JPH10204112A - Olefin polymerization catalyst, production of olefin polymer and olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular-weight olefin (co)polymer having a high comonomer content in very high polymerization activity by using a catalyst prepared by previously bringing a group IVB transition metal compound having a specified structure into contact with an organoaluminumoxy compound, etc. SOLUTION: This catalyst is obtained by previously bringing a group IVB transition metal compound represented by the formula into contact with an organoaluminumoxy compound and/or a compound which reacts with the transition metal compound to form an ionic pair and optionally an organoaluminum compound. In the formulas, M is a group IVB transition metal atom; at least one R<1> is a 11-20 20C aryl or the like, and the rest are hydrogen atoms or the like; R<2> is hydrogen, a 1-10C alkyl or the like; R<3> and R<4> are each hydrogen, a 1-10C alkyl or the like; X<1> and X<2> are each hydrogen, a 1-20C hydrocarbon group or the like; and Y is a 1-20C divalent hydrocarbon group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst, a method for producing an olefin polymer, and an olefin polymer. More specifically, an olefin (co) polymer having a very high polymerization activity and a large molecular weight can be obtained. An olefin polymerization catalyst which can provide an olefin copolymer having a high comonomer content even when the use ratio of a comonomer is small, an olefin (co) polymer having a very high polymerization activity and a large molecular weight can be obtained, and a comonomer The present invention relates to a method for producing an olefin polymer capable of obtaining an olefin copolymer having a high comonomer content even when the use ratio is small, and an olefin polymer obtained by such a method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, ethylene homopolymer,
As a method for producing an olefin (co) polymer such as an ethylene / α-olefin copolymer, a propylene homopolymer, or a propylene / α-olefin copolymer, a titanium catalyst comprising a titanium compound and an organoaluminum compound, Alternatively, a method is known in which an olefin is polymerized in the presence of a vanadium-based catalyst such as a vanadium compound and an organoaluminum compound.

Further, a method is known in which an olefin is polymerized in the presence of a metallocene catalyst comprising a transition metal compound such as zirconocene and an organoaluminum oxy compound (aluminoxane). It is known that an olefin (co) polymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained while being able to polymerize with high activity.

[0004] In recent years, the requirements for physical properties of olefin (co) polymers have been diverse, and olefin (co) polymers having various physical properties have been demanded. There is also a demand for an olefin polymerization catalyst capable of producing such an olefin (co) polymer.

Under such circumstances, Japanese Patent Laid-Open Publication No. 5-345
No. 793 proposes a transition metal compound having an indenyl group and a fluorenyl group as ligands as a new compound which can be a catalyst component for olefin polymerization. However, when an olefin is polymerized using this transition metal compound as a catalyst component, there is a problem that only a polymer having a low activity and a small molecular weight can be obtained.

A transition metal compound having an indenyl group and a fluorenyl group is also proposed in EP 0707016 A1, and a specific aryl group such as a phenyl group or a naphthyl group is introduced at a specific position (position 4) of the indenyl group. A disclosed catalyst is disclosed. However,
Even when an olefin is polymerized using this transition metal compound as a catalyst component, there is a problem that only a polymer having a low activity and a small molecular weight can be obtained.

The present inventors have conducted studies in view of such prior art, and as a result, introduced a specific substituent at a specific position of a fluorenyl group of a transition metal compound, and converted these specific transition metal compound into an organic aluminum oxy group. The present invention has been found to be able to produce an olefin (co) polymer having a higher molecular weight and a higher molecular weight and to obtain an olefin copolymer having a higher comonomer content by using a catalyst pre-contacted with a compound or the like. Was completed.

[0008]

An object of the present invention is to provide an olefin polymerization catalyst capable of obtaining an olefin (co) polymer having a very high polymerization activity and a high molecular weight and obtaining an olefin copolymer having a high comonomer content. An object of the present invention is to provide a method for producing an olefin polymer used and an olefin polymer obtained by such a method.

[0009]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A-1) a transition metal compound of Group IVB of the periodic table represented by the following general formula (I): (B) (B-1) an organoaluminum oxy compound, and / or
Or (B-2) a compound capable of reacting with the transition metal compound (A-1) to form an ion pair, or (C) an organic aluminum compound if necessary, by pre-contacting the compound. It is characterized by.

[0010]

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Wherein M is a transition metal atom of Group IVB of the periodic table, and R ^{1 s} may be the same or different, and at least one of them has 11 to 11 carbon atoms.
An aryl group having 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, an alkylaryl group having 12 to 40 carbon atoms or a silicon-containing group, or R ¹ in at least two neighboring groups of the groups indicated, together with the carbon atoms to which they are bonded, an aromatic ring or forms an aliphatic ring [in this case, the ring formed by R ¹ may have R ¹ 4 to 2 carbon atoms as a whole, including the bonding carbon atoms
0], the other R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group,
R ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkenyl having 2 to 10 carbon atoms. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms,
A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and at least two of the groups represented by R ² are, together with the carbon atom to which they are bonded, aromatic, ring or aliphatic ring may form [this case a ring formed by R ² has a number of carbon atoms in all including carbon atoms to which R ² is attached 4-2
0, the other R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group], and R ¹ and R ² may be the same or different from each other; R ³ and R ⁴ may be the same or different from each other, and have a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms.
Alkyl group, aryl group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, 7 to
40 arylalkyl groups, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups,
A nitrogen-containing group or a phosphorus-containing group, X ¹ and X
² may be the same or different from each other, and represent a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, or X ¹ and X
² is a conjugated diene residue formed from Y, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, and 1
-20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,
-O -, - CO -, - S -, - SO -, - SO 2 -, -
NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )-,-
BR ⁵ — or —AlR ⁵ — (where R ⁵ is a hydrogen atom,
Halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms]).

