JP6885451B2 - Method for producing olefin polymer - Google Patents

Description

The present invention relates to a method for producing an olefin polymer, and more particularly to a method for producing an olefin polymer, which can suppress a change in the performance of the obtained polymer even if the catalyst used for producing the olefin polymer is stored for a long period of time.

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

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

In a catalyst system that forms a polymer with long-chain branches by the macromer method as described above, there is a problem that the activity decreases as the catalyst deteriorates and deteriorates 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 describes a multi-peak catalyst system including a bisamide catalyst system and a non-bisamide catalyst system at a controlled temperature. Disclosed is a method of storing the polymer at (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 has been found that the multimodality of a polymer changes due to deterioration of a plurality of catalyst components at different rates, and a method of suppressing this has been shown.
However, the above suppression method merely focuses on the change in the molecular weight distribution of the polymer on the premise of a multimodal catalyst system, and when a catalyst system containing a plurality of transition metal compounds as catalyst components is used. , A method for suppressing a change in the performance of the polymer obtained by the macromer method has not yet been found.

Japanese Unexamined Patent Publication No. 2009-040959 Japanese Unexamined Patent Publication No. 2009-057542 JP-A-2009-108247 Japanese Unexamined Patent Publication No. 2011-144356 Japanese Unexamined Patent Publication No. 2010-196036 Japanese Patent Application Laid-Open No. 2001-525463 Special Table 2001-527589 Special Table 2010-509484

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

As a result of diligent research to achieve the above object, the present inventors have obtained a catalyst by storing the catalyst for a long period of time, particularly in a catalyst system in which a polymer having a long-chain branch is formed by the macromer method. As a result of examining the long-term storage of the catalyst in order to solve the problem that the performance of the obtained polymer changes due to deterioration and deterioration, by adopting a specific long-term storage method, a long period (2) It has been found that changes in the performance of the obtained polymer can be suppressed even by using a catalyst that has been stored for more than a year. The present invention has been completed based on these findings.

That is, according to the first invention of the present invention, an olefin polymerization catalyst containing the following components [A-1], [A-2], [B] and an organoaluminum compound is used as a component [A] with respect to the component [B]. The total amount of -1] and [A-2] used was 0.1 μmol to 1000 μmol with respect to 1 g of the component [B], and the amount of the organoaluminum compound with respect to the component [A-1] was 0. after producing at 01-5 × 10 ^6, and stored more than two years of the olefin polymerization catalyst at a controlled temperature to 20 ° C. less than 1 ° C., and by using the stored olefin polymerization catalyst, olefins Provided is a method for producing an olefin polymer, which comprises polymerizing.
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 independently cyclopentadienyl groups, indenyl groups, fluorenyl groups or azulenyl groups, and R ¹¹ and R ¹³ are independently halogen atoms and 1 to 20 carbon atoms, respectively. Hydrocarbon group or halogenated hydrocarbon group, silyl group having 1 to 20 carbon number hydrocarbon group or halogenated hydrocarbon group, silyl group having 1 to 20 carbon number hydrocarbon group or halogenated hydrocarbon group Represents 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, and R ¹² and R ¹⁴ are independent of each other. Then, 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 is represented, and the heteroaromatic group has a halogen atom and a carbon number of carbon atoms. 1 to 20 hydrocarbon groups or halogenated hydrocarbon groups, silyl groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a silyl group having a silyl group, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. ¹⁵ and R ¹⁶ independently have 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 an integer of 0 or 1-8, and p and p'when Z ¹¹ is (E ¹² ) (R ¹³ ) m'(R ¹⁴ ) p'. is one or both of the 1-8 ^{integer, Z 11} is -O -, - S -, - NR 15 - or ^{-PR 16} - in the case of the p is 0 or an integer from 1 to 8 , Q ¹¹ has a divalent hydrocarbon group, a hydrocarbon group silylene group have 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms May represent a gelmilene group, M ¹¹ represents titanium, zirconium or hafnium, and X ¹¹ and X ¹² are independently hydrogen atoms, halogen atoms, and 1 to 20 carbon atoms, respectively. Represents a hydrocarbon group or a halide 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 azurenyl group, and each may have a substituent, except that 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, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and represents M ^21. Represents titanium, zirconium or hafnium, and X ²¹ and X ²² independently have 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. 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 metallocene compounds [A-1] and [A-2] carried and converted into a cation, and [B-3] ion. Exchangeable layered silicate.

Further, according to the second invention of the present invention, there is provided a method for producing an olefin polymer according to the first invention, which comprises preserving a catalyst for olefin polymerization which has been dried under reduced pressure in advance.
Further, according to the third invention of the present invention, in the second invention, the production of the olefin polymer, which is characterized in that the amount of the residual solvent in the catalyst for olefin polymerization dried under reduced pressure is 0.5 wt% or less. The method is provided.
Further, according to the fourth invention of the present invention, in any one of the first to third inventions, the catalyst for olefin polymerization is in the range of 0.01 MPaG to 0.05 MPaG using an inert gas in a pressure vessel. Provided is a method for producing an olefin polymer, which comprises pressurizing and storing the olefin polymer.
Further, according to the fifth invention of the present invention, in any one of the first to fourth inventions, in the preservation, 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 comprises storing under conditions in which 1 to 70 moles are present with respect to moles.
Ingredient [C]: Organoaluminium compound.

According to the sixth invention of the present invention, in any one of the first to fifth inventions, the component [A-1] is a metallocene compound that forms a polymerization catalyst that produces an olefin macromer [provided that the olefin macromer is produced. The metallocene compound that forms a polymerization catalyst is a metallocene compound that forms 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. ], A method for producing an olefin polymer is provided.
Further, according to the seventh invention of the present invention, in any one of the first to sixth inventions, M ¹¹ and M ²¹ are described in a method for producing an olefin polymer, characterized in that one or both of them are hafnium. Provided.
Further, according to the eighth invention of the present invention, in any one of the first to seventh inventions, the olefin polymer has a branching index (g') of 0 at a molecular weight (M) of 1 million (log M = 6). Provided is a method for producing an olefin polymer, which is characterized by being .95 or less.

Further, according to the ninth invention of the present invention, in the first 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 independently halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups, and hydrocarbon groups or halogens having 1 to 20 carbon atoms, respectively. Cyril group having a hydrocarbon group, hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms having a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 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-membered ring or a 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, and Q ³¹ is a divalent hydrocarbon having 1 to 20 carbon atoms. It represents a hydrogen group, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and M ³¹ represents titanium or zirconium. Alternatively, it represents hafnium, and X ³¹ and X ³² independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group or halogen having 1 to 20 carbon atoms, respectively. Represents a silyl group having a hydrocarbon group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

Further, according to the tenth invention of the present invention, in any one of the first to seventh inventions, the olefin polymer is a propylene homopolymer or an α-olefin having propylene and 2 to 12 carbon atoms (excluding 3). Provided is a method for producing an olefin polymer, which is characterized by being 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, in a method for producing a polymer using a catalyst containing a plurality of transition metal compounds as catalyst components, a polymer obtained even if a catalyst stored for a long period of time is used. Performance change can be suppressed. In particular, the catalyst produces a polymer having a long-chain branch by polymerizing a monomer in one catalyst component to form a macromer, and in the other catalyst component by copolymerizing a monomer and a macromer. When the catalyst system is capable, the obtained polymer can stably develop a high melt tension.

