polymerization catalyst and olefin are contacted with each other. After producing the prepolymerized olefin polymerization catalyst, the prepolymerized olefin polymerization catalyst is stored for 2 years or more at a controlled temperature of 1° C. or higher and 20° C. or lower, and the stored olefin is stored. Provided is a method for producing an olefin polymer, which comprises polymerizing an olefin using a polymerization catalyst for polymerization.
Component [A-1]: A metallocene compound represented by the following general formula (1).

[In the general formula ^{(1), Z 11 is, - (E 12) (R} 13) m '(R 14) p' -, - O -, - S -, - NR 15 - or ^{-PR 16} - a represents , E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and R ¹¹ and R ¹³ are each independently a halogen atom, a carbon number of 1 to 20. Hydrocarbon group or halogenated hydrocarbon group, silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group Represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or an amino group having a halogenated hydrocarbon group, and R ¹² and R ¹⁴ are each independently. Represents a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, wherein the heteroaromatic group is a halogen atom or a carbon number. 1-20 hydrocarbon groups or halogenated hydrocarbon groups, silyl groups having 1-20 carbon atoms hydrocarbon groups or halogenated hydrocarbon groups, 1-20 carbon atoms hydrocarbon groups or halogenated hydrocarbon groups It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a silyl group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Represents a silyl group having, m and m′ represent 0 or an integer of 1 to 8, and p and p′ are when Z ¹¹ is (E ¹² )(R ¹³ )m′(R ¹⁴ )p′. One or both are an integer of 1 to 8, and when Z ¹¹ is —O—, —S—, —NR ¹⁵ — or —PR ¹⁶ —, p is 0 or an integer of 1 to 8. , Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Optionally represents a germylene group, M ¹¹ represents titanium, zirconium or hafnium, X ¹¹ and X ¹² are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 20. Represents a hydrocarbon group or a halogenated hydrocarbon group, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [A-2]: a metallocene compound represented by the following general formula (2).

[In the general formula (2), E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent, The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, and Q ²¹ has 1 to 20 carbon atoms. Represents a divalent hydrocarbon group of, a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, M ²¹ Represents titanium, zirconium or hafnium, and X ²¹ and X ²² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and 1 to 20 carbon atoms. It represents a silyl group having a hydrocarbon group or a halogenated hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: At least one selected from the following compound group.
[B-1] Supported aluminum oxy compound,
[B-2] An ionic compound or Lewis acid capable of reacting with the supported metallocene compounds [A-1] and [A-2] and converted into a cation, and a [B-3] ion. Exchangeable layered silicate.

Further, according to a third aspect of the present invention, there is provided a method for producing an olefin polymer according to the first or second aspect of the invention, characterized in that the catalyst for olefin polymerization that has been dried under reduced pressure is stored in advance.
Further, according to the fourth invention of the present invention, in the third invention, the amount of the residual solvent in the catalyst for olefin polymerization dried under reduced pressure is 0.5 wt% or less, and the production of an olefin polymer. A method is provided.
Further, according to a fifth invention of the present invention, in any one of the first to fourth inventions, the olefin polymerization catalyst is in a range of 0.01 MPaG to 0.05 MPaG using an inert gas in a pressure vessel. There is provided a method for producing an olefin polymer, which comprises pressurizing and storing.
Further, according to a sixth invention of the present invention, in any one of the first to fifth inventions, in the storage, the following component [C] is a total of 1 of the component [A-1] and the component [A-2]. Provided is a method for producing an olefin polymer, which is characterized by storing under the condition of 1 to 70 moles per mole.
Component [C]: Organoaluminum compound.

According to a seventh invention of the present invention, in any one of the first to sixth inventions, the component [A-1] is a metallocene compound forming a polymerization catalyst for producing an olefin macromer [provided that an olefin macromer is produced. The metallocene compound forming a polymerization catalyst is a metallocene compound forming a polymerization catalyst that produces a polymer having a terminal vinyl ratio (Rv) of 0.5 or more when olefin homopolymerization is performed at 70°C. Is. ] The manufacturing method of the olefin polymer characterized by the above is provided.
According to an eighth invention of the present invention, in any one of the first to seventh inventions, one or both of M ¹¹ and M ²¹ is hafnium, which is a method for producing an olefin polymer. Provided.
Furthermore, according to the ninth invention of the present invention, in any one of the first to eighth inventions, the olefin polymer has a branching index (g′) of 0 at a molecular weight (M) of 1,000,000 (logM=6). A method for producing an olefin polymer is provided, which is characterized in that it is 0.95 or less.

According to a tenth invention of the present invention, in the first or second invention, at least one of the components [A-1] and [A-2] is a metallocene compound represented by the following general formula (3). A method for producing an olefin polymer is provided.

[In the general formula (3), R ³¹ and R ³² are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or halogen. A silyl group having a hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms, or a silyl group having a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, having 1 to 1 carbon atoms An amino group having 20 hydrocarbon groups or halogenated hydrocarbon groups, or a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5- or 6-membered ring R ³³ and R ³⁴ each independently represent a halogen atom or an aryl group having 6 to 16 carbon atoms which may contain silicon, and Q ³¹ represents a divalent carbon atom having 1 to 20 carbon atoms. Represents a hydrogen group, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ³¹ represents titanium or zirconium Or hafnium, and X ³¹ and X ³² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen. It represents a silyl group having a modified hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

According to the eleventh invention of the present invention, in any one of the first to eighth inventions, the olefin polymer is a propylene homopolymer, or propylene and an α-olefin having 2 to 12 carbon atoms (excluding 3). There is provided a method for producing an olefin polymer, which is a copolymer with
In the present invention, unless otherwise specified, the metallocene compound also includes a half metallocene compound.

According to the method for producing an olefin polymer of the present invention, a polymer obtained by using a catalyst containing a plurality of transition metal compounds as a catalyst component is obtained even if a catalyst stored for a long period of time is used. The performance change of can be suppressed. In particular, a catalyst produces a macromer by polymerizing a monomer in one catalyst component, and a copolymer with a monomer and a macromer in the other catalyst component to produce a polymer having a long-chain branch. In the case of a catalyst system that can be used, the resulting polymer can stably exhibit a high melt tension.

FIG. 1 shows the melt tension (MT) with respect to the melt flow rate (MFR) (g/10 minutes) of the olefin polymer obtained in Examples (Example 1/Reference Example 1, 2/Comparative Example 1). )(G) is a diagram plotted.

Hereinafter, the present invention will be described in detail.
One of the olefin polymerization catalysts according to the present invention is to produce an olefin polymerization catalyst containing the following components [A-1], [A-2] and [B], and to produce the produced olefin polymerization catalyst. It was stored for a long period of time at a controlled temperature of 1°C or higher and 20°C or lower.
In addition, another one of the olefin polymerization catalysts according to the present invention is to produce an olefin polymerization catalyst containing the following components [A-1], [A-2] and [B], prepolymerize it, and The produced olefin polymerization catalyst is stored for a long period of time at a controlled temperature of 1° C. or higher and 20° C. or lower.
Then, the method for producing an olefin polymer of the present invention is to produce a polymer by polymerizing an olefin using the catalyst stored for a long period of time.
Component [A-1]: A metallocene compound represented by the following general formula (1).

[In the general formula ^{(1), Z 11 is, - (E 12) (R} 13) m '(R 14) p' -, - O -, - S -, - NR 15 - or ^{-PR 16} - a represents ,
E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group,
R ¹¹ and R ¹³ are each independently a silyl group having a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. , A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or halogen Represents an amino group having a hydrocarbon group,
R ¹² and R ¹⁴ each independently represent a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, and the heteroaromatic group The group group is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, a carbon group having 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a hydrogen group or a silyl group having a halogenated hydrocarbon group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. May be replaced with
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Represents a silyl group having
m and m′ represent 0 or an integer of 1 to 8,
In the case where Z ¹¹ is (E ¹² )(R ¹³ )m′(R ¹⁴ )p′, one or both of p and p′ are an integer of 1 to 8 and Z ¹¹ is —O—, −. S -, - ^{NR 15} - or ^{-PR 16} - in the case of, p is an integer of 0 or 1 to 8,
Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. May represent a germylene group,
M ¹¹ represents titanium, zirconium or hafnium,
X ¹¹ and X ¹² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. It represents a silyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [A-2]: a metallocene compound represented by the following general formula (2).

[In the general formula (2), E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent, The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in the 5- or 6-membered ring,
Q ²¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a good germylene group,
M ²¹ represents titanium, zirconium or hafnium,
X ²¹ and X ²² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. It represents a silyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

Component [B]: At least one selected from the following compound group.
[B-1] Supported aluminum oxy compound,
[B-2] An ionic compound or Lewis acid capable of reacting with the supported metallocene compounds [A-1] and [A-2] and converted into a cation, and a [B-3] ion. Exchangeable layered silicate.

Then, after storing the obtained catalyst for olefin polymerization under specific conditions, by performing olefin polymerization, a long-chain branched propylene polymer can be efficiently produced without degrading its performance. it can.
Hereinafter, the olefin polymerization catalyst, the method for producing the same, and the like will be described in detail for each item.

1. Catalyst Component of Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention essentially contains at least components [A-1], [A-2] and [B].

(1) Component [A-1]
The component [A-1] is a metallocene compound having the structure of the general formula (1) described above, and preferably a metallocene compound forming a polymerization catalyst for producing an olefin macromer. The metallocene compound forming the polymerization catalyst for forming the olefin macromer will be described later.
As the component [A-1], the following structure can be mentioned as one of preferred embodiments without limitation. That is, the component [A-1] is preferably a metallocene compound represented by the following general formula (3).