The catalyst for olefin polymerization according to the present invention includes:
Component (A-1) described above, component (B-1) and / or component
(B-2) or, if necessary, further pre-contacting the component (C), followed by being supported on a particulate carrier to form a solid catalyst. Olefin polymer produced by pre-polymerization in the presence,
If necessary, an embodiment that serves as a prepolymerization catalyst comprising the component (C) is also included.

The first method for producing an olefin polymer according to the present invention is characterized in that an olefin is homopolymerized or two or more olefins are copolymerized in the presence of the olefin polymerization catalyst. .

The present invention is directed to the homopolymerization of ethylene, the copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms,
It can be used for homopolymerization of propylene, copolymerization of propylene with an α-olefin other than propylene, and the like.

The first olefin polymer according to the present invention comprises:
It is characterized by being manufactured by the method as described above. The first ethylene-based polymer according to the present invention is characterized by being produced by the above method.

The second method for producing an olefin polymer according to the present invention comprises: (A-2) a transition metal compound of Group IVB of the periodic table represented by the following general formula (II): (B) (B) -1) an organic aluminum oxy compound, and / or
Or (B-2) a catalyst obtained by pre-contacting a compound which reacts with the transition metal compound (A-2) to form an ion pair, or if necessary, further (C) an organoaluminum compound. Is characterized by homopolymerizing an olefin or copolymerizing two or more olefins in the presence of

[0017]

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(Wherein M is a transition metal atom of Group IVB of the periodic table, R ⁶ may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl having 1 to 10 carbon atoms. group, an aryl group having a carbon number of 6-10, an alkenyl group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group having a carbon number of 2 to 10, R ⁷ is Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, carbon atom An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or phosphorus Containing group There, R ⁶ and R ⁷ may be the same or different from each other, R ⁸ and R ^9, one of them is an alkyl group having 1 to 5 carbon atoms, the other is a hydrogen atom, a halogen atom, An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and X ¹ and X ² are And may be the same or different from each other, and are the same as X ¹ and X ² in the general formula (I), and Y is the same as Y in the general formula (I). It can be used for homopolymerization, copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, homopolymerization of propylene, or copolymerization of propylene with an α-olefin other than propylene.

The second olefin polymer according to the present invention comprises:
It is characterized by being manufactured by the method as described above. The second ethylene-based polymer according to the present invention is characterized by being produced by the above method.

[0020]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the catalyst for olefin polymerization, the method for producing an olefin polymer, and the olefin polymer according to the present invention will be described in detail.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization. The term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises (A)
-1) a transition metal compound of Group IVB of the periodic table represented by the following general formula (I): (B) (B-1) an organoaluminum oxy compound, and / or
Or (B-2) a compound which reacts with the transition metal compound (A-1) to form an ion pair or, if necessary, further (C) an organic aluminum compound by pre-contacting the compound.

First, each component used in the olefin polymerization catalyst according to the present invention will be described. The (A-1) transition metal compound used in the present invention is a transition metal compound of Group IVB of the periodic table represented by the following general formula (I).

[0024]

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In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium.
R ¹ may be the same or different, and at least one of them is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms,
An arylalkenyl group having 13 to 40 carbon atoms, an alkylaryl group having 12 to 40 carbon atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ¹ are those Together with the carbon atom to which it is attached, it forms one or more aromatic or aliphatic rings. In this case, the ring formed by R ¹ is R ¹
Has a total of 4 carbon atoms including the carbon atom to which
-20.

Examples of the case where at least two adjacent groups among the groups represented by R ^{1 form one} or more aromatic or aliphatic rings together with the carbon atoms to which they are bonded are a condensed phenyl group Condensed cyclohexyl group, condensed cyclopentadienyl group, condensed dihydrocyclopentadienyl group, condensed indenyl group, condensed tetrahydroindenyl, condensed fluorenyl group, condensed tetrahydrofluorenyl group, condensed tetrahydrofluorenyl group, condensed octa And a hydrofluorenyl group. These groups may be substituted with a chain alkyl group, a cyclic alkyl group, a halogen atom, a halogen-substituted alkyl group, an aryl group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a phosphorus-containing group.

An aryl group, an arylalkyl group, an arylalkenyl group, an alkylaryl group and an aromatic ring;
R ¹ other than R ¹ to form an aliphatic ring is a hydrogen atom,
A halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group.