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

Hereinafter, the present invention will be described in detail.
One of the catalysts for olefin polymerization according to the present invention is a catalyst for olefin polymerization containing the following components [A-1], [A-2] and [B], and the produced catalyst for olefin polymerization is used. It was stored for a long period of time at a controlled temperature of 1 ° C. or higher and 20 ° C. or lower.
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 the catalyst, and then prepolymerize the catalyst. The produced catalyst for olefin polymerization 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 polymerize an olefin using the catalyst stored for a long period of time to produce a polymer.
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 independently cyclopentadienyl groups, indenyl groups, fluorenyl groups or azurenyl groups, respectively.
R ¹¹ and R ¹³ are independently silyl groups having a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, respectively. , A hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group or halogen having 1 to 20 carbon atoms. Represents an amino group with a hydrocarbon group
R ¹² and R ¹⁴ 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, respectively. Group groups include halogen atoms, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, silyl groups having hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, and hydrocarbons having 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a silyl group having a hydrogen group or a halogenated hydrocarbon group, or an amino group having a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms. May be replaced with
R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, or hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, respectively. Represents a silyl group with
m and m'represent an integer of 0 or 1-8
When Z ¹¹ is (E ¹² ) (R ¹³ ) m'(R ¹⁴ ) p', one or both of p and p'are integers 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 is has a divalent hydrocarbon group, a hydrocarbon group silylene group have 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Represents a hydrocarbon group that may be
M ¹¹ represents titanium, zirconium or hafnium,
X ¹¹ and X ¹² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. 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 azurenyl group, and may have a substituent, respectively. 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.
Q ²¹ is have a divalent hydrocarbon group, a hydrocarbon group of a hydrocarbon group which may have a silylene group or a C1-20 having 1 to 20 carbon atoms having 1 to 20 carbon atoms Represents a good gelmilene group,
M ²¹ represents titanium, zirconium or hafnium,
Each of X ²¹ and X ²² independently contains a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. 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 metallocene compounds [A-1] and [A-2] carried and converted into a cation, and [B-3] ion. Exchangeable layered silicate.

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

1. 1. Catalyst component of catalyst for olefin polymerization It is essential that the catalyst for olefin polymerization according to the present invention contains at least the components [A-1], [A-2] and [B].

(1) Ingredient [A-1]
The component [A-1] is a metallocene compound having the structure of the general formula (1) described above, and is preferably a metallocene compound that forms a polymerization catalyst that produces an olefin macromer. The metallocene compound that forms the polymerization catalyst that produces the olefin macromer will be described later.
As the component [A-1], the following structure can be mentioned as one of the non-limiting preferable embodiments. 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 independently halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups, and hydrocarbon groups or halogens having 1 to 20 carbon atoms, respectively. Cyril group having a hydrocarbon group, hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms having a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms An amino group having 20 hydrocarbon groups or a halogenated hydrocarbon group, or 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. 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 of carbon atoms. A hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms or a silyl group having 1 to 20 hydrocarbon groups or a halogenated hydrocarbon group, or a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms. It may be substituted with an amino group having a group, and R ³³ and R ³⁴ are independently oxygenated in an aryl group having 6 to 20 carbon atoms or an aryl hydrocarbon group, or 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, and the heteroaromatic group is 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, or an amino group having a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group may be substituted. ³¹ and R ^{32 and R 33} and R ³⁴ do not become groups other than heteroaromatic groups at the same time, and Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon having 1 to 20 carbon atoms. Represents a silylene group which may have a hydrogen group or a gelmilene 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 independently hydrogen atoms, halogen atoms, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, silyl groups having hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, and aminos. Represents a group or an alkylamino group having 1 to 20 carbon atoms. ]

The above R ³¹ and R ³² are each independently preferably a heteroaromatic group, more preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group or a substituted. It is a 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, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group can be used. Examples 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.
Further, as R ³¹ and R ³² , a 2- (5-methyl) -frill group is particularly preferable. Further, ^{it is preferable that R 31} and R ³² are the same as each other.

The above R ³³ and R ³⁴ 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 heteroelements selected from these. As the aryl group, one or more hydrocarbon groups having 1 to 6 carbon atoms and a trialkylsilyl having 1 to 6 carbon atoms are placed on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. It may have a group, a halogen-containing hydrocarbon group having 1 to 6 carbon atoms as a substituent.
Further, R ³³ and R ³⁴ may be heterocyclic groups having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Such heterocyclic groups are preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, a substituted 2-furfuryl group, and more preferably a substituted 2-. It is a frilled 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 , preferably at least one is a phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di. It is a t-butylphenyl group, a 4-phenyl-phenyl group, a chlorophenyl group, a naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-i-propyl group, a 4-trimethylsilyl group, a 4-t-butylphenyl group. , 4-Chlorophenyl group. Further, ^{it is preferable that R 33} and R ³⁴ are the same as each other.

In addition, X ³¹ and X ³² are co-ligands that react with component [B] to produce active metallocenes capable of olefin polymerization. Therefore, as long as this purpose is achieved ^{, the types of ligands of X 31} and X ³² are not limited, and each of them independently has a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. , A silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group or an alkylamino group having 1 to 20 carbon atoms.
Here, in the present invention, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group having 1 to 20 carbon atoms. ..

Q ³¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two 5-membered rings. Indicates either a silylene group which may have a hydrocarbon group of 1 to 20 or a gelmilene group which may have a hydrocarbon group of 1 to 20 carbon atoms. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ³¹ include an alkylene group such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc .; a cycloalkylene group; an arylalkylene group such as diphenylmethylene; a silylene group; methylcilylene, dimethylsilylene, etc. Alkyl silylene groups such as diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; diphenyl silylene, etc. Arylcyrylene group; Alkylolixylylene group such as tetramethyldisyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) ) (Alyl) gelmilene group; aryl gelmilene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.
Further, a substituent other than ^{R 31} , R ³² , R ³³ , and R ³⁴ may be provided on the indene ring of the above general formula (3). In that case, it can have a substituent at the 5- or 6-position of the indene ring. Examples thereof 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, it is preferable to use an indacen skeleton.

Among the compounds represented by the general formula (3), the preferred 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'-dimethylgelmilenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(6) Dichloro [1,1'-dimethylgelmilenebis {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 dichloromethane,
(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) Dichloromethane [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(20) Dichloromethane [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(21) Dichloromethane [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthrill) -indenyl}] hafnium,
(22) Dichloromethane [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthrill) -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) Dichloromethane [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(26) Dichloromethane [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.

Of these, more preferred are dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylgel. Millenbis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {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, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-biphenylyl-indenyl}] hafnium.

Particularly preferred are dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] naphthium, 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.

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

[In the general formula (4), Cp represents a cyclopentadienyl group, M ⁴¹ is Ti, Zr, or Hf, and Q ⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon. It is a silylene group which may have a hydrocarbon group of 1 to 20 or ^{a gelmilene group which may have a hydrocarbon group of 1 to 20 carbons, and Z 41} is an amide group, a phosphide group and an oxygen. It is an atom, a sulfur atom, a phenyleneoxy group or an alkylidene group.
X ⁴¹ and X ⁴² represent σ covalent covalent covalent ligands, which may be the same or different, the sum of q and r is 0-2, L is a neutral Lewis base, and s. Is 0 to 2, and the sum of q, r, and s is 0 to 4. Note that q + r + 2 represents the oxidation number of the ^{central metal M 41.}
R ⁴¹ and R ⁴² independently have 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. It is an aryl group of ~ 18 or an aryl halide group having 6 to 18 carbon atoms, which may be the same or different from each other, and may form a 5 to 10-membered ring with both ^{R 41} and R ^{42 adjacent to each other.} The 10-membered ring may contain an unsaturated bond. m and p are 0 or integers 1-8. ]

In the above general formula (4), M ⁴¹ is Ti, Zr, or Hf, preferably Ti, or Hf, and more preferably Ti.
Q ⁴¹ is have a divalent hydrocarbon group, a hydrocarbon group of a hydrocarbon group which may have a silylene group or a C1-20 having 1 to 20 carbon atoms having 1 to 20 carbon atoms It is also a good gelmilene group, and specific examples thereof include a dimethylsilylene group, a diethylsilylene group, a di-i-propylsilylene group, a diphenylcilylene group, a methylphenylcilylene group, a methyl-i-propylsilylene group, and a dimethylgelmilene group. Diethylgermylene group, di-i-propylgermylene group, diphenylgelmylene group, methylphenylgelmylene group, methyl-i-propylgermylene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, 1 Examples thereof include a −phenylethylene group, a 1,2-diphenylethylene group, a silacyclobutane group, a silacyclopentane group, a 2,5-dimethylsilacyclopentane group, a silacyclohexane group, a silafluorene group and a phenylene group.
Of these, dimethylsilylene group, di-i-propylsilylene group, diphenylsilylene group, silacyclobutane group, silacyclopentane group, silacyclohexane group and phenylene group are preferable, and dimethylsilylene group and diphenylsilylene are particularly preferable. The group is 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 or an oxygen atom, and most preferably an amide group.
X ⁴¹ and X ⁴² represent σ covalent covalent covalent ligands, which may be the same or different, and are not particularly limited, but preferred X ⁴¹ and X ⁴² are halogen atoms and hydrocarbon groups having 1 to 20 carbon atoms. , Substituent amino group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, 1 carbon number. Examples thereof include ~ 20 halogen-containing hydrocarbon groups. X ⁴¹ and X ⁴² may have a crosslinked structure.
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, which are preferable. Are ethers, amines and dienes, and the most preferable are ethers and dienes.