[In the general formula (3), R ³¹ and R ³² are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or halogen. A silyl group having a hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms, or a silyl group having a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, having 1 to 1 carbon atoms An amino group having 20 hydrocarbon groups or halogenated hydrocarbon groups, or a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5- or 6-membered ring, The heteroaromatic group represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a carbon number. Hydrocarbon group having 1 to 20 carbon atoms or silyl group having halogenated hydrocarbon group, or hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms or halogenated hydrocarbon group Optionally substituted with an amino group having a group, R ³³ and R ³⁴ are each independently an aryl group having 6 to 20 carbon atoms or a halogenated aryl group, or oxygen in a 5-membered ring or a 6-membered ring. Represents a monocyclic or polycyclic heteroaromatic group containing an atom, a sulfur atom or a nitrogen atom, wherein the heteroaromatic group is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. R may be substituted with a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, R ³¹ and R ³² and R ³³ and R ³⁴ are not groups other than a heteroaromatic group at the same time, and Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a carbon atom having 1 to 20 carbon atoms. Represents a silylene group which may have a hydrogen group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, M ³¹ represents titanium, zirconium or hafnium, and X ³¹ and X ³² Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and amino. Represents a group or an alkylamino group having 1 to 20 carbon atoms. ]

R ³¹ and R ³² are preferably each independently a heteroaromatic group, more preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group or a substituted group. 2-furfuryl group, more preferably a substituted 2-furyl group.
Further, as the substituent of the substituted 2-furyl group, the substituted 2-thienyl group, and the substituted 2-furfuryl group, a methyl group, an ethyl group, an alkyl group having 1 to 6 carbon atoms such as a propyl group, Examples thereof include a halogen atom such as a fluorine atom and a chlorine atom, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Furthermore, as R ³¹ and R ³² , a 2-(5-methyl)-furyl group is particularly preferable. Further, it is preferable that R ³¹ and R ³² are the same as each other.

R ³³ and R ³⁴ described above are aryl groups having 6 to 16 carbon atoms, which may contain a halogen atom, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. Further, the aryl group has, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms and trialkylsilyl groups having 1 to 6 carbon atoms on the aryl cyclic skeleton. And a halogen-containing hydrocarbon group having 1 to 6 carbon atoms may be included as a substituent.
In addition, R ³³ and R ³⁴ may be a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Such a heterocyclic group is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group or a substituted 2-furfuryl group, more preferably a substituted 2-furyl group. It is a frill group. Examples of these substituents include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group, a halogen atom such as a fluorine atom and a chlorine atom, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
As R ³³ and R ³⁴ , at least one is preferably a phenyl group, a 4-i-propyl group, a 4-trimethylsilyl group, a 4-t-butylphenyl group, a 2,3-dimethylphenyl group, and a 3,5-diphenyl group. t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, and more preferably phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group. , 4-chlorophenyl group. Further, R ³³ and R ³⁴ are preferably the same as each other.

Further, X ³¹ and X ³² are auxiliary ligands and react with the component [B] to generate an active metallocene having an olefin polymerization ability. Therefore, as long as this object is achieved, the types of ligands of X ³¹ and X ³² are not limited, and each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group or an alkylamino group having 1 to 20 carbon atoms.
Here, in the present invention, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group having 1 to 20 carbon atoms, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group. ..

Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings and bridges two conjugated five-membered ring ligands through a carbon atom having 1 or 2 carbon atoms; It represents either a silylene group which may have a hydrocarbon group of 1 to 20 or a germylene group which may have a hydrocarbon group of 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ³¹ described above include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; cycloalkylene groups; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, Alkylsilylene groups such as diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, and (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; diphenylsilylene and the like. Arylsilylene group; Alkyloligosilylene group such as tetramethyldisilirene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having the above divalent hydrocarbon group having 1 to 20 carbon atoms; )(Aryl)germylene group; arylgermylene group and the like.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.
Further, the indene ring of the general formula (3) may have a substituent other than R ³¹ , R ³² , R ³³ and R ³⁴ . In that case, it may have a substituent at the 5- or 6-position of the indene ring. Examples of such groups include a 5-position methyl group and a 6-position methyl group. Further, as another example, the substituents at the 5-position and the 6-position can be bonded to each other to form a cyclic structure. As such an example, an indacene skeleton is preferable.

Among the compounds represented by the general formula (3), preferable compounds are specifically exemplified below.
(1) dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-phenyl-indenyl}]hafnium,
(2) dichloro[1,1′-dimethylsilylenebis{2-(2-thienyl)-4-phenyl-indenyl}]hafnium,
(3) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(4) dichloro[1,1′-diphenylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(5) dichloro[1,1′-dimethylgermylene bis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(6) dichloro[1,1′-dimethylgermylene bis{2-(5-methyl-2-thienyl)-4-phenyl-indenyl}]hafnium,
(7) dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(8) dichloro[1,1′-dimethylsilylenebis{2-(5-trimethylsilyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(9) dichloro[1,1′-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl-indenyl}]hafnium,
(10) dichloro[1,1′-dimethylsilylenebis{2-(4,5-dimethyl-2-furyl)-4-phenyl-indenyl}]hafnium dichloride,
(11) dichloro[1,1′-dimethylsilylenebis{2-(2-benzofuryl)-4-phenyl-indenyl}]hafnium,
(12) dichloro[1,1′-dimethylsilylenebis{2-(2-furfuryl)-4-phenyl-indenyl}]hafnium,
(13) Dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]hafnium,
(14) Dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}]hafnium,
(15) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}]hafnium,
(16) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]hafnium,
(18) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]hafnium,
(19) dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(20) dichloro[1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
(21) dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium,
(22) dichloro[1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium,
(23) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(24) Dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
(25) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium,
(26) dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium,
(27) dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(1-naphthyl)-indenyl}]hafnium,
(28) dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium,
(29) dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium,
(30) dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium, and the like.

Among these, more preferable are dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium and dichloro[1,1′-dimethylgel. Mylene bis{2-(5-methyl-2-thienyl)-4-phenyl-indenyl}] hafnium, dichloro[1,1'-dimethylsilylene bis{2-(5-methyl-2-furyl)-4-( 4-chlorophenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]hafnium, dichloro[1, 1′-Dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5 -Methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-( 4-trimethylsilylphenyl)-indenyl}]hafnium and dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-biphenylyl-indenyl}]hafnium.

Further, particularly preferred are dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{ 2-(5-Methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)] -4-(4-i-Propylphenyl)-indenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl }] Hafnium.

In addition, as the component [A-1], a compound represented by the general formula (4) and the like can be mentioned as another example of a non-limiting preferred embodiment.
The component [A-1] is preferably a half metallocene compound represented by the following general formula (4).

[In general formula (4), Cp represents a cyclopentadienyl group, M ⁴¹ is Ti, Zr, or Hf, Q ⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, or carbon. A silylene group that may have a hydrocarbon group of 1 to 20 or a germylene group that may have a hydrocarbon group of 1 to 20 carbon atoms, and Z ⁴¹ represents an amide group, a phosphide group, or oxygen. An atom, a sulfur atom, a phenyleneoxy group or an alkylidene group.
X ⁴¹ and X ⁴² represent σ covalent auxiliary ligands, which may be the same or different, the sum of q and r is 0 to 2, L is a neutral Lewis base, and s Is 0 to 2, and the sum of q, r, and s is 0 to 4. In addition, q+r+2 represents the oxidation number of the central metal M ⁴¹ .
R ⁴¹ and R ⁴² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom-containing alkyl group having 1 to 8 carbon atoms, a silicon-containing alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms. To 18 aryl groups or halogenated aryl groups having 6 to 18 carbon atoms, which may be the same or different from each other, and adjacent R ⁴¹ and R ⁴² may both form a 5 to 10-membered ring. The 10-membered ring may contain an unsaturated bond. m and p are 0 or an integer of 1-8. ]

In the general formula (4), M ⁴¹ is Ti, Zr, or Hf, preferably Ti or Hf, and more preferably Ti.
Q ⁴¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. Is also a good germylene group, and specific examples thereof include a dimethylsilylene group, a diethylsilylene group, a di-i-propylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a methyl-i-propylsilylene group, a dimethylgermylene group, Diethylgermylene group, di-i-propylgermylene group, diphenylgermylene group, methylphenylgermylene group, methyl-i-propylgermylene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, 1 -Phenylethylene group, 1,2-diphenylethylene group, silacyclobutane group, silacyclopentane group, 2,5-dimethylsilacyclopentane group, silacyclohexane group, silafluorene group, phenylene group and the like can be mentioned.
Among these, a dimethylsilylene group, a di-i-propylsilylene group, a diphenylsilylene group, a silacyclobutane group, a silacyclopentane group, a silacyclohexane group, a phenylene group are preferable, and a dimethylsilylene group and a diphenylsilylene group are particularly preferable. And a silacyclohexane group.

Z ⁴¹ is an amide group, a phosphide group, an oxygen atom, a sulfur atom, a phenyleneoxy group or an alkylidene group, preferably an amide group, a phenyleneoxy group and an oxygen atom, and most preferably an amide group.
X ⁴¹ and X ⁴² represent σ covalent auxiliary ligands and may be the same or different and are not particularly limited, but preferable X ⁴¹ and X ⁴² are a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms. , A substituted amino group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom .About.20 halogen-containing hydrocarbon groups and the like. A crosslinked structure may be formed between X ⁴¹ and X ⁴² .
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, trimethylsilyl group. Examples thereof include a methyl group, a methoxy group and a phenoxy group. Among these, a halogen atom and a hydrocarbon group having 1 to 8 carbon atoms are preferable, and a chlorine atom, a methyl group, an i-butyl group and a benzyl group are particularly preferable.

L represents a neutral Lewis base, which may be the same or different and is not particularly limited, and examples thereof include ethers, amines, phosphines, dienes, and thioethers. Of these, preferred is Are ethers, amines and dienes, most preferably ethers and dienes.

R ⁴¹ and R ⁴² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom-containing alkyl group having 1 to 8 carbon atoms, a silicon-containing alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms. To 18 aryl groups or halogenated aryl groups having 6 to 18 carbon atoms, which may be the same or different from each other, and adjacent R ⁴¹ and R ⁴² may both form a 5 to 10-membered ring. The 10-membered ring may contain an unsaturated bond.
Specific examples of the alkyl group having 1 to 8 carbon atoms in R ⁴¹ and R ⁴² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, Examples thereof include t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
In addition, examples of the halogen atom of the halogen atom-containing alkyl group having 1 to 8 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the halogen containing alkyl group having 1 to 8 carbon atoms has 1 to 8 carbon atoms. A hydrogen atom on the skeleton of the alkyl group of 8 is substituted with a halogen atom.
Specific examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, 2,2,2. -Trifluoroethyl group, 2,2,1,1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, 5-chloropentyl group, 5,5,5 -Trichloropentyl, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, 6-chlorohexyl group, 6,6,6-trichlorohexyl group, 6-fluorohexyl group, 6,6,6-tri Examples thereof include fluorohexyl group, 8-fluorooctyl group, and 8,8,8-trifluorooctyl group.