The aryl group having 11 to 20 carbon atoms includes biphenylyl, anthryl, phenanthryl and the like, and the arylalkyl group having 12 to 40 carbon atoms includes phenanthrylmethyl, phenanthrylethyl, Phenanthryl propyl and the like, and examples of the arylalkenyl group having 13 to 40 carbon atoms include vinyl phenanthryl and the like.
Examples of the alkylaryl group to 40 include methylphenanthryl, ethylphenanthryl, propylphenanthryl, and the like, and halogen atoms include fluorine, chlorine, bromine, and iodine. ~ 1
Examples of the alkyl group of 0 include methyl, ethyl, propyl,
Butyl, hexyl, cyclohexyl, octyl, nonyl and the like.

Examples of the silicon-containing group include methylsilyl, phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl,
Examples include groups such as tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl.

The above alkyl group, aryl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen. R
² may be the same or different from each other, and represent a hydrogen atom,
A halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 to 1 carbon atoms
0 alkenyl group, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, silicon-containing group, oxygen-containing group, sulfur-containing Group, a nitrogen-containing group or a phosphorus-containing group.

At least two adjacent groups among the groups represented by R ² may form one or more aromatic or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ² is R
R having a total of 4 to 20 carbon atoms including the carbon atom to which ² is bonded and forming an aromatic ring or an aliphatic ring
R ² other than ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group.

The group constituted by two or more groups represented by R ² forming one or more aromatic or aliphatic rings includes an embodiment in which a fluorenyl group has the following structure. It is.

[0033]

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Examples of the alkyl group and halogen atom having 1 to 10 carbon atoms include the same groups and atoms as described above. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, biphenylyl, α- or β-naphthyl, anthryl, and phenanthryl. Examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl and phenylethyl. Phenylpropyl, phenanthrylmethyl, phenanthrylethyl, phenanthrylpropyl and the like, and the arylalkenyl group having 8 to 40 carbon atoms includes styryl, vinylphenanthryl and the like. Examples of the alkylaryl group having a carbon number of 7 to 40 include tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, methylnaphthyl, methylphenanthryl, ethylphenanthryl, and propylphenanthryl. Is 2 to 10 alkenyl groups Examples thereof include vinyl, propenyl, cyclohexenyl and the like.Examples of the silicon-containing group include the same groups as described above.Examples of the oxygen-containing group include a hydroxyl group, methoxy, ethoxy, propoxy and butoxy. , Phenoxy, methylphenoxy, dimethylphenoxy, aryloxy groups such as naphthoxy, phenylmethoxy, arylalkoxy groups such as phenylethoxy, and the like.As the sulfur-containing group, a substituent in which the oxygen of the oxygen-containing group is substituted with sulfur, And methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, Sulfonate groups such as pentafluorobenzenesulfonate, and sulfinate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate. Examples of the nitrogen-containing group include an amino group, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, an alkylamino group such as dicyclohexylamino, phenylamino, diphenylamino,
Examples thereof include an arylamino group such as ditolylamino, dinaphthylamino, and methylphenylamino or an alkylarylamino group. Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

Among them, R ² is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

A preferred example of such a fluorenyl group having R ² as a substituent is a 2,7-dialkyl-fluorenyl group. In this case, the alkyl group of the 2,7-dialkyl is preferably a carbon atom An alkyl group having 1 to 5 numbers is exemplified.

The above R ¹ and R ² may be the same or different from each other. R ³ and R ⁴ may be the same or different from each other, and include the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon atom Number 2-10
An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,
An alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Of these, at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and oxygen-containing Group, a sulfur-containing group or a nitrogen-containing group, or a conjugated diene residue formed from X ¹ and X ² , specifically, as a halogen atom, an oxygen-containing group, a sulfur-containing group and a nitrogen-containing group, The same atoms or groups as described above can be exemplified.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, and adamantyl; vinyl, propenyl, cycloalkyl Alkenyl groups such as hexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzyl Phenyl,
Aryl groups such as pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like;
Examples of the halogenated hydrocarbon group having from 20 to 20 include groups in which the above hydrocarbon group having from 1 to 20 carbon atoms is substituted with halogen.

The conjugated diene residue formed from X ¹ and X ² includes η ⁴ -1,4-diphenyl-1,3-butadiene, η ⁴
-1,3-butadiene, η ⁴ -1,4-dibenzyl-1,3-butadiene, η ⁴ -1-phenyl-1,3-pentadiene, η ⁴ -3-methyl-
1,3-pentadiene, η ⁴ -1,4-bis (trimethylsilyl)
-1,3-butadiene, 2,3-dimethylbutadiene, η ⁴ -2,4-
Hexadiene, isoprene and the like can be mentioned.