R ⁴¹ and R ⁴² independently have 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. It is an aryl group of ~ 18 or an aryl halide group having 6 to 18 carbon atoms, which may be the same or different from each other, and may form a 5 to 10-membered ring with both ^{R 41} and R ^{42 adjacent to each other.} 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, and 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, cyclooctyl group and the like.
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 atom-containing alkyl group having 1 to 8 carbon atoms has 1 to 8 carbon atoms. A halogen atom is substituted with a hydrogen atom on the skeleton of the alkyl group of 8.
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 Fluorohexyl groups, 8-fluorooctyl groups, 8,8,8-trifluorooctyl groups and the like can be mentioned.

Further, the silicon-containing alkyl group having 1 to 20 carbon atoms is one in which a silicon atom is substituted with a carbon atom on the skeleton of the alkyl group. Specific examples thereof 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 a phenyl group, a methylphenyl group, an n-propylphenyl group, an i-propylphenyl group, an n-butylphenyl group, an i-butylphenyl group and an 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 aryl halide group having 6 to 18 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an aryl halide group having 6 to 18 carbon atoms is an aryl having 6 to 18 carbon atoms. A halogen atom is replaced with a hydrogen atom on the skeleton of the group.
Specific examples include a pentafluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a perfluoronaphthyl group, and a perfluorobiphenyl group.
^{Also, R 41} and ^{R 42,} may form a 5-10 membered ring with both ^{R 41, R 42} adjacent, 5-10 membered ring may form an unsaturated bond. Specific examples of the cycloalkazienyl ring formed by forming a ring of R ⁴¹ and R ⁴² include an indenyl ring, a benzoindenyl ring, a tetrahydroindenyl ring, and an azulenyl ring.

Among the compounds represented by the general formula (4), the preferred compounds are specifically exemplified below.
(1) Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(2) Dimethylsilyl (tetramethylcyclopentadienyl) (cyclohexyl-amide) titanium dichloride,
(3) Dimethylsilyl (tetramethylcyclopentadienyl) (1-adamantylamide) titanium dichloride,
(4) Dimethylsilyl (tetramethylcyclopentadienyl) (t-butylamide) titanium dichloride,
(5) Dimethylsilyl (tetramethylcyclopentadienyl) (s-butylamide) titanium dichloride,
(6) Dimethylsilyl (tetramethylcyclopentadienyl) (n-butyramide) titanium dichloride,
(7) Dimethylsilyl (tetramethylcyclopentadienyl) (exo-2-norbornylamide) titanium dichloride,
(8) Diethylsilyl (tetramethylcyclopentadienyl) (cyclododecyl-amide) titanium dichloride,
(9) Diethylsilyl (tetramethylcyclopentadienyl) (exo-2-norbornylamide) titanium dichloride,
(10) Diethylsilyl (tetramethylcyclopentadienyl) (cyclohexylamide) titanium dichloride,
(11) Diethylsilyl (tetramethylcyclopentadienyl) (1-adamantylamide) titanium dichloride,
(12) Methylene (tetramethylcyclopentadienyl) (cyclododecyl-amide) titanium dichloride,
(13) Methylene (tetramethylcyclopentadienyl) (exo-2-norbornylamide) titanium dichloride,
(14) Methylene (tetramethylcyclopentadienyl) (cyclohexylamide) titanium dichloride,
(15) Methylene (tetramethylcyclopentadienyl) (1-adamantylamide) titanium dichloride,
(16) Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecyl-amide) titanium dimethyl,
(17) Dimethylsilyl (Tetramethylcyclopentadienyl) (Exo-2-norbornylamide) Titaniumdimethyl,
(18) Dimethylsilyl (tetramethylcyclopentadienyl) (cyclohexyl-amide) titanium dimethyl,
(19) Dimethylsilyl (Tetramethylcyclopentadienyl) (1-adamantylamide) Titaniumdimethyl,
(20) Dimethylsilyl (2,5-dimethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,

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

The most preferred compounds are:
Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (cyclohexyl-amide) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-adamantyl) Amide) Titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (exo-2-norbornylamide) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dimethyl, dimethylsilyl (tetra) Methylcyclopentadienyl) (cyclohexyl-amide) titanium dimethyl, dimethylsilyl (tetramethylcyclopentadienyl) (1-adamantylamide) titanium dimethyl, and dimethylsilyl (tetramethylcyclopentadienyl) (exo-2-nor) Bornylamide) Titanium dimethyl.

As described above, component [A-1] is preferably a metallocene compound that forms a polymerization catalyst that produces olefin macromers. However, the metallocene compound forming the polymerization catalyst that produces olefin macromer has a terminal vinyl ratio (terminal vinyl ratio) when the olefin having the highest molar content among the monomer units constituting the olefin polymer is homopolymerized at 70 ° C. It is a metallocene compound that forms a polymerization catalyst that produces a polymer having Rv) of 0.5 or more.

Here, the terminal vinyl ratio (Rv) and the terminal vinylidene ratio (Rvd) are defined by the following equations, respectively.
(Rv) = (Mn / M) x 2 x [Vi] / 1000
(Rvd) = (Mn / M) x 2 x [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 1000C calculated from ^{13 C-NMR, and [Vd] is 13} C-NMR. It is the number of terminal vinylidene groups per 1000C calculated from the above. Here, 1000C means 1000 total skeleton-forming carbons, and the total skeleton-forming carbon means branching of a branch length of carbon number 2 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 of terminal vinyl groups per 1000 total skeleton-forming carbons. 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 end of the vinylidene structure represented by the following structural formula (2-b) is formed. When hydrogen is used, chain transfer usually occurs preferentially to hydrogen, and a saturated end (isobutyl structure) as shown in the structural formula (2-c) is generated at the end.
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. Polymers are produced (references: Macromol. Rapid Commun. 2000, 21, 1103-1107). In addition, when a complex having a very special structure exemplified in the present invention is used, surprisingly, when hydrogen is used, the β-methyl elimination reaction preferentially occurs although the activity is increased. It has been found that the propenyl structure (vinyl structure) of the formula (2-a) is mainly produced.

Of the structural formulas (2-a), structural formulas (2-b), and structural formulas (2-c), those that can be copolymerized with a metallocene complex or a Ziegler catalyst have a vinyl structure represented by structural formula (2-a). Only.
Therefore, among all the terminal structures, the higher the copolymerizable terminal vinyl ratio, the higher the efficiency as macromer. Therefore, the component [A-1], which is a 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. More preferably, it is 0.80 or more, ideally 1.0 (all terminals are vinyl groups).

Here, the details of the measurement methods of [Vi] and [Vd] are as follows.
After 390 mg of the sample was completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), the measurement was carried out at 125 ° C. by the proton complete decoupling method. The chemical shift set the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 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 range: -20 ppm to 179 ppm
The terminal vinyl ratio and the terminal vinylidene ratio of this 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 bisinden complex having a bulky heterocyclic group at the 2-position and an aryl group which may be substituted at the 4-position.
This selectivity can also be controlled by changing the polymerization temperature. For example, in the complex shown in Examples, the higher the polymerization temperature, the higher the terminal vinyl ratio can be.

[Vi] utilizes the fact that carbon 1 and carbon 2 of the structural formula (2-a) are detected at 115.5 ppm and 137.6 ppm, and [Vd] is the carbon 3 of the structural formula (2-b). And carbon 4 are detected at 111.2 ppm and 144.5 ppm, respectively, and are calculated as the number for 1000 total skeleton-forming carbons as shown in the following formula. Here, the total skeleton-forming carbon means all carbon atoms other than methyl carbon.
[Vi] = [Peak intensity of carbon 1] / [Total peak intensity of total skeleton-forming carbon] × 1000
[Vd] = [Peak intensity of carbon 3] / [Total peak intensity of total skeleton-forming carbon] × 1000

The terminal vinyl ratio has been described by taking a propylene polymer as an example, but even when the olefin is other than propylene, it can be determined by the example of propylene.
It is shown in JP-A-2009-299045 that the above-mentioned component [A-1] can form a polymerization catalyst for producing a propylene polymer having a terminal vinyl chloride ratio (Rv) of 0.5 or more. There is.