The silicon-containing alkyl group having 1 to 20 carbon atoms is a group in which a silicon atom is substituted for a carbon atom on the skeleton of the alkyl group. Specific examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a trimethylsilylmethyl group and a 2-trimethylsilylethyl group.
Further, specific examples of the aryl group having 6 to 18 carbon atoms include phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, i-butylphenyl group, s-butylphenyl group. , T-butylphenyl group, n-hexylphenyl group, trimethylphenyl group, pentamethylphenyl group, biphenyl group, naphthyl group and the like.
Examples of the halogen atom of the halogenated aryl group having 6 to 18 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the halogenated aryl group having 6 to 18 carbon atoms is an aryl group having 6 to 18 carbon atoms. A hydrogen atom on the skeleton of the group is replaced with a halogen atom.
Specific examples thereof include a pentafluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a perfluoronaphthyl group and a perfluorobiphenyl group.
In addition, R ⁴¹ and R ⁴² may form a 5- to 10-membered ring with both adjacent R ⁴¹ and R ⁴² , or the 5- to 10-membered ring may form an unsaturated bond. Specific examples of the cycloalkadienyl ring formed by R ⁴¹ and R ⁴² forming a ring include an indenyl ring, a benzoindenyl ring, a tetrahydroindenyl ring, and an azulenyl ring.

Among the compounds represented by the general formula (4), preferable compounds are specifically exemplified below.
(1) dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamide)titanium dichloride,
(2) dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dichloride,
(3) dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(4) dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride,
(5) dimethylsilyl(tetramethylcyclopentadienyl)(s-butylamido)titanium dichloride,
(6) dimethylsilyl(tetramethylcyclopentadienyl)(n-butylamido)titanium dichloride,
(7) dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(8) diethylsilyl(tetramethylcyclopentadienyl)(cyclododecyl-amido)titanium dichloride,
(9) diethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(10) diethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(11) diethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(12) methylene(tetramethylcyclopentadienyl)(cyclododecyl-amido)titanium dichloride,
(13) methylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(14) methylene(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(15) methylene(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(16) dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecyl-amido)titanium dimethyl,
(17) dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,
(18) dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dimethyl,
(19) Dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,
(20) dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclododecylamide)titanium dichloride,

(21) dimethylsilyl(2,5-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(22) dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(23) dimethylsilyl(2,5-dimethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(24) dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclopentadodecylamide)titanium dichloride,
(25) dimethylsilyl(3,4-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(26) dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(27) dimethylsilyl(3,4-dimethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(28) dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclododecylamide)titanium dichloride,
(29) dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(30) dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(31) Dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(32) dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclododecylamido)titanium dichloride,
(33) dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(34) dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(35) dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(36) Dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclododecylamido)titanium dichloride,
(37) dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,
(38) Dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclohexylamido)titanium dichloride,
(39) Dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(1-adamantylamido)titanium dichloride,
(40) dimethylsilyl(2-tetrahydroindenyl)(cyclododecylamido)titanium dichloride,
(41) dimethylsilyl(2-tetrahydroindenyl)(cyclohexylamido)titanium dichloride,
(42) Dimethylsilyl(2-tetrahydroindenyl)(1-adamantylamido)titanium dichloride,
(43) Dimethylsilyl(2-tetrahydroindenyl)(exo-2-norbornylamido)titanium dichloride and the like.

The most preferred compounds are:
Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamide)titanium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantyl Amido) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (exo-2-norbornylamido) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamido) titanium dimethyl, dimethylsilyl (tetra Methylcyclopentadienyl)(cyclohexyl-amido)titanium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl, and dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-nor Bornylamido)titanium dimethyl.

As described above, the component [A-1] is preferably a metallocene compound that forms a polymerization catalyst that produces an olefin macromer. However, the metallocene compound forming the polymerization catalyst for producing an olefin macromer is the terminal vinyl ratio (when the homopolymerization of the olefin having the largest molar content among the monomer units constituting the olefin polymer is carried out at 70° C. Rv) is a metallocene compound that forms a polymerization catalyst that produces a polymer satisfying 0.5 or more.

Here, the terminal vinyl ratio (Rv) and the terminal vinylidene ratio (Rvd) are respectively defined by the following formulas.
(Rv)=(Mn/M)×2×[Vi]/1000
(Rvd)=(Mn/M)×2×[Vd]/1000
(However, Mn is the number average molecular weight determined by GPC, M is the molecular weight of the monomer, [Vi] is the number of terminal vinyl groups per 1000 C calculated from ¹³ C-NMR, and [Vd] is ¹³ C-NMR. It is the number of terminal vinylidene groups per 1000 C calculated by 1000 C. Here, 1000 C means the total skeleton-forming carbon, and the total skeleton-forming carbon is a branch having a branch length of 2 carbon atoms of the monomer. It means all carbon atoms other than the constituent carbons, that is, [Vi] is the number of terminal vinyl groups per 1000 total skeleton-forming carbons, and [Vd] is the number per 1000 total skeleton-forming carbons. It is the number of terminal vinylidene groups.)

In the polymerization of olefins, β hydrogen is generally eliminated, and when the olefin is propylene, for example, the terminal of the vinylidene structure represented by the following structural formula (2-b) is generated. Further, when hydrogen is used, chain transfer to hydrogen usually occurs preferentially and a saturated terminal (isobutyl structure) as shown in the structural formula (2-c) is generated at the terminal.
However, when a complex having a special structure is used, a special chain transfer reaction generally called β-methyl elimination occurs, and the propenyl structure (vinyl structure) represented by the structural formula (2-a) is terminated. A polymer is produced (reference document: Macromol. Rapid Commun. 2000, 21, 1103-1107). In the case of using the complex having a very special structure exemplified in the present invention, when hydrogen is used, surprisingly, the β-methyl elimination reaction occurs preferentially although the activity is increased. It has been found that the propenyl structure (vinyl structure) of formula (2-a) is mainly produced.

Among structural formulas (2-a), structural formulas (2-b), and structural formulas (2-c), those copolymerizable with a metallocene complex or a Ziegler catalyst have a vinyl structure represented by structural formula (2-a). Only.
Therefore, among the all terminal structures, the higher the copolymerizable terminal vinyl ratio, the higher the efficiency as a macromer. Therefore, the component [A-1], which is the macromer-forming complex used in the present invention, is a metallocene compound having a terminal vinyl-forming ability such that the terminal vinyl ratio (Rv) is 0.5 or more. Further, as a preferable metallocene compound, the terminal vinyl ratio is preferably 0.70 or more, more preferably 0.75 or more. It is more preferably 0.80 or more, and ideally 1.0 (all ends are vinyl groups).

Here, details of the measuring method of [Vi] and [Vd] are as follows.
A sample (390 mg) was completely dissolved in deuterated 1,1,2,2-tetrachloroethane (2.5 ml) in an NMR sample tube (10φ), and then measured at 125° C. by a complete proton decoupling method. The chemical shift was set such that the central peak of the three deuterated 1,1,2,2-tetrachloroethane peaks was 74.2 ppm. Chemical shifts of other carbon peaks are based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Accumulation frequency: 10,000 times or more Observation area: -20 ppm to 179 ppm
The terminal vinyl content and terminal vinylidene content of the propylene polymer can be controlled by selecting a complex having a special structure that selectively causes the β-methyl elimination reaction with respect to the β-hydrogen elimination reaction. Examples of such a complex structure include a bisindene complex having a bulky heterocyclic group at the 2-position and an optionally substituted aryl group at the 4-position.
This selectivity can also be controlled by changing the polymerization temperature. For example, in the complexes shown in the examples, the higher the polymerization temperature, the higher the terminal vinyl ratio can be.

[Vi] utilizes that carbon 1 and carbon 2 of structural formula (2-a) are detected at 115.5 ppm and 137.6 ppm, and [Vd] is carbon 3 of structural formula (2-b). Using the fact that carbon 4 and carbon 4 are detected at 111.2 ppm and 144.5 ppm, the number is calculated as shown below in terms of the number with respect to 1000 total skeleton-forming carbons. Here, the total skeleton-forming carbon means all carbon atoms other than methyl carbon.
[Vi]=[peak intensity of carbon 1]/[sum of peak intensities of all skeleton-forming carbons]×1000
[Vd]=[peak intensity of carbon 3]/[sum of peak intensities of all skeleton-forming carbons]×1000

The terminal vinyl ratio has been described by taking a propylene polymer as an example, but the terminal vinyl ratio can be determined by the example of propylene even when the olefin is other than propylene.
It is shown in JP2009-299045A that the above-mentioned component [A-1] can form a polymerization catalyst for producing a propylene polymer having a terminal vinyl ratio (Rv) of 0.5 or more. There is.

(2) Component [A-2]
Component [A-2]: a metallocene compound represented by the following general formula (2).

[In the general formula (2), E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent, The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, and Q ²¹ has 1 to 20 carbon atoms. Represents a divalent hydrocarbon group of, a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, M ²¹ Represents titanium, zirconium or hafnium, and X ²¹ and X ²² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and 1 to 20 carbon atoms. It represents a silyl group having a hydrocarbon group or a halogenated hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

The above E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent. The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in the 5- or 6-membered ring.
Of these, a substituted cyclopentadienyl group, a substituted indenyl group, and a substituted azulenyl group are preferable.

As the component [A-2], a compound that forms a polymerization catalyst capable of copolymerizing an olefin monomer and an olefin macromer is preferable. Such a compound may be a compound which simultaneously forms a catalyst capable of producing a macromer.
Moreover, as a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are substituted indenyl groups, the following structures can be exemplified.

[In general formula (5), R ⁵¹ and R ⁵³ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ⁵² and R ⁵⁴ are each independently halogen, silicon, Alternatively, it is an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. X ⁵¹ and X ⁵² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms, and Q ⁵¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, Represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁵¹ represents zirconium or hafnium. ]

The above R ⁵¹ and R ⁵³ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like, preferably methyl. , Ethyl, n-propyl, i-propyl.
Further, R ⁵² and R ⁵⁴ are an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these, and as the aryl group, Containing one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. It may have a hydrocarbon group as a substituent.
As R ⁵² and R ⁵⁴ , at least one is preferably a phenyl group, a 4-i-propyl group, a 4-trimethylsilyl group, a 4-t-butylphenyl group, a 2,3-dimethylphenyl group, and a 3,5-diphenyl group. t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group. , 4-chlorophenyl group. Further, it is preferable that R ⁵² and R ⁵⁴ are the same as each other.