The conjugated diene residue formed from X ¹ and X ² includes 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene. Groups are preferred, and these residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing group is preferred. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, Valent tin-containing group, -O-, -CO-, -S-,-
_{SO -, - SO 2 -,} - NR 5 -, - P (R 5) -, -
^{P (O) (R 5)} -, - BR 5 - or -AlR ⁵ -
[However, R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms], and specifically, methylene, dimethylmethylene , 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, and other alkylene groups, diphenylmethylene, diphenyl An arylalkylene group such as -1,2-ethylene having 1 to 20 carbon atoms
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n- Alkyl silylenes such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, and aryl A divalent silicon-containing group such as an alkyldisilylene, an alkylaryldisilylene, or an aryldisilylene group such as a silylene group, tetramethyl-1,2-disilylene, or tetraphenyl-1,2-disilylene; A divalent germanium-containing group in which silicon in the group is replaced with germanium; Examples include a divalent tin-containing group in which silicon of the i-containing group is substituted with tin.

Among these divalent groups, those in which the shortest connecting part of -Y- represented by the general formula (I) is composed of one or two atoms are preferable. Also, R
⁵ is the same halogen atom and 1 to 2 carbon atom as described above.
0 hydrocarbon group and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Of these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and is preferably a divalent silicon-containing group. More preferably, alkyl silylene,
Particularly preferred is alkylarylsilylene or arylsilylene.

Specific examples of the transition metal compound (A-1) represented by the above general formula (I) are shown below. Ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, ethylene 2-methyl
-4 (9-phenanthryl) -1-indenyl {(2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl}
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4, 5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t
-Butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, ethylene (2,6-dimethyl-4, 5-benzo-1-indenyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, ethylene (2 -Methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride;
Ethylene (2-methyl-α-acenaphth-1-indenyl)
(2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphth-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene ｛2 -Methyl-4 (9-phenanthryl) -1-indenyl {(9-fluorenyl) zirconium dichloride, dimethylsilylene} 2-n-propyl-4
(9-phenanthryl) -1-indenyl {(9-fluorenyl) zirconium dichloride, dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium dichloride, Dimethylsilylene 2-methyl-4 (9-phenanthryl) -1-
Indenyl｝ (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5
-Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2 -Methyl-
4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride , Dimethylsilylene (2-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-α-acenaphth-1-indenyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4
(9-phenanthryl) -1-indenyl} (2,7-dimethyl-
9-fluorenyl) zirconium dichloride, diphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl- 4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Silylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium Dichloride,

Diphenylsilylene (2-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-
Methyl-α-acenaphth-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene ｛2-methyl-4 (9-phenanthryl)
-1-indenyl {(9-fluorenyl) zirconium dichloride, methylphenylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene 2-methyl-4 (9-phenanthryl) -1-indenyl {(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-
Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride,
Methylphenylsilylene (2-methyl-α-acenaphth-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl
-α-acenaphth-1-indenyl) (2,7-di-t-butyl-9-
Fluorenyl) zirconium dichloride, ethylene 3-
Methyl-4 (9-phenanthryl) -1-indenyl {(9-fluorenyl) zirconium dichloride, ethylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) zirconium Dichloride, ethylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5-benzo-1) -Indenyl) (9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-4,5 -Benzo-1-indenyl) (2,7-di
-t-butyl-9-fluorenyl) zirconium dichloride,
Ethylene (3-methyl-α-acenaphth-1-indenyl)
(9-Fluorenyl) zirconium dichloride, ethylene (3-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-α-acenaphth-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, dimethylsilylene {3-methyl-4 (9- Phenanthryl) -1-indenyl {(2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene} 3-
Methyl-4 (9-phenanthryl) -1-indenyl｝ (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo) -1-indenyl)
(2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethyl Silylene (3-methyl-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-α-acenaphth-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride ,

Dimethylsilylene (3-methyl-α-acenaphth-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene ｛3-
Methyl-4 (9-phenanthryl) -1-indenyl {(9-fluorenyl) zirconium dichloride, diphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5- Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9-Fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α-acenaphth-1-
Indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α-acenaphth-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (3-methyl-α
-Acenaphth-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium Dichloride, methylphenylsilylene {3-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, methylphenylsilylene ｛3-
Methyl-4 (9-phenanthryl) -1-indenyl｝ (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-4,5-benzo-1-
Indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-4,5-benzo-1-
Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphth-1-indenyl) (9-
Fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphth-1-indenyl)
(2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-α-acenaphth-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene ( 2-methyl-4,5
-Benzo-1-indenyl) (2,7-ditrimethylsilyl-9-
Fluorenyl) zirconium dichloride, ethylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2,7-dimethyl-4,5- (2-methyl-benzo)
1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, dimethylsilylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-ditrimethylsilyl)
-9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) Zirconium bis (trifluoromethanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconiumbis (trifluoromethanemethanesulfonate) Nato),

Dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-
Dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1
-Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-
4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo
-9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, Dimethylsilylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,
7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2 , 7-Dimethyl-4,5- (2
-Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-
Benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-
Fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-
4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1
-Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7 -Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1
-Methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) ( 2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5
-(1-Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1
-Indenyl) (2,7-di-i-propyl-9-fluorenyl)
Zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-
Dimethyl-9-fluorenyl) zirconium dichloride,
Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo) 1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonate),