(2) Ingredient [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 azurenyl group, and each may have a substituent, except that 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, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms, and represents M ^21. Represents titanium, zirconium or hafnium, and X ²¹ and X ²² independently have 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. 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 E ²¹ and E ²² are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azurenyl group, and may each 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.
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 compounds may also be compounds that form catalysts capable of producing macromers at the same time.
Further, as a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are substituted indenyl groups, the following structure can be exemplified.

[In the general formula (5), R ⁵¹ and R ⁵³ are independently aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and R ⁵² and R ⁵⁴ are independently halogen and silicon, respectively. 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 independently have 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, and halogenation having 1 to 20 carbon atoms. hydrocarbon group, an amino group or an alkylamino group having a carbon number of 1 to 20, Q ⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, have a hydrocarbon group having 1 to 20 carbon atoms It represents a gelmilene group which may have a good silylene group or a hydrocarbon group having 1 to 20 carbon atoms, and M ⁵¹ represents zirconium or hafnium. ]

The above-mentioned R ⁵¹ and R ⁵³ are independently aliphatic hydrocarbon groups having 1 to 6 carbon atoms, preferably alkyl groups 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, with preference given to methyl. , Ethyl, n-propyl, i-propyl.
Further, the above-mentioned R ⁵² and R ⁵⁴ are aryl groups having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of heteroelements selected from these, and the aryl groups include. At least one hydrocarbon group having 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, and a halogen having 1 to 6 carbon atoms are contained 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 , preferably at least one is a phenyl group, 4-i-propyl group, 4-trimethylsilyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di. It is a t-butylphenyl group, a 4-phenyl-phenyl group, a chlorophenyl group, a naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-i-propyl group, a 4-trimethylsilyl group, a 4-t-butylphenyl group. , 4-Chlorophenyl group. Further, ^{it is preferable that R 52} and R ⁵⁴ are the same as each other.

In addition, X ⁵¹ and X ⁵² are co-ligands that react with component [B] to produce active metallocenes capable of olefin polymerization. To achieve this purpose, X ⁵¹ and X ⁵² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 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, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group having 1 to 20 carbon atoms.
Also, Q ⁵¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms for cross-linking two conjugated five-membered ring ligands through a carbon of 1 or 2 carbon atoms, Indicates either a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ⁵¹ include an alkylene group such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc .; an arylalkylene group such as diphenylmethylene; a silylene group; a methylsilylene, a dimethylsilylene, a diethylsilylene, a diphenylene. Alkyl silylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; Alkyloligosilylene group such as tetramethyldisyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germilene group; aryl gelmilene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene 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) Dichloromethane [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) Dichloromethane [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'-dimethylgelmilenebis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] hafnium,
(19) Dichloro [1,1'-dimethylgelmilenebis {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.

Further, as a non-limiting preferred example of the component [A-2], when E ²¹ and E ²² are substituted azurenyl groups, the following structure 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 aryl groups having 6 to 30 carbon atoms, which may independently contain halogen, silicon, or a plurality of hetero elements selected from these. Q ⁶¹ is have a divalent hydrocarbon group, a hydrocarbon group of a hydrocarbon group which may have a silylene group or a C1-20 having 1 to 20 carbon atoms having 1 to 20 carbon atoms M ⁶¹ represents zirconium or hafnium, and X ⁶¹ and Y ⁶¹ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents a silyl group having a hydrocarbon group of 1 to 20, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ]

The R ⁶¹ and R ⁶² are independently hydrocarbon groups having 1 to 6 carbon atoms, preferably alkyl groups, and more preferably alkyl groups 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, with preference given to methyl. , Ethyl, n-propyl.

Further, each of the above R ⁶³ and R ⁶⁴ has 6 to 30 carbon atoms, preferably 6 to 6 carbon atoms, which may independently contain a halogen atom, silicon, or a plurality of heteroelements selected from these. There are 24 aryl groups. Such aryl groups are phenyl groups, biphenylyl groups and naphthyl groups which may have a substituent. 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, Examples thereof include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl and 3,5-dichloro-4-trimethylsilylphenyl.

The X ⁶¹ and Y ⁶¹ are co-ligands and react with the component [B] to produce an active metallocene having an olefin polymerization ability. Therefore, as long as this object is achieved ^{, the types of ligands of X 61} and Y ⁶¹ are not limited, and each of them independently contains a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. Alkoxy groups having 1 to 20 carbon atoms, alkylamide groups having 1 to 20 carbon atoms, trifluoromethanesulfonic acid groups, phosphorus-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, etc. Shown.

Q ⁶¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms for cross-linking two conjugated five-membered ring ligands through a carbon of 1 or 2 carbon atoms, carbon atoms Indicates either a silylene group which may have a hydrocarbon group of 1 to 20 or a gelmilene group which may have a hydrocarbon group of 1 to 20 carbon atoms. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ^61, methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, alkylene group and the like; arylalkylene group such as diphenylmethylene; silylene group; methylsilylene, dimethylsilylene, diethyl silylene, di Alkyl silylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; Alkyloligosilylene group such as tetramethyldisyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germilene group; aryl gelmilene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.
Further, the M ⁶¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the metallocene compound represented by the above general formula (6) include the following.
However, only representative example compounds are described, avoiding a large number of complicated examples. Moreover, although the compound whose central metal is hafnium is described, it is obvious that a similar zirconium compound can be used, and various ligands, cross-linking groups or auxiliary ligands can be arbitrarily used.
(1) Dichloro {1,1'-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium,
(2) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(3) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium,
(4) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(5) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium,
(6) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium,
(7) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(8) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(9) Dichloromethane [1,1'-dimethylsilylenebis {2-methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium,
(10) Dichloromethane [1,1'-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium,
(11) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(12) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(13) Dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(14) Dichloromethane [1,1'-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium,
(15) Dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(16) Dichloro [1,1'-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(17) Dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium,
(18) Dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(19) Dichloro [1,1'-dimethylgelmilenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(20) Dichloro [1,1'-dimethylgelmilenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium,
(21) Dichloro [1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(22) Dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(23) Dichloro [1,1'-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(24) Dichloro [1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, And so on.

Of these, preferably dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, 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 -Hydroazulenyl}] hafnium, dichloromethane [1,1'-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl}] hafnium, dichloromethane [1,1'-dimethylsilylenebis {2-Ethyl-4- (3-Methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium, dichloro [1,1'-(9-silafluorene-9,9-dichloromethane) 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-hydroazurenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2-ethyl). -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloromethane [1,1'-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazulenyl}] Hafnium, Dichloro [1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] Hafnium.

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

[In the general formula (7), R ⁷¹ and R ⁷⁴ are independently aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and R ⁷² and R ⁷⁵ are independently having 1 to 6 carbon atoms, respectively. 6 is a hydrocarbon group, and R ⁷³ and R ⁷⁶ are independently hydrogen atoms or hydrocarbon groups having 1 to 6 carbon atoms. X ⁷¹ and Y ⁷¹ independently have 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, and halogenation having 1 to 20 carbon atoms. hydrocarbon group, an amino group or an alkylamino group having a carbon number of 1 to 20, Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, have a hydrocarbon group having 1 to 20 carbon atoms It represents a gelmilene group which may have a good silylene group or a hydrocarbon group having 1 to 20 carbon atoms, and M ⁷¹ represents zirconium or hafnium. ]

The R ⁷¹ and R ⁷⁴ are independently aliphatic hydrocarbon groups having 1 to 6 carbon atoms, preferably alkyl groups 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, with preference given to methyl. , Ethyl, n-propyl, and particularly preferably a methyl group.
Each of the above R ⁷² and R ⁷⁵ is 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 group.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. These are preferably methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl.
Each of the above R ⁷³ and R ⁷⁶ is independently a hydrogen atom or 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, particularly. It is preferably a methyl group.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like. These are preferably methyl, ethyl, n-propyl, i-propyl, t-butyl and phenyl.