Further, X ⁵¹ and X ⁵² are auxiliary ligands, and react with the component [B] to generate an active metallocene having an olefin polymerization ability. To achieve this object, X ⁵¹ and X ⁵² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, It represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group or an alkylamino group having 1 to 20 carbon atoms.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group having 1 to 20 carbon atoms, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group.
Q ⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings and bridges two conjugated five-membered ring ligands via a carbon atom having 1 or 2 carbon atoms; Either a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms is shown. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc.; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene. An alkylsilylene group such as (n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, an (alkyl)(aryl)silylene group such as methyl(phenyl)silylene; an arylsilylene group such as diphenylsilylene; Alkyloligosilylene group such as tetramethyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl) (aryl) Germylene group; arylgermylene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

Among these compounds represented by the general formula (5), preferably,
(1) dichloro{1,1′-dimethylsilylenebis(2-methyl-4-phenylindenyl)}hafnium,
(2) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)indenyl}]hafnium,
(3) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-t-butylphenyl)indenyl}]hafnium,
(4) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-trimethylsilylphenyl)indenyl}]hafnium,
(5) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-chloro-4-t-butylphenyl)indenyl}]hafnium,
(6) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-methyl-4-t-butylphenyl)indenyl}]hafnium,
(7) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-chloro-4-trimethylsilylphenyl)indenyl}]hafnium,
(8) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-methyl-4-trimethylsilylphenyl)indenyl}]hafnium,
(9) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(1-naphthyl)indenyl}]hafnium,
(10) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-naphthyl)indenyl}]hafnium,
(11) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-fluoro-4-biphenyl)indenyl}]hafnium,
(12) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-chloro-4-biphenyl)indenyl}]hafnium,
(13) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(9-phenanthryl)indenyl}]hafnium,
(14) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chloro-2-naphthyl)indenyl}]hafnium,
(15) dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(4-chlorophenyl)indenyl}]hafnium,
(16) dichloro[1,1′-dimethylsilylenebis{2-n-propyl-4-(3-chloro-4-trimethylsilylphenyl)indenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(3-chloro-4-t-butylphenyl)indenyl}]hafnium,
(18) Dichloro[1,1′-dimethylgermylenebis{2-methyl-4-(2-fluoro-4-biphenyl)indenyl}]hafnium,
(19) dichloro[1,1′-dimethylgermylene bis{2-methyl-4-(4-t-butylphenyl)indenyl}]hafnium,
(20) Dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(4-chlorophenyl)indenyl}]hafnium.

Moreover, as a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are substituted azulenyl groups, the following structures can be exemplified.

[In the general formula (6), R ⁶¹ and R ⁶² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ⁶³ and R ⁶⁴ are each independently a halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ⁶¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. Also represents a germylene group, M ⁶¹ represents zirconium or hafnium, X ⁶¹ and Y ⁶¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents a silyl group having a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]

R ⁶¹ and R ⁶² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like, preferably methyl. , Ethyl and n-propyl.

Further, R ⁶³ and R ⁶⁴ each independently have 6 to 30 carbon atoms, preferably 6 to 30 carbon atoms, which may contain a halogen atom, silicon, or a plurality of hetero elements selected from these. 24 aryl groups. Examples of such an aryl group include a phenyl group which may have a substituent, a biphenylyl group and a naphthyl group. Preferred examples are phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4-(2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like can be mentioned.

The above X ⁶¹ and Y ⁶¹ are auxiliary ligands, and react with the component [B] to generate an active metallocene having an olefin polymerization ability. Therefore, as long as this object is achieved, X ⁶¹ and Y ⁶¹ are not limited in the kind of ligand, and each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and the like. Show.

Q ⁶¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings and bridges two conjugated five-membered ring ligands through a carbon atom having 1 or 2 carbon atoms; It represents either a silylene group which may have a hydrocarbon group of 1 to 20 or a germylene group which may have a hydrocarbon group of 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ⁶¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc.; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diene. An alkylsilylene group such as (n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, an (alkyl)(aryl)silylene group such as methyl(phenyl)silylene; an arylsilylene group such as diphenylsilylene; Alkyloligosilylene group such as tetramethyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl) (aryl) Germylene group; arylgermylene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.
Further, M ⁶¹ is zirconium or hafnium, preferably hafnium.

The following can be mentioned as non-limiting examples of the metallocene compound represented by the above general formula (6).
However, only the representative exemplified compounds are described, avoiding many complicated examples. Further, although a compound in which the central metal is hafnium is described, it is obvious that the same zirconium compound can be used and various ligands, bridging groups or auxiliary ligands can be optionally used.
(1) dichloro{1,1′-dimethylsilylenebis(2-methyl-4-phenyl-4-hydroazulenyl)}hafnium,
(2) dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(3) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(4) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(5) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(6) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-methyl-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(7) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(8) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(9) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}]hafnium,
(10) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-naphthyl)-4-hydroazulenyl}]hafnium,
(11) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium,
(12) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(13) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-chloro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(14) dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(9-phenanthryl)-4-hydroazulenyl}]hafnium,
(15) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(16) dichloro[1,1′-dimethylsilylenebis{2-n-propyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(17) dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(18) dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium,
(19) dichloro[1,1′-dimethylgermylenebis{2-methyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(20) dichloro[1,1′-dimethylgermylene bis{2-methyl-4-(4-t-butylphenyl)-4-hydroazulenyl}]hafnium,
(21) dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium,
(22) dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium,
(23) dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl}]hafnium,
(24) dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(3,5-dichloro-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium, And so on.

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

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

As a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are substituted cyclopentadienyl groups, the following structures can be exemplified.

[In general formula (7), R ⁷¹ and R ⁷⁴ are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ⁷² and R ⁷⁵ are each independently 1 to 1 carbon atoms. 6 is a hydrocarbon group, and R ⁷³ and R ⁷⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. X ⁷¹ and Y ⁷¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an amino group or an alkylamino group having 1 to 20 carbon atoms, and Q ⁷¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, Represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ⁷¹ represents zirconium or hafnium. ]

R ^<71> and R ^<74> are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like, preferably methyl. , Ethyl and n-propyl, and particularly preferably a methyl group.
R ⁷² and R ⁷⁵ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably methyl. It is a base.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. Of these, methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl are preferable.
R ⁷³ and R ⁷⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly A methyl group is preferred.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. Of these, methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl are preferable.

In the above, X ⁷¹ and Y ⁷¹ are auxiliary ligands, which react with the component [B] to produce an active metallocene having olefin polymerization ability. To achieve this object, X ⁷¹ and Y ⁷¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, It represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group or an alkylamino group having 1 to 20 carbon atoms.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group having 1 to 20 carbon atoms, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group.

In the above, Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings and bridges two conjugated five-membered ring ligands through a carbon atom having 1 or 2 carbon atoms. Represents a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁷¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc.; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene. An alkylsilylene group such as (n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, an (alkyl)(aryl)silylene group such as methyl(phenyl)silylene; an arylsilylene group such as diphenylsilylene; Alkyloligosilylene group such as tetramethyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl) (aryl) Germylene group; arylgermylene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

Among these compounds represented by the general formula (7), preferably,
(1) dichloro{dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)}hafnium,
(2) dichloro{diphenylsilylenebis(2,3,5-trimethylcyclopentadienyl)}hafnium,
(3) dichloro{dimethylgermylene bis(2,3,5-trimethylcyclopentadienyl)}hafnium,
(4) dichloro{dimethylsilylenebis(2,5-dimethyl-3-phenylcyclopentadienyl)}hafnium,
(5) dichloro{dimethylsilylenebis(2-ethyl-3-phenyl-5-methylcyclopentadienyl)}hafnium,
(6) dichloro{dimethylsilylenebis(2,3,5-triethylcyclopentadienyl)}hafnium,
(7) dichloro{dimethylsilylenebis(2,5-dimethyl-3-ethylcyclopentadienyl)}hafnium,
(8) dichloro{dimethylsilylenebis(2,3-dimethyl-5-ethylcyclopentadienyl)}hafnium,
(9) dichloro{dimethylsilylenebis(2,5-dimethyl-3-i-propylcyclopentadienyl)}hafnium,
(10) dichloro{dimethylsilylenebis(2,4-dimethylcyclopentadienyl)}hafnium,
More preferably, dichloro{dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)}hafnium, dichloro{diphenylsilylenebis(2,3,5-trimethylcyclopentadienyl)}hafnium, dichloro{dimethylgel Mylene bis(2,3,5-trimethylcyclopentadienyl)} hafnium, dichloro{dimethylsilylene bis(2,5-dimethyl-3-phenylcyclopentadienyl)} hafnium, dichloro{dimethylsilylene bis(2,4) -Dimethylcyclopentadienyl)} hafnium.

In addition, as a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are a cyclopentadienyl group and a fluorenyl group, the following structures can be exemplified.

In the general formula (8), R ⁸² is selected from a silyl group having a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and preferably methyl group, ethyl group, isopropyl group, t A butyl group and a trimethylsilyl group. R ⁸¹ , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, They may be the same or different and adjacent substituents R ^{85 to} R ⁸⁸ may be bonded to each other to form a ring.
Further, the above X ⁸¹ and Y ⁸¹ are auxiliary ligands and react with the component [B] to generate an active metallocene having an olefin polymerization ability. In order to achieve this object, X ⁸¹ and Y ⁸¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. And an alkylamide group, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms.

Further, Q ⁸¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two 5-membered rings and bridges two conjugated 5-membered ring ligands through a carbon atom having 1 or 2 carbon atoms. Represents a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁸¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di( alkylsilylene groups such as n-propyl)silylene, di(i-propyl)silylene and di(cyclohexyl)silylene, (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; arylsilylene groups such as diphenylsilylene; tetra Alkyloligosilylene group such as methyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl)(aryl)germylene Group; an arylgermylene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.
Further, M ⁸¹ is zirconium or hafnium, preferably hafnium.