Dimethylsilylene (2-methyl-4,5-benzo-
1-indenyl) (2,7-di-t-butoxy-9-fluorenyl)
Zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-
Di-t-butoxy-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-
Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-
4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonate),
Dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9-Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonate),
Dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1
-Indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2, 7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-dimethyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di -
t-butyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5-
(1-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-
4,5- (1-methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1 -Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-
Fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium bis (methane Sulfonato), dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonate ), Dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1
-Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium bis (methanesulfonato), dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo
-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9- (4,5- Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di
-t-butoxy-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl
-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-
(4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl) ) Zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium dichloride,

Dimethylsilylene (2-methyl-4,5-benzo-
1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl
-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-
4,5- (2-methyl-benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4, 5- (2
-Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy)
-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-
Methyl-benzo) -1-indenyl) (2,7-diphenyl-9-
(4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-) 9-
(4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9- (4 ,Five-
Methylenephenanthryl)) zirconium dichloride,
Dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium Dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo)
-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,
5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-
Benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo)
1-indenyl) (2,7-di-t-butoxy-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl- Benzo) -1
-Indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl ) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1 -Indenyl) (2,7-dimethyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-
Methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-
9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5- Methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl) )) Zirconium dichloride, dimethylsilylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl))
Zirconium dichloride, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium dichloride,

Dimethylsilylene (2,7-dimethyl-4,5- (2
-Methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylmethylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-
Dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9
-Fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di
-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethyl Methylene (2-methyl-4,5
-Benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,
6-dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,
7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Dibromo-9-fluorenyl) zirconium dichloride,
Dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,
7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl- 9-
Fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7 -Dimethyl-4,5-
(1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1
-Indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7- Dibromo-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-
Methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-
9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2 , 7-dimethyl-
4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-
Propyl-9-fluorenyl) zirconium dichloride,
Dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7 -Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-
Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2,6-dimethyl
-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo)
1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-
Di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium η ⁴ -1- Phenyl-1,3-pentadiene,
Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)
Zirconium η ⁴ -1,4-diphenylbutadiene, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-
Dibromo-9-fluorenyl) zirconium η ⁴ -2,4-hexadiene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) Zirconium η ⁴ -1,4-diphenyl-1,3-butadiene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium η ⁴ -3-methyl-1,3-pentadiene,
Dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium η ⁴ -2,4-hexadiene, diphenylsilylene (2-methyl
-4,5-benzo-1-indenyl) (2,7-ditrimethylsilyl)
-9-Fluorenyl) zirconium dichloride, diphenylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylsilylene (2,
7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethyl) silyl-9-fluorenyl) ) Zirconium dichloride, methylphenylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2,7-dimethyl-4,5-
Benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-7-trimethylsilyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-7-trimethylsilyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride , Dimethylsilylene (2-
Methyl-4,5-benzo-1-indenyl) (2,7-dimethylamino-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2-
Methylamino-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-diethylamino-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4, Five-
Benzo-1-indenyl) (2-ethylamino-9-fluorenyl) zirconium dichloride and the like.

In the above-mentioned zirconium compound, a compound in which zirconium is replaced with titanium or hafnium can also be used. Among the above zirconium compounds, for example, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) The structural formula of zirconium dichloride is shown below.

[0053]

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Further, dimethylsilylene (2,6-dimethyl-
4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-
The structural formula of butyl-9-fluorenyl) zirconium dichloride is shown below.

[0055]

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When the above transition metal compound (A-1) is used as an olefin polymerization catalyst in combination with, for example, an organoaluminum oxy compound, an olefin (co) polymer having a high molecular weight is obtained, and An olefin copolymer having a high comonomer content can be obtained even when the use ratio is small.

The transition metal compound (A-1) can be produced, for example, as follows. First, a substituted fluorenyl anion (compound (i)) represented by the following general formula (i) and a compound (compound (ii)) represented by the following general formula (ii) are reacted in a solvent. The following general formula (iii)
Is obtained.

[0058]

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In the general formula (i), R ² may be the same or different, and is the same as R ² in the general formula (I). In the general formula (ii), Y
Is the same as R ² in formula (I), and X ³
And X ⁴ may be the same or different, and each represents a hydrogen atom, a halogen atom, an —OR group, a —OCOR group, a —S
R group, -OSO ₂ R group, -SO ₂ R group, -NRR 'group (where R and R' may be the same or different from each other, and have a hydrogen atom, a halogen atom, a carbon atom number of 1 to 1).
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms,
It is an alkylaryl group having 7 to 30 carbon atoms. )
Is shown.

In the general formula (iii), R ² , Y and X ⁴ are the same as those in the general formulas (i) and (ii).
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and mesitylene; and aliphatic hydrocarbons such as pentane, hexane, and heptane. Among them, diethyl ether, tetrahydrofuran, toluene and hexane are preferred.

In the reaction between the compound (i) and the compound (ii), the compound (ii) is used in a molar ratio to the compound (i) in an amount of 0.5 to 200, preferably 1 to 60. The solvent is used in a weight ratio of 1 to 10 with respect to the compound (ii).
It is used in an amount of 0, preferably 1-20.