Among the above, X ⁷¹ and Y ⁷¹ are co-ligands and react with the component [B] to produce an active metallocene having an olefin polymerization ability. To achieve this purpose, X ⁷¹ and Y ⁷¹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 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, a dialkylarylsilyl group, an alkyldiarylsilyl group, or a triarylsilyl group having 1 to 20 carbon atoms.

Among the above, Q ⁷¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two 5-membered rings and bridges two conjugated five-membered ring ligands via carbons having one or two carbon atoms. , A silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ⁷¹ include an alkylene group such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc .; an arylalkylene group such as diphenylmethylene; a silylene group; a methylsilylene, a dimethylsilylene, a diethylsilylene, a diphenylene. Alkyl silylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; Alkyloligosilylene group such as tetramethyldisyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germilene group; aryl gelmilene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene 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 {dimethylgelmilenebis (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 Millenbis (2,3,5-trimethylcyclopentadienyl)} hafnium, dichloro {dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl)} hafnium, dichloro {dimethylsilylenebis (2,4) -Dimethylcyclopentadienyl)} hafnium.

Further, 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 structure 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, preferably a methyl group, an ethyl group, an isopropyl group, or t. -Butyl group, trimethylsilyl group. R ⁸¹ , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are selected from hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms or silicon-containing hydrocarbon groups with 1 to 20 carbon atoms. They may be the same or different, and ^{adjacent substituents from R 85 to} R ⁸⁸ may be bonded to each other to form a ring.
Further, X ⁸¹ and Y ⁸¹ are auxiliary ligands and react with the component [B] to produce an active metallocene having an olefin polymerization ability. To achieve this purpose, X ⁸¹ and Y ⁸¹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkoxyamide group, trifluoromethanesulfonic acid group, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and the like.

Further, Q ⁸¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which bridges two conjugated five-membered ring ligands via carbon having one or two carbon atoms, which bonds two five-membered rings. , A silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ⁸¹ include an alkylene group such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc .; an arylalkylene group such as diphenylmethylene; a silylene group; a methylsilylene, a dimethylsilylene, a diethylsilylene, a di (di). Alkyl silylene groups such as n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; aryl silylene groups such as diphenyl silylene; tetra Alkyloligosilylene group such as methyldicyrylene; Germilene group; Alkyl gelmilene group in which silicon of the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) gelmilene Group: An arylgelmilene group and the like can be mentioned.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.
Further, the 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-dit-butylfluorenyl) zirconium,
(14) Dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(15) Dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(16) Dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(17) Dichlorodimethylmethylene (3-i-propyl-5-methylcyclopentadienyl) (2,7-dit-butylfluorenyl) zirconium,
(18) Dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-dit-butylfluorenyl) zirconium,
(19) Dichlorodimethylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (2,7-dit-butylfluorenyl) zirconium,
(20) Dichlorodimethylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (2,7-dit-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-dit-butylfluorenyl) zirconium,
(26) Dichlorodiphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(27) Dichlorodiphenylmethylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(28) Dichlorodiphenylmethylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(29) Dichlorodimethylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(30) Dichlorodimethylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(31) Dichlorodimethylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(32) Dichlorodimethylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(33) Dichlorodiphenylsilylene (3-i-propyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(34) Dichlorodiphenylsilylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(35) Dichlorodiphenylsilylene (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium,
(36) Dichlorodiphenylsilylene (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-dit-butylfluorenyl) zirconium, and the like.

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

(3) Ingredient [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 metallocene compounds [A-1] and [A-2] carried and converted into a cation, and [B-3] ion. Exchangeable layered silicate.

(3-1) Ingredient [B-1]
Specific examples of the aluminum oxy compound of the component [B-1] include compounds represented by the following general formulas (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 1 to 6 carbon atoms. Further, the plurality of R ⁹¹ , R ¹⁰¹ and R ¹¹¹ may be the same or different from each other. Further, p represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (9) and (10) are compounds also called alumoxane, and among these, methylalmoxane or methylisobutylarmoxane is preferable.
It is also possible to use a plurality of types of the above-mentioned armoxane in combination within each group and between each group. The above-mentioned almoxane can be prepared under various known conditions.
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 an alkylboronic acid represented by the following general formula (12). It can be obtained by a reaction of 1 (molar ratio).
In the general formulas (11) and (12), R ¹¹² and R ¹²¹ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group.

Here, the aluminum oxy compound is used by supporting it on a carrier.
The carrier is not particularly limited in terms of its elemental composition and compound composition, and examples thereof include carriers composed of inorganic or organic compounds. Examples of the inorganic carrier include silica, alumina, silica-alumina magnesium chloride, activated carbon, and inorganic silicates. Alternatively, it may be a mixture of these.
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 hydrocarbons such as styrene and divinylbenzene. Examples thereof include a particulate carrier of a porous polymer composed of a polymer of hydrogen or the like. Alternatively, it may be a mixture of these.
These carriers are usually 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm, and have a particle size at 50% cumulative when the particle size frequency distribution is measured by a laser diffraction / scattering type particle size distribution meter. It is preferable that the particles have a diameter).

(3-2) Ingredient [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.
The ionic compound is a complex of cations such as carbonium cations and ammonium cations and cations of organoboron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron. Examples include isomers.
Examples of Lewis acid include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
It should be noted that 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 grasped as a sex compound. Therefore, the compound belonging to both the Lewis acid and the ionic compound described above shall 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 terms of its elemental composition and compound composition, and examples thereof include fine particle carriers composed of inorganic or organic compounds. Examples of the inorganic carrier include silica, alumina, silica-alumina magnesium chloride, activated carbon, and inorganic silicates. Alternatively, it may be a mixture of these.
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 hydrocarbons such as styrene and divinylbenzene. Examples thereof include a particulate carrier of a porous polymer composed of a polymer of hydrogen or the like. Alternatively, it may be a mixture of these.
These carriers are usually 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm, and have a particle size at 50% cumulative when the particle size frequency distribution is measured by a laser diffraction / scattering type particle size distribution meter. It is preferable that the particles have a diameter).

(3-3) Ingredient [B-3]
The component [B-3] is an ion-exchangeable layered silicate (hereinafter, simply abbreviated as silicate).
In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel by a bonding force, and the contained ions can be exchanged. Say. Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (quartz, cristobalite, etc.) other than ion-exchange layered silicates, but they are included. But it may be. Specific examples of silicates include the following layered silicates described in "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995).
That is, montmorillonite, sauconite, byderite, nontronite, saponite, hectorite, stevensite and other smectites, vermiculite and other vermiculite, mica, illite, serisite, glauconite and other mica, attapargit, sepiolite, parigolskite. , Bentonite, pyrophyllite, talc, chlorite group, etc.

The silicate used as a raw material in the present invention is preferably a silicate having a 2: 1 type structure as a main component silicate, 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 a main component of the interlayer cation is preferable from the viewpoint that it can be obtained relatively easily and inexpensively 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 preferable to carry out a chemical treatment. Here, as the chemical treatment, either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the structure of clay can be used. Specific examples of the chemical treatment in the present invention include (a) acid treatment, (b) salt treatment, (c) alkali treatment, and (d) organic substance treatment described below.

(A) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of the cations such as Al, Fe, and Mg in the 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. The number of salts and acids used in the treatment may be two or more. The conditions for treatment with salts and acids are not particularly limited, but usually, the conditions for 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 of eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in aqueous solutions.

(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-exchangeable layered silicate before being treated with salts are described below. It is preferable to exchange ions with cations dissociated from the salts shown.

The salts used in the salt treatment for the purpose of such ion exchange are a group consisting of a cation containing at least one atom selected from the group consisting of groups 1 to 14 atoms, a halogen atom, an inorganic acid and an organic acid. A compound consisting of at least one selected anion, more preferably a cation containing at least one atom selected from the group consisting of group 2-14 atoms and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), 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 , tea _{4 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, etc., 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, etc., 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 can be mentioned.