Among these compounds represented by the general formula (8), preferably,
(1) dichlorodimethylmethylene(3-i-propylcyclopentadienyl)fluorenyl)zirconium,
(2) dichlorodimethylmethylene (3-t-butylcyclopentadienyl)fluorenyl)zirconium,
(3) dichlorodimethylmethylene(3-trimethylsilylcyclopentadienyl)fluorenyl)zirconium,
(4) dichlorodimethylmethylene (3-(t-butyldimethylsilyl)cyclopentadienyl)fluorenyl)zirconium,
(5) dichlorodimethylmethylene(3-i-propyl-5-methylcyclopentadienyl)fluorenyl)zirconium,
(6) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl)fluorenyl)zirconium,
(7) dichlorodimethylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)fluorenyl)zirconium,
(8) dichlorodimethylmethylene(3-(t-butyldimethylsilyl)-5-methylcyclopentadienyl)fluorenyl)zirconium,
(9) dichlorodimethylmethylene(3-i-propyl-5-ethylcyclopentadienyl)fluorenyl)zirconium,
(10) dichlorodimethylmethylene (3-t-butyl-5-ethylcyclopentadienyl)fluorenyl)zirconium,
(11) dichlorodimethylmethylene(3-trimethylsilyl-5-ethylcyclopentadienyl)fluorenyl)zirconium,
(12) dichlorodimethylmethylene(3-(t-butyldimethylsilyl)-5-ethylcyclopentadienyl)fluorenyl)zirconium,
(13) Dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium,
(14) Dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium,
(15) Dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium,
(16) Dichlorodimethylmethylene (3-(t-butyldimethylsilyl)-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium,
(17) dichlorodimethylmethylene(3-i-propyl-5-methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium,
(18) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium,
(19) dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium,
(20) Dichlorodimethylmethylene (3-(t-butyldimethylsilyl)-5-methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium,

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

When the component [A-2] having the above structure is selected, the component [A-1] having a different structure is selected.

(3) Component [B]
The component [B] is at least one selected from the following compound group.
[B-1] Supported aluminum oxy compound,
[B-2] An ionic compound or Lewis acid capable of reacting with the supported metallocene compounds [A-1] and [A-2] and converted into a cation, and a [B-3] ion. Exchangeable layered silicate.

(3-1) Component [B-1]
Specific examples of the aluminum oxy compound of the component [B-1] include compounds represented by the following general formula (9), (10) or (11).

In each of the above general formulas, R ⁹¹ , R ¹⁰¹ and R ¹¹¹ represent a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. Further, a plurality of R ⁹¹ , R ^101, and R ¹¹¹ may be the same or different. Moreover, p shows the integer of 0-40, preferably 2-30.
The compounds represented by the general formulas (9) and (10) are compounds also called alumoxane, and of these, methylalumoxane or methylisobutylalumoxane is preferable.
It is also possible to use a plurality of the alumoxanes in combination in each group and between each group. The alumoxane can be prepared under various known conditions.
In addition, the compound represented by the general formula (11) is 10:1 to 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and the following alkylboronic acid represented by the general formula (12). It can be obtained by a reaction of 1 (molar ratio).
In formulas (11) and (12), R ¹¹² and R ¹²¹ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group.

Here, the aluminum oxy compound is used by being supported on a carrier.
The carrier is not particularly limited in its elemental composition and compound composition, but a carrier composed of an inorganic or organic compound can be exemplified. Examples of the inorganic carrier include silica, alumina, silica-alumina magnesium chloride, activated carbon, and inorganic silicate. Alternatively, it may be a mixture thereof.
Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated carbonization such as styrene and divinylbenzene. A fine particle carrier of a porous polymer made of a polymer of hydrogen and the like can be mentioned. Alternatively, it may be a mixture thereof.
These carriers are usually 1 μm to 5 mm, preferably 5 μm to 1 mm, and more preferably 10 μm to 200 μm in particle diameter frequency distribution measured by a laser diffraction/scattering type particle size distribution meter. It is preferable that the particles are fine particles having a diameter.

(3-2) Component [B-2]
The ionic compound or Lewis acid of the component [B-2] reacts with the metallocene compounds [A-1] and [A-2] to convert [A-1] and [A-2] into cations. It is a possible compound.
As the ionic compound, a complex of a cation such as a carbonium cation and an ammonium cation with a cation of an organoboron compound such as triphenylboron, tris(3,5-difluorophenyl)boron and tris(pentafluorophenyl)boron. And the like.
Examples of the Lewis acid include various organic boron compounds such as tris(pentafluorophenyl)boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
Incidentally, some of the above Lewis acids are ions capable of reacting with [A-1] and [A-2] to convert [A-1] and [A-2] into cations. It can also be understood as a sex compound. Therefore, the compounds belonging to both the above-mentioned Lewis acid and ionic compound belong to either one.
Here, the ionic compound or Lewis acid is used by supporting it on a carrier.
The carrier is not particularly limited in its elemental composition and compound composition, but a fine particle carrier made of an inorganic or organic compound can be exemplified. Examples of the inorganic carrier include silica, alumina, silica-alumina magnesium chloride, activated carbon, and inorganic silicate. Alternatively, it may be a mixture thereof.
Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated carbonization such as styrene and divinylbenzene. A fine particle carrier of a porous polymer made of a polymer of hydrogen and the like can be mentioned. Alternatively, it may be a mixture thereof.
These carriers are usually 1 μm to 5 mm, preferably 5 μm to 1 mm, and more preferably 10 μm to 200 μm in particle diameter frequency distribution measured by a laser diffraction/scattering type particle size distribution meter. It is preferable that the particles are fine particles having a diameter.

(3-3) Component [B-3]
The component [B-3] is an ion-exchange layered silicate (hereinafter simply referred to as silicate).
In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and the contained ions are exchangeable. Say. Since most silicates are naturally produced mainly as the main components of clay minerals, impurities other than ion-exchange layered silicates (quartz, cristobalite, etc.) are often contained, but they are also included. But it's okay. Specific examples of the silicate include the following layered silicates described in "Clay Mineralogy" written by Haruo Shiramizu, Asakura Shoten (1995).
That is, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculites such as vermiculite, mica, illite, sericite, mica such as glauconite, attapulgite, sepiolite, palygorskite. , Bentonite, pyrophyllite, talc, chlorite, etc.

The silicate used as a raw material in the present invention is preferably a silicate whose main component silicate has a 2:1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of the interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as the main component of the interlayer cation is preferable from the viewpoint of being relatively easily and inexpensively available as an industrial raw material.
The silicate used in the present invention can be used as it is without any particular treatment, but it is preferably subjected to a chemical treatment. Here, as the chemical treatment, both a surface treatment for removing impurities adhering to the surface and a treatment for affecting the structure of clay can be used. Specific examples of the chemical treatment in the present invention include the following (a) acid treatment, (b) salt treatment, (c) alkali treatment, (d) organic substance treatment, and the like.

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

(B) Salt Treatment In the present invention, 40% or more, preferably 60% or more, of the cations of the exchangeable Group 1 metal contained in the ion-exchange layered silicate before being treated with salts are shown below. Ion exchange with a cation dissociated from the salt shown is preferred.

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

_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li _{3 PO 4, CaCl 2, CaSO} 4, CaC 2 O 4, Ca (NO 3) 2, Ca 3 (C 6 H 5 O 7) 2, MgCl 2, MgBr 2, MgSO 4, Mg (PO 4) 2, _{mg (ClO 4) 2, MgC} 2 O 4, mg (NO 3) 2, mg (OOCCH 3) 2, MgC 4 H 4 O 4 and the like _{and, Ti (OOCCH 3) 4,} Ti (CO 3) 2, Ti (NO ₃ ) ₄ , Ti(SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr(OOCCH ₃ ) ₄ , Zr(CO ₃ ) ₂ , Zr(NO ₃ ) ₄ , Zr(SO ₄ ) ₂ , ZrF ₄ , _{ZrCl 4, ZrOCl 2, ZrO (} NO 3) 2, ZrO (ClO 4) 2, ZrO (SO 4), HF (OOCCH 3) 4, HF (CO 3) 2, HF (NO 3) 4, HF (SO _{4) 2, HFOCl 2, HFF} 4, HFCl 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, VCl 4, VBr 3 , etc. _{and, Cr (CH 3 COCHCOCH 3)} 3, Cr ( _{OOCCH 3) 2 OH, Cr (} NO 3) 3, Cr (ClO 4) 3, CrPO 4, Cr 2 (SO 4) 3, CrO 2 Cl 2, CrF 3, CrCl 3, CrBr 3, CrI 3, Mn ( _{OOCCH 3) 2, Mn (CH} 3 COCHCOCH 3) 2, MnCO 3, Mn (NO 3) 2, MnO, Mn (ClO 4) 2, MnF 2, MnCl 2, Fe (OOCCH 3) 2, Fe (CH 3 COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe(NO ₃ ) ₃ , Fe(ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O _7, etc. , Co(OOCCH ₃ ) ₂ , Co(CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co(NO ₃ ) ₂ , CoC ₂ O ₄ , Co(ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni( _{NO 3) 2, NiC 2 O} 4, Ni (ClO 4) 2, NiSO 4, NiCl 2, NiBr 2 or the like _{and, Zn (OOCCH 3) 2,} Zn (CH 3 COCHCOCH 3) 2, ZnCO 3, Zn (NO ₃ ) ₂ , Zn(ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al _{2 (C 2 O 4) 3,} Al (CH 3 COCHCOCH 3) 3, Al (NO 3) 3, AlPO 4, GeCl 4, GeBr 4, GeI 4 , and the like.

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

(D) Organic substance treatment Further, examples of the organic substance used for the organic substance treatment include trimethylammonium, triethylammonium, N,N-dimethylanilinium, triphenylphosphonium and the like.
Furthermore, as the anion constituting the organic substance treating agent, in addition to the anion exemplified as the anion constituting the salt treating agent, for example, hexafluorophosphate, tetrafluoroborate, tetraphenylborate, etc. are exemplified. However, the present invention is not limited to these.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, these adsorbed water and interlayer water are preferably removed and used as the component [B].
The heat treatment method of the adsorbed water of the ion-exchange layered silicate and the interlayer water is not particularly limited, but it is desirable to select the conditions so that the interlayer water does not remain and the structure is not destroyed. The heating time is 0.5 hours or longer, preferably 1 hour or longer. At that time, the water content of the component [B] after removal is 3% by weight or less, when the water content when dehydrated for 2 hours under conditions of a temperature of 200° C. and a pressure of 1 mmHg is 0% by weight, preferably not more than 3% by weight. Is preferably 1% by weight or less.