The reaction temperature between compound (i) and compound (ii) is -78 ° C to 150 ° C, preferably -78 ° C to 50 ° C.
And the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

The compound (i) can be obtained by reacting a substituted fluorene with a base in a solvent or without a solvent. Here, examples of the base include elemental metals such as sodium metal, potassium potassium and lithium metal; hydride compounds such as potassium hydride and sodium hydride; and organic lithium compounds such as methyl lithium and n-butyl lithium. Of these, sodium metal, sodium hydride, and n-butyllithium are preferable, and n-butyllithium is particularly preferable.

Examples of the solvent used for the reaction between the substituted fluorene and the base include the same solvents as those used for the reaction between the compound (i) and the compound (ii). Among them, diethyl ether, tetrahydrofuran, Toluene and hexane are preferred, and diethyl ether and toluene are particularly preferred.

In the reaction of the substituted fluorene with a base,
The base is used in a molar ratio of 0.5 to 2.
0, preferably in the range of 0.90 to 1.5, the solvent being 1 to 10 by weight relative to the substituted fluorene.
It is used in an amount of 0, preferably 1-20.

The reaction temperature between the substituted fluorene and the base is-
The reaction temperature is in the range of 78 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1 to 50 hours.
~ 25 hours.

Next, the compound (compound (iii)) represented by the general formula (iii) is reacted with a substituted indenyl anion (compound (iv)) represented by the following general formula (iv) to give the following: A compound represented by the general formula (v) is produced.

[0068]

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[0069] In the general formula (iv), R ^1, R ³ and R ⁴ are the same as R ^1, R ³ and R ⁴ in the general formula (I), Z is lithium, sodium, potassium, etc. Represents an alkali metal.

In the general formula (v), R ¹ , R ² ,
R ³ , R ⁴ and Y are the same as R ¹ , R ² , R ³ , R ⁴ and Y in the general formula (I). In the reaction of compound (iii) with compound (iv), compound (i)
ii) represents a compound (iv) in a molar ratio of 0.5 to 10,
Preferably used in an amount ranging from 0.5 to 5, the solvent is
It is used in an amount of 1 to 100, preferably 1 to 20 by weight relative to compound (iv).

The reaction temperature of compound (iii) with compound (iv) is -78 ° C to 150 ° C, preferably -78 ° C to 5 ° C.
It is in the range of 0 ° C. and the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

By reacting the compound (iii) with the compound (iv) under such conditions, the compound represented by the general formula (v)
A cross-linked substituted indenyl-substituted fluorenyl compound represented by the following formula can be obtained.

The compound (iv) can be obtained by reacting a substituted indene with a base in a solvent or without a solvent. Examples of the base used in the reaction include the same bases as those used in producing the substituted fluorenyl anion. Among these, sodium metal, sodium hydride, and n-butyllithium are preferable, and particularly, n-Butyllithium is preferred.

Examples of the solvent used in the reaction include the same solvents as those used in the reaction between the compound (i) and the compound (ii). Of these, diethyl ether, tetrahydrofuran, toluene and hexane are preferable. Particularly, diethyl ether and toluene are preferred.

In the reaction between the substituted indene and the base, the base is used in a molar ratio of 0.5 to 2.0 with respect to the substituted indene,
It is preferably used in an amount in the range of 0.90 to 1.5, and the solvent is used in an amount of 1 to 100, preferably 1 to 20 by weight relative to the substituted indene.

The reaction temperature between the substituted indene and the base is -7
The temperature is in the range of 8 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1 to 50 hours.
25 hours.

The transition metal compound (A-1) represented by the general formula (I) is represented by the following general formula (vii) together with the anion of the crosslinked substituted indenyl-substituted fluorenyl compound produced as described above. By reacting the compound with a compound in a solvent.

[0078]

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In the general formula (vi), R ¹ , R ² ,
R ³ , R ⁴ and Y are the same as R ¹ , R ² , R ³ , R ⁴ and Y in the general formula (I). In Formula (vii), M is the same as M in the general formula (I), X ⁵ may be the same or different from each other, a hydrogen atom, a halogen atom, -OR group, -OC
X represents an OR group, —SR group, —OSO ₂ R group, or —SO ₂ R group, and X ⁶ represents a hydrogen atom, a halogen atom, an —OR group, —O
COR group, -SR group, -OSO ₂ R group, -SO ₂ R group,
-NRR 'group (where R and R' may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 7 to 30 carbon atoms), and n is 1 or 2. When n = 2, X ⁶ may be the same or different.

In the reaction between the anion of the substituted substituted indenyl-substituted fluorenyl compound represented by the general formula (vi) (compound (vi)) and the compound represented by the general formula (vii) (compound (vii)) The compound (vii) is used in a molar ratio of 0.1 to 200, preferably 0.5 to 5.0 with respect to the compound (vi), and the solvent is used with respect to the substituted indenyl anion. It is used in an amount of 1 to 100, preferably 1 to 20 by weight.