(C) Alkaline 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) Treatment of Organic Substances Examples of the organic matter used for the treatment of organic substances include trimethylammonium, triethylammonium, N, N-dimethylanilinium, and triphenylphosphonium.
Further, as the anions constituting the organic matter treatment agent, in addition to the anions exemplified as the anions constituting the salt treatment agent, for example, hexafluoroborate, tetrafluoroborate, tetraphenylborate and the like can be exemplified. , Not limited to these.

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

As described above, in the present invention, particularly preferable component [B] is an ion-exchangeable layered silicate having a water content of 3% by weight or less obtained by salt treatment and / or acid treatment. Is.
The ion-exchangeable layered silicate can be treated with an organoaluminum compound described later before catalyst formation or use as a catalyst, which is preferable. The amount of the organoaluminum compound used with respect to 1 g of the ion-exchangeable layered silicate is not limited, but is usually 20 mmol or less, preferably 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, 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 also possible and preferable to wash after the treatment. As the solvent, a hydrocarbon solvent similar to the solvent used in the prepolymerization or slurry polymerization described later is used.

Further, as the component [B], it is preferable to use spherical particles having an average particle size of 5 μm or more. If the shape of the particles is spherical, a natural product or a commercially available product may be used as it is, or a particle whose shape and particle size are controlled by granulation, granulation, separation, or the like may be used.
Examples of the granulation method used here include a stirring granulation method and a spray granulation method, but commercially available products can also be used.
In addition, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used for granulation.

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 formation of fine powder in the polymerization step. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited, especially when prepolymerization is performed.
Among the above-mentioned components [B], a particularly preferable one is [B-3] ion-exchangeable layered silicate.

(4) Organoaluminium Compound The catalyst for olefin polymerization of the present invention may contain an organoaluminum compound, if necessary.
The following general formula:
AlR ¹³¹ _q Z _3-q ... General formula (13)
The organic aluminum compound represented by is suitable.
Needless to say, in the present invention, the compounds represented by this formula can be used alone, in combination of two or more, or in combination. 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, and an amino group. q is a number greater than 0 and up to 3. As R ¹³¹ , an alkyl group is preferable, and Z has chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 carbon atom 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. Examples thereof include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, trialkylaluminum and dialkylaluminum hydride with q = 3 are preferable. More preferably, ^{it is trialkylaluminum in which R 131} has 1 to 8 carbon atoms.

In addition to the components [A-1], [A-2], and [B] and the organoaluminum compound used as needed, the catalyst used in the present invention is used as long as the object of the present invention is not impaired. Commonly used polymers such as polyethylene and polypropylene, and solid inorganic oxides such as silica and titania may be added.

2. Preparation (formation) / prepolymerization of catalyst In the catalyst in the present invention, the above components [A-1], [A-2] and component [B] are simultaneously or continuously or continuously in a (preliminary) polymerization tank. It can be formed by contacting them at one time or multiple times.
Further, when the components [A-1] and [A-2] are brought into contact with the component [B], the organoaluminum compounds may be brought into contact with each other simultaneously or continuously, or at one time or multiple times. In particular, in the case of the component [A-1] or [A-2], when X ¹¹ and X ¹² or X ²¹ and X ²² are a hydrocarbon group other than the hydrocarbon group having 1 to 20 carbon atoms, for example, a halogen group, it is organic. It is preferable to use an aluminum compound.
The contact order can be any combination for the purpose of purpose, but particularly preferable ones are as follows for each component.
When an organoaluminum compound is used, before the component [A-1], [A-2] and the component [B] are brought into contact with each other, the component [A-1], [A-2], or the component [B] is used. ] And, or contacting both the components [A-1], [A-2] and the component [B] with the organoaluminum compound, or the components [A-1], [A-2] and the component [B]. ] Is brought into contact with the organoaluminum compound at the same time, or the organoaluminum compound can be brought into contact with the components [A-1] and [A-2] and the organoaluminum compound after being brought into contact with each other. However, preferably, it is a method of contacting the organoaluminum compound with any of the components [A-1] and [A-2] before contacting the component [B].
Contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between −20 ° C. and 150 ° C.
After contacting each component, it is possible to wash with an aliphatic hydrocarbon or an 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, based on 1 g of the component [B]. Is the range of.
Further, the component [A-1], the amount of the organoaluminum compound to the [A-2] is, in a molar ratio of transition metal, preferably 0.01 to 5 × 10 ^6, particularly preferably 0.1 to 1 × 10 The range of ^{4 is preferable.}

The component [A-1] and the component [A-2] used in the present invention relate to the ratio of the molar amount of [A-1] to the total molar amount of the components [A-1] and [A-2]. 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, which is the basic performance of the polymerization catalyst.
For example, in order to produce a polymer having a reduced branching index (g') by increasing the amount of branching, the amount is preferably 0.30 or more, more preferably 0.40 or more, still more preferably 0.50 or more. It is particularly preferably 0.70 or more. Further, in order to obtain a polymer with high catalytic activity, it can be 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] in the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen.

The catalyst according to the present invention is preferable because it is possible to carry out prepolymerization in which an olefin is brought into contact with the catalyst and polymerized in a small amount.
By performing the prepolymerization, in addition to the effect that the two complexes are activated before the main polymerization and fixed on the component [B], the active site is covered with the prepolymerized polymer, and the active site is activated by the polymer. 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 prepolymerization, it is possible to improve the melt tension and suppress the generation of gel when the main polymerization is performed. It is considered that the reason is that the branched components can be uniformly distributed among the polymer particles when the main polymerization is performed.
The amount of polymer to be prepolymerized is preferably 0.1 or more, more preferably 0.3 or more in terms of weight ratio with respect to the component [B], and is preferably 10 or less, more preferably 10 or less, for economic efficiency 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 for the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, etc. Styrene and the like can be exemplified, and propylene is preferable.
The olefin feeding method can be any method such as a feeding method for maintaining the olefin in the reaction vessel at a constant speed or a constant pressure state, a combination thereof, and a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C., 5 minutes to 24 hours, respectively.
Further, it is preferable to wash after the completion of prepolymerization.

3. 3. Drying the catalyst In the present invention, the catalyst for olefin polymerization 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 catalyst for olefin polymerization changes from a so-called mud-like state to a powder-like state.
Further, in order to suppress catalyst deterioration during storage, it is preferable to add or add an organoaluminum compound as the component [C] to the catalyst for olefin polymerization used in the present invention, and then dry under reduced pressure. ..
By adding the organoaluminum compound of component [C], the presence of the organoaluminum compound component of component [C] around the active site plays a role of scavenging against a trace amount of toxic substance from the outside. Deterioration of the catalyst can be suppressed by performing the operation in the polymerization catalyst. At this time, by performing vacuum drying, the added organoaluminum compound acts directly on the active site and is fixed around the active site before causing a side reaction such as a decomposition reaction of the active site. Point storage can be performed efficiently.
Among the organoaluminum compounds listed above, triisobutylaluminum and triethylaluminum are particularly preferable as the organoaluminum compound of the component [C] used during storage.
The organoaluminum compound of the component [C] is preferably added or added so as to have a condition of 1 to 70 mol with respect to a total of 1 mol of the components [A-1] and [A-2].
The mechanism for suppressing the deterioration of the above-mentioned catalyst of the organoaluminum compound of the component [C] is the same for the non-prepolymerized olefin polymerization catalyst used in the present invention and the prepolymerized olefin polymerization catalyst. I think it is a mechanism.
On the other hand, if the amount of the 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 come into contact with each other using the residual solvent as a medium even after the drying step. It has been found that the number is increased, and the deterioration reaction of the complex due to the organoaluminum compound is likely to proceed.
Therefore, in order to prevent the added organoaluminum compound from acting directly on the active site and excessively promoting side reactions such as the decomposition reaction of the active site, the residual solvent amount of the olefin polymerization catalyst of the present invention is 0. It is preferably .50 wt% or less, more preferably 0.45 wt% or less, and more preferably 0.40 wt% or less.
Method for Quantifying Residual Solvent Components About 20 to 50 g of the polyolefin catalyst component after the drying step is accurately weighed and introduced into a well-dried flask, and the inside of the flask is depressurized at 60 ° C. and dried for 4 hours. , Weigh the polyolefin catalyst component.
The amount of residual solvent (wt%) is calculated by the following formula.
Residual solvent amount (wt%) = ([Catalyst weight before decompression]-[Catalyst weight after decompression]) / [Catalyst weight before decompression] x 100

4. Preservation of catalyst In the present invention, the catalyst for olefin polymerization 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 catalyst for olefin polymerization 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. It is possible to produce a polymer without.