As described above, in the present invention, as the component [B], particularly preferable one is an ion-exchange layered silicate having a water content of 3% by weight or less, which is obtained by performing salt treatment and/or acid treatment. Is.
The ion-exchange layered silicate is preferable because it can be treated with an organoaluminum compound described below before forming a catalyst or using it as a catalyst. The amount of the organoaluminum compound to be used per 1 g of the ion-exchange layered silicate is not limited, but is usually 20 mmol or less, preferably 0.5 mmol or more and 10 mmol or less. The treatment temperature and time are not limited, and the treatment temperature is usually 0° C. or higher and 70° C. or lower, and the treatment time is 10 minutes or longer and 3 hours or shorter. It is possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as the solvent used in the prepolymerization or slurry polymerization described later is used.

As the component [B], it is preferable to use spherical particles having an average particle diameter of 5 μm or more. As long as the particles have a spherical shape, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation or the like may be used.
The granulation method used here includes, for example, a stirring granulation method and a spray granulation method, but a commercially available product can also be used.
Further, at the time of granulation, an organic substance, an inorganic solvent, an inorganic salt or various binders may be used.

The spherical particles obtained as described above preferably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization step. In the case of such a particle strength, the effect of improving the particle property is effectively exhibited, particularly when prepolymerization is carried out.
Among the above-mentioned components [B], particularly preferable one is [B-3] ion-exchange layered silicate.

(4) Organoaluminum Compound The olefin polymerization catalyst of the present invention may contain an organoaluminum compound, if necessary.
The following general formula:
AlR ¹³¹ _q Z _3-q ... General formula (13)
Organoaluminum compounds represented by are preferred.
In the present invention, it goes without saying that the compounds represented by this formula can be used alone or in combination of two or more kinds. In this formula (13), R ¹³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen atom, a hydrogen atom, an alkoxy group or an amino group. q is a number greater than 0 and up to 3. R ¹³¹ is preferably an alkyl group, and Z is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and a carbon atom of 1 when it is an amino group. -8 amino groups are preferred.

Specific examples of preferred organic aluminum compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl. Aluminum sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethylamide, diisobutyl aluminum hydride, diisobutyl aluminum chloride and the like can be mentioned.
Of these, trialkylaluminum and dialkylaluminum hydride with q=3 are preferable. More preferably, R ¹³¹ is trialkylaluminum having 1 to 8 carbon atoms.

In addition to the components [A-1], [A-2], [B] and the organoaluminum compound used as the case requires, the catalyst used in the present invention has a range that does not impair the object of the present invention. Polymers commonly used such as polyethylene and polypropylene, solids of inorganic oxides such as silica and titania may be added.

2. Preparation (Formation)/Preliminary Polymerization of Catalyst In the catalyst of the present invention, the above-mentioned components [A-1], [A-2] and component [B] are simultaneously or continuously in a (preliminary) polymerization tank, or It can be formed by contacting at once or multiple times.
When the components [A-1] and [A-2] and the component [B] are brought into contact with each other, the organoaluminum compound may be brought into contact with each other simultaneously or continuously, or once or plural times. In particular, in the component [A-1] or [A-2], when X ¹¹ and X ¹² or X ²¹ and X ²² are other than a hydrocarbon group having 1 to 20 carbon atoms, for example, a halogen group, organic It is preferable to use an aluminum compound.
The order of contact may be any combination that is purposeful, but the particularly preferable ones will be shown below for each component.
When an organoaluminum compound is used, before the components [A-1] and [A-2] are contacted with the component [B], the components [A-1] and [A-2] or the component [B] are used. ], or both the components [A-1], [A-2] and the component [B] are contacted with an organoaluminum compound, or the components [A-1], [A-2] and the component [B]. ] And the organoaluminum compound may be brought into contact with the same at the same time, or the organoaluminum compound may be brought into contact after bringing the components [A-1] and [A-2] into contact with the component [B]. However, the method is preferably such that the components [A-1] and [A-2] are brought into contact with any one of the organoaluminum compounds before being brought into contact with the component [B].
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but it is preferably carried out between -20°C and 150°C.
After contacting each component, it is possible to wash with an aliphatic hydrocarbon or aromatic hydrocarbon solvent.

The amounts of the components [A-1], [A-2], [B] and the organoaluminum compound used in the present invention are arbitrary. For example, the total amount of the components [A-1] and [A-2] used with respect to the component [B] is preferably 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the component [B]. Is the range.
Moreover, the amount of the organoaluminum compound with respect to the components [A-1] and [A-2] is preferably 0.01 to 5×10 ⁶ , and particularly preferably 0.1 to 1×10 ⁶ in terms of a transition metal molar ratio. ^It is preferably within the range of ⁴ .

Regarding the ratio of the molar amount of [A-1] to the total molar amount of the components [A-1] and [A-2], the component [A-1] and the component [A-2] used in the present invention are as follows. It is preferably 0.20 or more and 0.99 or less. By changing this ratio, it is possible to adjust the balance between the melt tension of the polymer and the catalytic activity as the basic performance of the polymerization catalyst.
For example, in order to produce a polymer having a reduced branching index (g′) by further increasing the branching amount, it is preferably 0.30 or more, more preferably 0.40 or more, still more preferably 0.50 or more. And particularly preferably 0.70 or more. Further, in order to obtain a polymer with high catalytic activity, it is preferably 0.95 or less, more preferably 0.93 or less, still more preferably 0.90 or less, and particularly preferably 0.85 or less.
Further, by using the component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the hydrogen amount.

The catalyst according to the present invention is preferable since it is possible to carry out a preliminary polymerization, which comprises contacting it with an olefin and polymerizing it in a small amount.
By carrying out the prepolymerization, the two complexes are activated before the main polymerization and fixed on the component [B], and in addition to the effect that the prepolymerized polymer covers the active sites, By fixing the space around the point, that is, by fixing it chemically and physically, it has the effect of suppressing the deterioration of the catalyst.
Further, by performing the preliminary polymerization, it is possible to improve the melt tension and suppress the generation of gel when the main polymerization is performed. The reason for this is considered to be that the branched component can be uniformly distributed among the polymer particles when the main polymerization is carried out.
The amount of the polymer to be pre-polymerized is preferably 0.1 or more, more preferably 0.3 or more, in weight ratio with respect to the component [B], and preferably 10 or less, more preferably from the viewpoint of economy and handling. Is 5 or less. Here, the weight ratio of the polymer to the component [B] may be expressed as a prepolymerization ratio.

The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Examples thereof include styrene, and propylene is preferable.
The olefin feed method may be any method such as a feed method for maintaining the olefin in the reaction tank at a constant rate or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of -20°C to 100°C and 5 minutes to 24 hours, respectively.
Further, it is preferable to wash after the completion of the prepolymerization.

3. Drying of Catalyst In the present invention, the olefin polymerization catalyst obtained above can be dried under reduced pressure in advance before storage. The solvent component can be distilled off by drying. By this step, the olefin polymerization catalyst changes from a so-called mud state to a powder state.
Further, to the olefin polymerization catalyst used in the present invention, it is preferable to add or add an organoaluminum compound as a component [C] in order to suppress catalyst deterioration during storage, and then perform vacuum drying. ..
By adding the organoaluminum compound of the component [C], the organoaluminum compound component of the component [C] is present around the active site, so that it acts as a scavenger against a trace amount of poisonous substances from the outside. By carrying out in a polymerization catalyst, deterioration of the catalyst can be suppressed. At this time, by drying under reduced pressure, the added organoaluminum compound acts directly on the active site and is fixed around the active site before causing side reactions such as decomposition reaction of the active site. It is possible to save points efficiently.
Among the organoaluminum compounds listed above, triisobutylaluminum and triethylaluminum are particularly preferred as the organoaluminum compound of the component [C] used during storage.
It is preferable that the organoaluminum compound of the component [C] is added or added so that the condition is 1 to 70 mols based on 1 mol of the total of the components [A-1] and [A-2].
The mechanism of suppressing the deterioration of the above-mentioned catalyst of the organoaluminum compound of the component [C] is the same for the catalyst for olefin polymerization not used in the present invention and the catalyst for prepolymerized olefin polymerization. I think it is a mechanism.
On the other hand, if the amount of residual solvent is large after the drying step, the probability that the complex [A-1] or [A-2] in the catalyst component and the organoaluminum compound will contact with the residual solvent as a medium even after the drying step is increased. It has been found that the amount of the compound increases and the deterioration reaction of the complex due to the organoaluminum compound easily proceeds.
Therefore, in order to prevent the added organoaluminum compound from directly acting on the active site and excessively promoting a side reaction such as a decomposition reaction of the active site, the residual solvent amount of the olefin polymerization catalyst of the present invention is 0. The content is preferably 0.50 wt% or less, more preferably 0.45 wt% or less, and further preferably 0.40 wt% or less.
Quantitative Method of Residual Solvent Component Into a well-dried flask in advance, about 20 to 50 g of the polyolefin catalyst component after the drying step was accurately weighed and introduced, and the flask was evacuated at 60° C. and dried for 4 hours. , Measure the weight of the polyolefin catalyst component.
The residual solvent amount (wt%) is calculated by the following formula.
Amount of residual solvent (wt%)=([weight of catalyst before pressure reduction]−[weight of catalyst after pressure reduction])/[weight of catalyst before pressure reduction]×100

4. Storage of Catalyst In the present invention, the olefin polymerization catalyst obtained above is stored at a controlled temperature of 1° C. or higher and 20° C. or lower.
In the method for producing an olefin polymer of the present invention, by storing the olefin polymerization catalyst at a controlled temperature of 1° C. or higher and 20° C. or lower, a change in the performance of the obtained polymer, particularly a decrease in melt tension occurs. Without, a polymer can be produced.

The olefin polymerization catalyst obtained above is preferably stored under a pressure of 0.01 MPaG to 0.05 MPaG using an inert gas in a pressure vessel. This is because impurities such as water and oxygen are not mixed in the pressure container by storing at a pressure higher than atmospheric pressure.
Further, it is preferable to use nitrogen gas as the inert gas, and for the nitrogen gas used at this time, for example, high-purity nitrogen having a purity of 99.999 vol% or more is used, and further, moisture removed through a molecular sieve or the like. Preference is given to using.