The reaction temperature between compound (vi) and compound (vii) is -78 ° C to 150 ° C, preferably -78 ° C to 5 ° C.
It is in the range of 0 ° C. and the reaction time is 0.1 to 50 hours, preferably 1 to 25 hours.

The compound (vi) can be obtained by reacting a cross-linked substituted indenyl-substituted fluorenyl compound (compound (v)) with a base in a solvent or without solvent.

Examples of the base used in the reaction include the same bases as used in producing the above substituted fluorenyl anion. Among them, sodium metal, sodium hydride and n-butyllithium are exemplified. Preferably
Particularly, n-butyllithium is preferable.

Examples of the solvent used in the reaction include the same solvents as those used in the reaction between the compound (i) and the compound (ii), and among these, diethyl ether, tetrahydrofuran, toluene and hexane are preferable. Particularly, diethyl ether and toluene are preferred.

In the reaction of the compound (v) with a base, the base is used in a molar ratio of 1.0 to 10.3 with respect to the compound (v).
0, preferably used in an amount ranging from 1.5 to 3.0,
The solvent is used in an amount of 1 to 100, preferably 1 to 20 by weight relative to compound (v).

The reaction temperature between the substituted indene and the base is -7
The temperature is in the range of 8 ° C to 150 ° C, preferably -78 ° C to 50 ° C, and the reaction time is 0.1 to 50 hours, preferably 1 to 50 hours.
25 hours.

The transition metal compound (A) obtained as described above
-1) can be purified by removing the inorganic salt by a usual operation and then crystallization. Further, the transition metal compound (A-1) can also be produced by the following method. First, the compound (iv) and the compound (ii) are reacted to produce a compound represented by the following general formula (viii) (compound (viii)).

[0088]

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Next, the compound (viii) is reacted with a substituted fluorenyl anion (compound (i)) to obtain a crosslinked substituted indenyl-substituted fluorenyl compound (compound (v)). Subsequently, the compound (vi) obtained by anionizing the compound (v) is reacted with the compound (vii) to obtain a transition metal compound (A-1). In this production method, the same reaction conditions as described above can be employed for each reaction condition.

Further, the transition metal compound (A-1) can also be produced by the following method. First, a substituted indene represented by the following general formula (ix) (compound (i
x)) and a substituted ketone (compound (x)) represented by the following formula (x) to produce a compound represented by the following general formula (xi) (compound (xi)).

[0091]

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In the reaction, the substituted indene is converted to a substituted indenyl anion using the above-mentioned base, and then the substituted ketone is converted to a substituted indenyl anion in a molar ratio of 0.1 to 1 with respect to the substituted indenyl anion.
The reaction is carried out by adding an amount of 00, preferably 0.1 to 20.

Next, the obtained compound (xi) is reacted with a substituted fluorenyl alunion (compound (i)) to obtain a cross-linked substituted indenyl-substituted fluorenyl compound (compound (v)). This compound (xi) and compound (i)
In the reaction with the compound (i), the molar ratio of the compound (i) to the compound (xi) is 0.1 to 100, preferably 0.5 to 5.0.
Used in amounts ranging from zero. Subsequently, the anion of the cross-linked substituted indenyl-substituted fluorenyl compound is reacted with the compound (vii) in a solvent to form the transition metal compound (A-1).
Get. In this production method, the same reaction conditions as described above can be employed for each reaction condition.

The organoaluminum oxy compound (B-1) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. It may be a compound.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride, etc. A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the preparation of the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trialkylalkyl such as trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
The organoaluminum compound used in the preparation of the aluminoxane is represented by the formula (i-C ₄ H ₉ ) _x Al _y (C
₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧ 2)
x. ) Can also be used.

The above-mentioned organoaluminum compounds can be used in combination of two or more. Solvents used in the preparation of aluminoxane include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. , Cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Hydrocarbon solvents such as chlorides, especially chlorides and bromides.

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred. Further, as the arnoxane that can be used in the present invention, there is one that is further treated with water in the presence or absence of the solvent. Usually, the water treatment is carried out by contacting a solution of aluminoxane with water or an active hydrogen-containing compound.

Examples of the active hydrogen-containing compound include alcohols such as methanol, ethanol, n-propanol and isopropal, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid. Of these, alcohols and diols are preferred, and alcohols are particularly preferred.

The water or active hydrogen-containing compound to be brought into contact with the aluminoxane solution is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, etc., an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or It can be used in vapor, solid or solid form. In addition, as water, crystallization water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, cerous chloride, etc., or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide and the like are adsorbed. Adsorbed water or the like can also be used.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out in a solvent such as a hydrocarbon solvent. As the solvent used at this time, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene, pentane, hexane, heptane,
Hydrocarbon solvents such as aliphatic hydrocarbons such as octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane; petroleum fractions such as gasoline, kerosene, and gas oil; Halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, in particular, halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran can also be used. Among these media, aromatic hydrocarbons are particularly preferred.