Further, the catalyst for olefin polymerization obtained above is preferably stored under 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 do not get mixed in the pressure vessel by storing at a pressure higher than the atmospheric pressure.
The inert gas is preferably nitrogen gas, and the nitrogen gas used at this time is, for example, high-purity nitrogen having a purity of 99.999 vol% or more, and further removing water through a molecular sieve or the like. It is preferable to use it.

Usually, the deterioration of the catalyst refers to the decomposition of active sites that causes 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 points, which causes a decrease in activity.
In a solid catalyst supporting a single transition metal complex, the main problem is a decrease in activity simply due to a decrease in the number of active sites. Therefore, as long as the decomposition of the transition metal complex is in a slow range, the storage conditions can be arbitrarily set. I was able to set it.
Further, in a multi-dimensional catalyst using a plurality of transition metal complexes as described in Japanese Patent Application Laid-Open 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, if the deterioration progresses without being decomposed, the originally expected activity of each transition metal complex changes. As a result, when a catalyst stored for a long period of time is used and polymerized under the same conditions as a catalyst that has just been produced, not only the activity is simply deteriorated, but also the change in molecular weight distribution and the case where a comonomer is used , Appears as a phenomenon that the composition distribution changes.
When such a deterioration phenomenon appears, when operating, the fluidity can be adjusted by adjusting the hydrogen concentration or the amount of comonomer by using activation by hydrogen or comonomer. It is possible to make adjustments and take measures to suppress deterioration of quality.

However, even in the case of a multi-element catalyst using a plurality of transition metal complexes, in the case of a multi-dimensional catalyst in which one complex and the other complex interact with each other to exhibit certain characteristics, for example, macromers are generated from one of them. In the case of a multi-catalyst system in which the other complex in the vicinity is copolymerized, the primary structure such as the amount of long-chain branching and the branching distribution changes due to the difference in the deactivation method of each complex, and the melt tension. Causes deterioration of primary physical properties.
This leads to not only productivity but also loss due to changes in quality when considering industrial production.
Among multiple catalysts, especially when a metallocene compound containing a heteroatom is used, the lone pair of electrons of the heteroatom is coordinated to the other active point to cause an active point. There is a mechanism in which the heteroatom is altered, and a mechanism in which the unshared electron pair of the heteroatom is deactivated with the decomposition of the metallocene compound after being coordinated to the organic aluminum compound component.
Therefore, in the present invention, when a dual catalyst containing a complex containing a hetero atom is used, the storage temperature is controlled in the range of 1 ° C. or higher and 20 ° C. or lower, and the mixture is industrially stored. It has also been found that not only does it not cause a decrease in activity, but it can also prevent a decrease in quality.
When the metallocene compound containing a heteroatom as described above and the metallocene not containing the heteroatom are stored for several days at a temperature exceeding 20 ° C., which is a state where the storage temperature is different from the storage temperature of the present invention and is stored at the atmospheric temperature in summer. Non-uniform deactivation occurs with the compound, which also affects the active point ratio of special macromer copolymerization, and causes a decrease in melt tension due to a decrease in the long-chain branching ratio.

Therefore, it is necessary to control the storage temperature in the range of 20 ° C. or lower for the binary catalyst containing the metallocene compound [A-1] containing the heteroatom of the present invention.
On the contrary, it is economically disadvantageous and not preferable to keep the temperature below 1 ° C., and when stored for a long period of time, the unshared electron pair of the heteroatom as described above is arranged in the organoaluminum compound component. Both are different in temperature dependence between the decomposition reaction accompanied by deactivation due to coordination and the reaction in which an unshared electron pair of a heteroatom is coordinated to the other complex to change the active point. It is conceivable that there will be a difference in the reaction progress ratio, and as a result, the melt tension will decrease due to the decrease in the long chain branching ratio.
Therefore, it is necessary to control the storage temperature in the range of 1 ° C. or higher for the binary catalyst containing the metallocene compound [A-1] containing the heteroatom of the present invention.
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 when a polymer is polymerized using a catalyst stored in such a state, it is possible to obtain a polymer without deteriorating performance such as melt tension.
Therefore, it was found that the temperature can be preferably controlled to 10 ° C. or higher and 20 ° C. or lower in consideration of economic efficiency and the like.
Further, by storing the catalyst shown in the present invention at a controlled temperature in this range, the performance is deteriorated in a range of more than 10 days, 2 years or more, and about 800 days immediately after the catalyst is manufactured. In particular, it is possible to produce a polymer in which a long-chain branch has been introduced without causing the above.
At present, as shown in the examples, it has been confirmed that the melt tension does not decrease within the range of 800 days (2.2 years).

5. Use of catalyst / Olefin polymerization In the polymerization mode, the monomer efficiently contacts the catalyst for olefin polymerization containing the above-mentioned component [A-1], component [A-2], component [B] and, if necessary, an organoaluminum compound. Then, any style can be adopted.
Specifically, the slurry method using an inert solvent, the so-called bulk method in which the monomer itself (for example, propylene) is used as a solvent without substantially using the inert solvent, the solution polymerization method, or substantially no liquid solvent is used. A vapor phase method that keeps each monomer 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, multi-stage polymerization of two or more stages is also possible.

In the case of slurry polymerization, a single or mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the polymerization solvent.
The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. The upper limit is preferably 80 ° C. or lower, more preferably 75 ° C. or lower.
Further, when gas phase polymerization is used, it 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 bulk polymerization is used, it is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Further, when gas phase polymerization is used, it is preferably 1.0 MPa or more, more preferably 1.5 MPa or more. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Further, as a molecular weight modifier and for the effect of improving the activity, hydrogen is supplementarily used in the range of ^{1.0 × 10-6} or more and 1.0 × ^{10-2 or less with respect to the monomer.} be able to.
In addition to the average molecular weight of the polymer produced by changing the amount of hydrogen used, the molecular weight distribution, the bias of the molecular weight distribution toward the high molecular weight side, the extremely high molecular weight component, and the branching (amount, length, Distribution) can be controlled, thereby controlling the melt properties such as strain hardening degree, melt tension, and melt ductility.
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 with an α-olefin having 2 to 20 carbon atoms other than propylene. Can be used.

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

6. Physical Properties of Olefin Polymer In the olefin polymer obtained from the production method of the present invention, the branching index (g') is characterized by being 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 the present specification, 3D-GPC means a GPC device to which three detectors are connected. These three detectors are a differential refractometer (RI), a viscosity detector (Viscometer) and a multi-angle laser light scattering detector (MALLS).
The Alliance GPCV2000 from Waters was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer).
Further, as the light scattering detector, DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) was used.
The detectors were connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-triclolobene (addition of the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As the column, two MHHR-H (S) HTs manufactured by Tosoh Corporation were connected and used. The temperature of the column, the 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.
The data processing software ASTRA (version 4.73.04) attached to MALLS was used to obtain the absolute molecular weight (M) obtained from MALLS, the squared radius of inertia (Rg), and the ultimate viscosity ([η]) obtained from Viscometer. , The calculation was performed with reference to the following documents.

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

[Calculation of branch index (g')]
The branching index (g') is defined as the ratio (ηbranch / ηlin) of the ultimate viscosity (ηbrunch) obtained by measuring the sample with the Viscometer and the ultimate viscosity (ηlin) obtained by separately measuring the linear polymer. ,calculate.
When a long-chain branch is introduced into a polymer molecule, the radius of inertia is smaller than that of a linear polymer molecule having the same molecular weight. As the radius of inertia decreases, the ultimate viscosity decreases. Therefore, as long-chain branching is introduced, the ratio of the ultimate viscosity (ηbranch) of the branched polymer to the ultimate viscosity (ηlin) of the linear polymer having the same molecular weight (ηbranch / ηlin). Is getting smaller.
Therefore, when the branch index (g'= ηbrunch / ηlin) becomes a value smaller than 1, it means that a branch is introduced, and as the value becomes smaller, the introduced long chain branch 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.
A method for measuring the melt tension (MT) will be described.
Using Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the tension detected by the pulley when the resin is extruded into a string shape and wound on a roller under the following conditions is defined as melt tension (MT).
Capillary: 2.1 mm in diameter
Cylinder diameter: 9.6 mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 190 ° C
Here, the larger the MT value, the higher the melting tension.