Usually, the deterioration of the catalyst refers to decomposition of active sites and the like that cause a decrease in polymerization activity. In particular, in a solid catalyst supporting a transition metal complex, the decomposition of the transition metal complex causes a decrease in the number of active sites, which causes a decrease in activity.
In the case of a solid catalyst carrying a single transition metal complex, the main problem is a decrease in activity due to a decrease in the number of active sites, so if the decomposition of the transition metal complex is in a slow range, storage conditions can be arbitrarily set. I was able to set it.
Further, in a multi-way catalyst using a plurality of transition metal complexes as disclosed in Japanese Patent Publication No. 2010-509484 of Patent Document 8, since the temperature dependence of the decomposition reaction of each transition metal complex is different, it is uniform. As a result, when the deterioration proceeds without being decomposed, the expected activity of each transition metal complex changes. As a result, when the catalyst was stored for a long period of time and polymerized under the same conditions as the catalyst that was just produced, not only the deterioration of the activity but also the change of the molecular weight distribution, when the comonomer was used, , Appears as a phenomenon that the composition distribution changes.
When such a deterioration phenomenon appears, when operating, the fluidity can be improved by adjusting the hydrogen concentration and the comonomer amount by utilizing the activation by hydrogen and comonomer. It is possible to make adjustments and prevent deterioration of quality.

However, also in the case of a multi-way catalyst using a plurality of transition metal complexes, in the case of a multi-way catalyst in which one complex interacts with the other complex to exhibit a certain property, for example, a macromer is generated from one side. In the case of a multi-way catalyst system in which another complex in the vicinity is copolymerized, the primary structure such as the amount of long-chain branching or the distribution of branching changes due to the difference in the deactivation of each complex, and the melt tension Causes deterioration of primary physical properties.
This leads to not only productivity but also loss due to quality change in the case of industrial production.
Among the multi-way catalysts, in particular, when a metallocene compound containing a hetero atom in one of them is used, the unshared electron pair of the hetero atom is coordinated to the other active site to form an active site. There is a mechanism of degeneration of the metallocene compound and a mechanism of deactivating the metallocene compound after the unshared electron pair of the heteroatom is coordinated to the organoaluminum compound component.
Therefore, in the present invention, when a two-way catalyst containing a complex containing a hetero atom is used, the storage temperature is controlled to be in the range of 1° C. or higher and 20° C. or lower, and storage is industrially conducted. It has been found that not only does it not cause a decrease in activity, but also a decrease in quality can be prevented.
When the storage temperature of the present invention is deviated and the product is stored for a few days at a temperature exceeding 20° C., which is a condition for storage at atmospheric temperature in summer, the metallocene compound containing a hetero atom as described above and the metallocene not containing it are contained. Non-uniform deactivation occurs with the compound, which also affects the active site ratio of the special macromer copolymerization, causing a decrease in the melt tension due to a decrease in the long chain branching ratio.

Therefore, it is necessary to control the storage temperature of the two-way catalyst containing the metallocene compound [A-1] containing a hetero atom of the present invention within the range of 20° C. or lower.
On the other hand, if the temperature is lower than 1°C, it is not economically preferable, and not only is it unfavorable, but also when stored for a long period of time, the above-mentioned unshared electron pair possessed by a hetero atom is distributed to the organoaluminum compound component. Since the decomposition reaction accompanied by deactivation due to the coordination and the reaction in which the unshared electron pair of the heteroatom coordinates to the other complex alters the active site, the temperature dependence is different. It is conceivable that a difference occurs in the rate of reaction progress, and as a result, the long-chain branching ratio decreases, causing a decrease in melt tension.
Therefore, in the binary catalyst containing the metallocene compound [A-1] containing a hetero atom of the present invention, it is necessary to control the storage temperature in the range of 1°C or higher.
As shown in this example, it was shown that, when stored at 10° C. or higher for a specific number of days, there was no deterioration in performance when stored for a long period of time. It has been found that it is possible to obtain a polymer when polymerizing using a catalyst stored in such a state without lowering the performance such as melt tension.
Therefore, it has been found that it is possible to control the temperature to preferably 10° C. or higher and 20° C. or lower in consideration of economical efficiency and the like.
In addition, by storing the catalyst of the present invention at a controlled temperature in this range, the performance of the catalyst deteriorates in a range of more than 10 days, more than 2 years, and up to about 800 days immediately after the catalyst is manufactured. In particular, it is possible to produce a polymer in which a long chain branch is introduced without causing the above phenomenon.
At the present time, as shown in the examples, it has been confirmed that the melt tension does not decrease in the range up to 800 days (2.2 years).

5. Use of Catalyst/Olefin Polymerization As for the polymerization mode, the olefin polymerization catalyst containing the above-mentioned component [A-1], component [A-2], component [B] and optionally an organoaluminum compound is in efficient contact with the monomer. Then, any style can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a monomer itself (for example, propylene) as a solvent without substantially using an inert solvent, a solution polymerization method or substantially without using a liquid solvent A vapor phase method or the like in which each monomer is kept in a gaseous state can be adopted. Further, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, it is also possible to carry out multi-stage polymerization of two or more stages.

In the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or as a mixture as a polymerization solvent.
The polymerization temperature is 0°C or higher and 150°C or lower. Especially when bulk polymerization is used, the temperature is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 80°C or lower, more preferably 75°C or lower.
Further, when using gas phase polymerization, the temperature is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 100°C or lower, more preferably 90°C or lower.

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

Further, as a molecular weight regulator, and for the purpose of improving the activity, hydrogen is supplementarily used in a molar ratio of 1.0×10 ⁻⁶ to 1.0×10 ⁻² with respect to the monomer. be able to.
Further, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias toward the high molecular weight side of the molecular weight distribution, very high molecular weight component, branching (amount, length, The distribution) can be controlled, and thereby the melt physical properties such as strain hardening degree, melt tension and melt spreadability can be controlled.
The olefin as a monomer that can be used in the present invention is an α-olefin having 2 to 20 carbon atoms. Examples of the olefin polymer include a homopolymer of a single monomer and a copolymer between two or more kinds of monomers.
Further, the olefin polymerization catalyst obtained from the method for producing an olefin polymerization catalyst according to the present invention is suitable for homopolymerization of propylene and copolymerization of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene. Can be used.

Further, in addition to the propylene monomer, copolymerization using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer may be performed. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and it is possible to use a plurality of types of the above comonomer. Specifically, it is ethylene, 1-butene, 1-hexene, 1-octene or 4-methyl-1-pentene.
Among them, ethylene is preferably used in an amount of 5 mol% or less in order to obtain the propylene polymer according to the present invention in a well-balanced melt property and catalytic activity. In particular, in order to obtain a polymer having high rigidity, ethylene is preferably used so that the ethylene content in the polymer is 1 mol% or less, and more preferably propylene homopolymerization.

6. Physical Properties of Olefin Polymer The olefin polymer obtained by the production method of the present invention is characterized in that the branching index (g′) is 0.95 or less at a molecular weight (M) of 1,000,000, and further, It is preferably 0.90 or less.

[Branch structure analysis by 3D-GPC]
In this specification, 3D-GPC refers to a GPC device to which three detectors are connected. Such three detectors are a differential refractometer (RI), a viscosity detector (Viscometer) and a multi-angle laser light scattering detector (MALLS).
An Alliance GPCV2000 manufactured by Waters was used as a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer).
Also, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) Wyatt Technology DAWN-E was used.
The detector was connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (antioxidant Irganox 1076 added at a concentration of 0.5 mg/mL). The flow rate is 1 mL/min. As a column, two Tohso GMHHR-H(S)HTs were connected and used. The temperature of the column, sample injection part and each detector is 140°C. The sample concentration was 1 mg/mL. The injection volume (sample loop volume) is 0.2175 mL.
In order to obtain the absolute molecular weight (M) obtained from MALLS, the radius of gyration (Rg) and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation was performed with reference to the following documents.

References:
1. Developments in polymer characterisation, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4. Macromolecules, 33, 6945-6952 (2000).

[Calculation of branching index (g')]
The branching index (g′) is defined as a ratio (ηbranch/ηlin) of an intrinsic viscosity (ηbranch) obtained by measuring a sample with the Viscometer and an intrinsic viscosity (ηlin) separately obtained by measuring a linear polymer. ,calculate.
When a long-chain branch is introduced into a polymer molecule, the radius of gyration becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of gyration becomes smaller, the ratio of the intrinsic viscosity (ηbranch) of the branched polymer to the intrinsic viscosity (ηlin) of the linear polymer having the same molecular weight (ηbranch/ηlin) as the long-chain branch is introduced. Is getting smaller.
Therefore, when the branching index (g′=ηbranch/ηlin) becomes a value smaller than 1, it means that the branch is introduced, and as the value becomes smaller, the number of long-chain branches introduced increases. It means to do.

[Measurement of melt tension (MT)]
In the olefin polymer according to the present invention, the melt tension (MT) is preferably 5 g or more.
The method for measuring the melt tension (MT) will be described.
Using Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the resin is extruded in a string shape under the following conditions, and the tension detected by the pulley when wound on a roller is defined as the melt tension (MT).
Capillary: Diameter 2.1 mm
Cylinder diameter: 9.6 mm
Cylinder extrusion speed: 10 mm/min Winding speed: 4.0 m/min Temperature: 190°C
Here, the larger the value of MT, the higher the melt tension.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

1. Synthesis of catalyst (preliminary polymerization catalyst) [Synthesis example 1 of catalyst component [A-1]]:
(1) Synthesis of dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium: (Component [A-1] (Synthesis of complex 1)):
The synthesis of rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium is described in JP2012-149160A. Was carried out in the same manner as the method described in Synthesis Example 1 of.

[Synthesis example 2 of catalyst component [A-2]]:
(2) Synthesis of rac-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium: (Synthesis of component [A-2] (complex 2) ):
The synthesis of rac-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium was carried out by the method described in Example 7 of JP-A No. 11-240909. It carried out similarly to.

[Synthesis Example of Catalyst Component [B]]
(3) Chemical treatment of ion-exchange layered silicate:
96% sulfuric acid (668 g) was added to 2264 g of distilled water in a separable flask, and then 400 g of montmorillonite (Benclay SL manufactured by Mizusawa Chemical Co., Ltd.: average particle size 19 μm) was added as a layered silicate. The slurry was heated at 90°C for 210 minutes. This reaction slurry was added to 4000 g of distilled water and then filtered to obtain 810 g of a cake-like solid.
Next, 432 g of lithium sulfate and 1924 g of distilled water were added to a separable flask to prepare a lithium sulfate aqueous solution, and the whole amount of the cake-like solid was charged. This slurry was reacted at room temperature for 120 minutes. 4000 g of distilled water was added to this slurry and then filtered to obtain a cake-like solid. The operation of adding 4000 g of distilled water to the cake-like solid and filtering was repeated, and the slurry was washed until the pH became 5 to 6 and filtered to obtain 760 g of cake-like solid.
220 g of chemically treated montmorillonite was obtained by predrying the obtained solid at 100° C. for one day under a nitrogen stream, removing coarse particles of 53 μm or more, and further drying under reduced pressure at 200° C. for 2 hours.
The composition of this chemically treated montmorillonite was: Al: 6.45% by weight, Si: 38.30% by weight, Mg: 0.98% by weight, Fe: 1.88% by weight, Li: 0.16% by weight, It was Al/Si=0.175 [mol/mol].