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

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

[Synthesis Example 2 of Catalyst Component [A-2]]:
(2) Synthesis of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: Synthesis of (component [A-2] (complex 2) ):
The synthesis of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is described in Example 7 of JP-A-11-240909. It was carried out in the same manner as.

[Synthesis example of catalyst component [B]]
(3) Chemical treatment of ion-exchangeable 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 Industrial Chemicals, Inc .: 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 an aqueous solution of lithium sulfate, and the entire amount of the cake-like solid was put into the flask. The slurry was reacted at room temperature for 120 minutes. After adding 4000 g of distilled water to this slurry, it was filtered to obtain a cake-like solid. The operation of adding 4000 g of distilled water to the cake-like solid and filtering the slurry was repeated until the pH of the slurry became 5 to 6, and filtration was performed to obtain 760 g of the cake-like solid.
The obtained solid was pre-dried at 100 ° C. under a nitrogen stream for a whole day and night, coarse particles of 53 μm or more were removed, and further dried under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated montmorillonite.
The composition of this chemically treated montmorillonite is 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. Al / Si = 0.175 [mol / mol].

(4) Catalyst preparation and prepolymerization:
10 g of the chemically treated montmorillonite obtained above was placed in a three-necked flask (volume 1 L), and heptane (66 mL) was added to form a slurry, to which 34 triisobutylaluminum (25 mmol: concentration 143 mg / mL heptane solution) was added. .0 mL) was added and stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 50 mL.
Further, in another flask (volume 200 mL), the 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.
Further, in another flask (volume 200 mL), the rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) produced in Synthesis Example 2 of the catalyst component [A-2] was prepared. ) -4-Haloazurenyl}] Hafnium (45 μmol) was dissolved in toluene (9 mL) to prepare Solution 2.

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

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

(polymerization)
The 3L autoclave was dried well in advance by circulating nitrogen under heating, and 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 N ml of hydrogen was introduced.
Then, after introducing 750 g of liquid propylene, the temperature was raised to 70 ° C.
Then, 50 mg of the prepolymerized catalyst excluding 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 the polymer was obtained.

[Reference example 2]
In Reference Example 1 above, the same polymerization was carried out except that 36 N ml of hydrogen was introduced. As a result, 175 g of the polymer was obtained.

[Example 1]
The prepolymerization catalyst synthesized above is stored in a refrigerated warehouse in which 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 summers have passed), the same polymerization as in Reference Example 1 was carried out.

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

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

The evaluation sample was added to the obtained polymer as additives: Irganox 1010 (manufactured by Ciba Specialty Chemicals) 1250 ppm, Irgafos 168 (manufactured by Ciba Specialty Chemicals) 1250 ppm, and calcium stearate (NOF CORPORATION). (Manufactured by) 1250 ppm was added, and KZW15TW-45MG manufactured by Technobel Co., Ltd. was melt-kneaded and pelletized using a co-directional meshing twin-screw extruder.

From Table 1 and FIG. 1, the method for producing an olefin polymer (Example 1) using the catalyst storage method according to the present invention is equivalent to Reference Example 1 even though the catalyst storage days have passed 800 days. It can be seen that it has the catalytic activity of the above and the performance of the obtained olefin polymer. On the other hand, it can be seen that in Comparative Example 1 using the catalyst stored at room temperature, 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 the catalyst according to the present invention, an olefin (co) polymer can be produced with high activity even after 800 days have passed. It can be used industrially.

Claims (9)

Use of an olefin polymerization catalyst containing the following components [A-1], [A-2], [B] and an organoaluminum compound in total of the components [A-1] and [A-2] with respect to the component [B]. amount 0.1μmol~1000μmol the component [B] 1 g, after the amount of the organoaluminum compound to the component [a-1] prepared in 0.01 to 5 × 10 ⁶ in a molar ratio of transition metal, the The olefin polymerization catalyst is stored under pressure in the range of 0.01 MPaG to 0.05 MPaG using an inert gas in a pressure vessel for 2 years or more at a controlled temperature of 1 ° C. or higher and 20 ° C. or lower, and the olefin polymerization catalyst is stored. A method for producing an olefin polymer, which comprises polymerizing an olefin using a 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 independently cyclopentadienyl groups, indenyl groups, fluorenyl groups or azurenyl groups, respectively.
R ¹¹ and R ¹³ are independently silyl groups having a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, respectively. , A hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms or a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group or halogen having 1 to 20 carbon atoms. Represents an amino group with a hydrocarbon group
R ¹² and R ¹⁴ 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, respectively. Group groups include halogen atoms, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, silyl groups having hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, and hydrocarbons having 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a silyl group having a hydrogen group or a halogenated hydrocarbon group, or an amino group having a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms. May be replaced with
R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms, hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, or hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, respectively. Represents a silyl group with
m and m'represent an integer of 0 or 1-8
When Z ¹¹ is (E ¹² ) (R ¹³ ) m'(R ¹⁴ ) p', one or both of p and p'are integers 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 is has a divalent hydrocarbon group, a hydrocarbon group silylene group have 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Represents a hydrocarbon group that may be
M ¹¹ represents titanium, zirconium or hafnium,
X ¹¹ and X ¹² independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. 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 azurenyl group, and may have a substituent, respectively. 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.
Q ²¹ is have a divalent hydrocarbon group, a hydrocarbon group of a hydrocarbon group which may have a silylene group or a C1-20 having 1 to 20 carbon atoms having 1 to 20 carbon atoms Represents a good gelmilene group,
M ²¹ represents titanium, zirconium or hafnium,
Each of X ²¹ and X ²² independently contains a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. 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 metallocene compounds [A-1] and [A-2] carried and converted into a cation, and [B-3] ion. Exchangeable layered silicate. The method for producing an olefin polymer according to claim 1, wherein the catalyst for olefin polymerization, which has been dried under reduced pressure in advance, is stored. The method for producing an olefin polymer according to claim 2, wherein the amount of the residual solvent in the catalyst for olefin polymerization dried under reduced pressure is 0.5 wt% or less. The storage is characterized in that the following component [C] is stored under the condition that 1 to 70 mol of the following component [C] is present in a total of 1 mol of the component [A-1] and the component [A-2]. The method for producing an olefin polymer according to any one of 3 to 3.
Ingredient [C]: Organoaluminium compound. The component [A-1] is a metallocene compound that forms a polymerization catalyst that produces olefin macromer [However, when the metallocene compound that forms a polymerization catalyst that produces olefin macromer is subjected to olefin homopolymerization at 70 ° C. 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. ], The method for producing an olefin polymer according to any one of claims 1 to 4. The method for producing an olefin polymer according to any one of claims 1 to 5 , wherein one or both of ^{M 11} and M ^{21 are hafnium.} The olefin according to any one of claims 1 to 6 , wherein the olefin polymer has a branching index (g') of 0.95 or less at a molecular weight (M) of 1 million (log M = 6). Method for producing polymer. The method for producing an olefin polymer according to claim 1, wherein at least one of the components [A-1] and [A-2] is a metallocene compound represented by the following general formula (3).

[In the general formula (3), R ³¹ and R ³² are independently halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups, and hydrocarbon groups or halogens having 1 to 20 carbon atoms, respectively. Cyril group having a hydrocarbon group, hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms having a silyl group having a halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 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-membered ring or a 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 is have a divalent hydrocarbon group, a hydrocarbon group of a hydrocarbon group which may have a silylene group or a C1-20 having 1 to 20 carbon atoms having 1 to 20 carbon atoms Represents a good gelmilene group,
M ³¹ represents titanium, zirconium or hafnium,
Each of X ³¹ and X ³² independently contains a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Represents a silyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. ] The invention according to any one of claims 1 to 6 , wherein the olefin polymer is a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 12 carbon atoms (excluding 3). Method for producing an olefin polymer of.

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