(4) Catalyst preparation and prepolymerization:
In a three-necked flask (volume 1 L), 10 g of the chemically treated montmorillonite obtained above was put, heptane (66 mL) was added to make a slurry, and triisobutylaluminum (25 mmol: heptane solution having a concentration of 143 mg/mL was added to the flask). 0.0 mL) was added and the mixture was stirred for 1 hour, then washed with heptane until the residual liquid ratio became 1/100, and the total volume was adjusted to 50 mL.
In another flask (volume 200 mL), rac-dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl) prepared in Synthesis Example 1 of the catalyst component [A-1] was prepared. )-4-(4-i-Propylphenyl)indenyl}]hafnium (105 μmol) was dissolved in toluene (21 mL) to prepare solution 1.
Furthermore, in another flask (volume: 200 mL), rac-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl) prepared in Synthesis Example 2 of the catalyst component [A-2] was prepared. )-4-Hydroazurenyl}]hafnium (45 μmol) was dissolved in toluene (9 mL) to prepare solution 2.

Triisobutylaluminum (0.42 mmol: 0.6 mL of 143 mg/mL heptane solution) was added to a 1 L flask containing the chemically treated montmorillonite, then the above solution 1 (21 mL) was added and stirred for 20 minutes at room temperature. did.
Then, after further adding triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg/mL), the above solution 2 was added, and the mixture was stirred at room temperature for 1 hour.
Then, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After setting the internal temperature of the autoclave to 40° C., propylene was fed at a rate of 5 g/hour to carry out preliminary polymerization while maintaining 40° C. for 4 hours. Then, the propylene feed was stopped and the residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg/mL) was added to the remaining portion and stirred for 5 minutes.
The solid was dried under reduced pressure at 40° C. for 1 hour to obtain 26.1 g of a prepolymerized catalyst. The pre-polymerization ratio of the pre-polymerization catalyst (value obtained by dividing the amount of pre-polymerized polymer by the amount of solid catalyst) was 1.61, and as a result of elemental analysis, the Al/Hf molar ratio was 62 and the amount of residual solvent was 0.35% by weight. Met.

[Reference Example 1]
After the completion of the above prepolymerization step, the following polymerization was carried out using the prepolymerization catalyst that had been kept at room temperature for 7 days.

(polymerization)
The 3 L autoclave was dried in advance by circulating nitrogen under heating, then, the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (143 mg/mL), 24 NmL of hydrogen was introduced.
Then, after introducing 750 g of liquid propylene, the temperature was raised to 70°C.
Then, 50 mg of the above-mentioned prepolymerized catalyst, excluding the weight of the prepolymerized polymer, was pressure-fed to the polymerization tank with high-pressure argon to initiate polymerization. After holding at 70° C. for 1 hour, 5 ml of ethanol was press-fitted to terminate the polymerization. As a result, 127.5 g of a polymer was obtained.

[Reference Example 2]
The same polymerization as in Reference Example 1 was carried out except that 36 Nml of hydrogen was introduced. As a result, 175 g of a polymer was obtained.

[Example 1]
The prepolymerized catalyst synthesized above is stored in a refrigerated warehouse where the temperature is controlled in the range of 10°C to 20°C in a state of being pressurized to 0.03 MPaG with high-purity nitrogen passed through a molecular sieve in a pressure vessel, After storing for 800 days (about 2.2 years, two seasons of summer have passed), the same polymerization as in Reference Example 1 was performed.

[Comparative Example 1]
The same polymerization as in Reference Example 1 was carried out using a prepolymerization catalyst stored in a room without a temperature control facility for the same period as in Example 1 for 800 days (about 2.2 years and two seasons of summer). ..

Table 1 shows the evaluation results of Reference Examples 1 and 2, Example 1 and Comparative Example 1. Further, FIG. 1 shows the results of plotting MFR (unit: g/10 min) and MT (unit: g) of the obtained propylene homopolymer.

The evaluation sample was obtained by adding Irganox 1010 (manufactured by Ciba Specialty Chemicals) 1250 ppm, Irgafos 168 (manufactured by Ciba Specialty Chemicals) 1250 ppm, and calcium stearate (NOF Corporation) to the obtained polymer. 1250 ppm, and melt-kneaded using a KZW15TW-45MG same-direction meshing twin-screw extruder manufactured by Techno Bell Co., Ltd., and pelletized.

From Table 1 and FIG. 1, in the method for producing an olefin polymer using the method for storing a catalyst according to the present invention (Example 1), although the number of days for storing the catalyst was 800 days, it was the same as Reference Example 1. It can be seen that it has the catalytic activity of and the performance of the obtained olefin polymer. On the other hand, in Comparative Example 1 using the catalyst stored at room temperature, it is found that the catalytic activity is inferior to that of Reference Example 1 and the performance of the obtained olefin polymer is also inferior.

In the method for producing an olefin polymer of the present invention, for example, by using the method for preserving a catalyst according to the present invention, an olefin (co)polymer can be produced with high activity even after 800 days have passed. It is possible and highly industrially applicable.

Claims (10)

An olefin polymerization catalyst containing the following components [A-1], [A-2] and [B] was produced, and the olefin polymerization catalyst was contacted with the olefin to produce a prepolymerized olefin polymerization catalyst. And then storing the prepolymerized olefin polymerization catalyst for 2 years or more at a controlled temperature of 1° C. or higher and 20° C. or lower, and polymerizing olefins using the stored olefin polymerization catalyst. A method for producing an olefin polymer, comprising:
Component [A-1]: A metallocene compound represented by the following general formula (1).
[In the general formula ^{(1), Z 11 is, - (E 12) (R} 13) m '(R 14) p' -, - O -, - S -, - NR 15 - or ^{-PR 16} - a represents ,
E ¹¹ and E ¹² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group,
R ¹¹ and R ¹³ are each independently a silyl group having a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. , A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or halogen Represents an amino group having a hydrocarbon group,
R ¹² and R ¹⁴ each independently represent a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5-membered ring or a 6-membered ring, and the heteroaromatic group The group group is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, a carbon group having 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a hydrogen group or a silyl group having a halogenated hydrocarbon group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. May be replaced with
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Represents a silyl group having
m and m′ represent 0 or an integer of 1 to 8,
In the case where Z ¹¹ is (E ¹² )(R ¹³ )m′(R ¹⁴ )p′, one or both of p and p′ are an integer of 1 to 8 and Z ¹¹ is —O—, −. S -, - ^{NR 15} - or ^{-PR 16} - in the case of, p is an integer of 0 or 1 to 8,
Q ¹¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. May represent a germylene group,
M ¹¹ represents titanium, zirconium or hafnium,
X ¹¹ and X ¹² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. It represents a silyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [A-2]: a metallocene compound represented by the following general formula (2).
[In the general formula (2), E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and each may have a substituent, The substituent is not a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in the 5- or 6-membered ring,
Q ²¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a good germylene group,
M ²¹ represents titanium, zirconium or hafnium,
X ²¹ and X ²² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. It represents a silyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ]
Component [B]: At least one selected from the following compound group.
[B-1] Supported aluminum oxy compound,
[B-2] An ionic compound or Lewis acid capable of reacting with the supported metallocene compounds [A-1] and [A-2] and converted into a cation, and a [B-3] ion. Exchangeable layered silicate. The method for producing an olefin polymer according to claim 1 , wherein the olefin polymerization catalyst dried under reduced pressure is stored in advance. The method for producing an olefin polymer according to claim 2 , wherein the residual solvent amount in the olefin polymerization catalyst dried under reduced pressure is 0.5 wt% or less. The olefin polymerization catalyst, with an inert gas at a pressure vessel according to any one of claims 1 to 3, characterized in that storing pressurized in the range of 0.01MPaG~0.05MPaG Process for producing olefin polymer. The said preservation|save is preserve|saved on condition that 1-70 mol of the following components [C] exist with respect to a total of 1 mol of a component [A-1] and a component [A-2]. process for producing an olefin polymer according to any one of 1-4.
Component [C]: Organoaluminum compound. Component [A-1] is a metallocene compound that forms a polymerization catalyst that forms an olefin macromer [however, when the olefin homopolymerization is carried out at 70° C. with a metallocene compound that forms a polymerization catalyst that forms an olefin macromer. In addition, it is a metallocene compound that forms a polymerization catalyst that produces a polymer having a terminal vinyl ratio (Rv) of 0.5 or more. Process for producing an olefin polymer according to any one of claims 1 to 5, characterized in that is a. M ¹¹ and M ²¹ are process for producing an olefin polymer according to any one of claims 1 to 6, characterized in that one or both are hafnium. Olefin polymer, olefin according to any one of claims 1 to 7, ten thousand molecular weight (M) is 100 (logM = 6) in the branching index (g ') is characterized in that 0.95 or less Method for producing polymer. Component [A-1] and at least one of the [A-2], process for producing an olefin polymer according to claim 1, characterized in that the metallocene compound represented by the following general formula (3).
[In the general formula (3), R ³¹ and R ³² are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or halogen. A silyl group having a hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms, or a silyl group having a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, having 1 to 1 carbon atoms An amino group having 20 hydrocarbon groups or halogenated hydrocarbon groups, or a monocyclic or polycyclic heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom in a 5- or 6-membered ring Yes,
R ³³ and R ³⁴ each independently represent a halogen atom or an aryl group having 6 to 16 carbon atoms which may contain silicon,
Q ³¹ has a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a good germylene group,
M ³¹ represents titanium, zirconium or hafnium,
X ³¹ and X ³² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. It represents a silyl group, an amino group or an alkylamino group having 1 to 20 carbon atoms. ] The olefin polymer is a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 12 carbon atoms (excluding 3), and the olefin polymer is any one of claims 1 to 8. A method for producing an olefin polymer.