The water or active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on Al atoms in the aluminoxane solution. The concentration in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water in the system is usually 2
× 10 ^{-4 to} 5 mol / l, preferably 2 × 10 ^-3 to
Desirably, the concentration is 3 mol / liter.

The contact of the aluminoxane solution with water or an active hydrogen-containing compound may be carried out specifically as follows. (1) A method in which a solution of aluminoxane is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound. (2) A method of contacting the aluminoxane with the vapor by, for example, blowing the vapor of water or an active hydrogen-containing compound into the solution of the aluminoxane. (3) A method in which a solution of aluminoxane is brought into direct contact with water, ice or an active hydrogen-containing compound. (4) A solution of aluminoxane and a hydrocarbon suspension of a compound containing adsorbed water or a compound of water of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound has been adsorbed are mixed to form aluminoxane and adsorbed water or A method of contacting with water of crystallization.

The aluminoxane solution described above may contain other components as long as the reaction between the aluminoxane and water or the active hydrogen-containing compound is not adversely affected.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out at -50 to 150 ° C.
Preferably it is 0-120 degreeC, More preferably, it is 20-10.
It is performed at a temperature of 0 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 0.5 to 300 hours, preferably about 1 to 150 hours.

Among them, it is preferable to perform water treatment by blowing water, preferably water vapor, or an active hydrogen-containing compound, preferably an inert gas containing the vapor, into a solution of aluminoxane. Here, the inert gas includes
There is nitrogen gas and the like.

In this case, the temperature of the aluminoxane solution and the inert gas is usually 0 to 100 ° C., preferably 0 to 100 ° C.
６０60 ° C. The organoaluminum oxy compound used in the present invention has a molar ratio ((Me + R) of an alkyl group (a total of a methyl group (Me) and another alkyl group (R)) to an aluminum atom (Al) in the organoaluminum oxy compound. ) / Al) is desirably 1.85 or less, preferably in the range of 1.8 to 1.2. Also, M
e / R is 95/5 or less, especially 95/5 to 10/9.
It is preferably in the range of 0.

Next, the method of obtaining the (Me + R) / Al ratio is as follows.
The case where R is an isobutyl (i-Bu) group will be described as an example. First, the hexane of this aluminoxane hexane solution is removed by evaporation. This is to remove isobutane mixed in hexane. The dried aluminoxane is diluted with normal hexane so that the Al concentration becomes 5 to 6% by weight. The aluminum concentration of this solution is measured.

Next, a solution of an organic aluminum oxy compound in an amount of 2 mmol in terms of aluminum atoms is charged into a flask sufficiently purged with nitrogen. At this time, hexane is added and adjusted so that the total amount of the solution becomes 40 ml. After cooling the system to 20 ° C., 10 ml of a 0.5 N aqueous sulfuric acid solution is added dropwise. The gas generated by this operation is collected by a gas burette. The methane and isobutane generated at this time are quantified. Actually analyze the gas phase and liquid phase.

For the gas phase, after confirming that the gas generation has been completely stopped, the gas generation amount (a milliliter) and the gas temperature (t ° C.) are measured, and the generated gas molar amount is determined. On the other hand, for the liquid phase, the methane and isobutane generated by the hydrolysis of the aqueous sulfuric acid are quantified (mol) by the internal standard GLC method. The amount of aluminum atoms in the organic aluminum oxy compound is measured by plasma emission spectroscopy.

The transition metal compound (A) used in the present invention
Examples of the compound (B-2) (hereinafter sometimes referred to as “ionized ionic compound”) which reacts with -1) to form an ion pair include JP-A-1-501950 and JP-A-1-502.
No. 036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321
No. 106 or the like, Lewis acids, ionic compounds, borane compounds, and carborane compounds.

Examples of the Lewis acid include a magnesium-containing Lewis acid, an aluminum-containing Lewis acid, a boron-containing Lewis acid, and among them, a boron-containing Lewis acid is preferable.

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following formula (III). BR ¹¹ R ¹² R ¹³ (III) (wherein, R ¹¹ , R ¹² and R ¹³ may be the same or different and have a substituent such as a fluorine atom, a methyl group, a trifluoromethyl group, etc.) A phenyl group,
Or a fluorine atom. Specific examples of the compound represented by the above formula (III) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoro Methylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, tris ｛3,5-di (trifluoro Methylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the transition metal compound (A-1) by reacting with the transition metal compound (A-1), thereby stabilizing the transition metal cation species by forming an ion pair. Such anions include organoboron compound anions,
There are an organic arsenic compound anion, an organic aluminum compound anion and the like, and those which are relatively bulky and stabilize transition metal cation species are preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, a ferrocenium cation, etc.

Of these, ionic compounds containing a boron compound as an anion are preferred.
For example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron , Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron , Tri (n-butyl) ammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) boron and other trialkyl-substituted ammonium salts; N, N-dimethyl N, N-dialkylanilinium salts such as Nilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron; Dialkylammonium salts such as (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammoniumtetra (phenyl) boron; triphenylphosphoniumtetra (phenyl) boron, tri (methylphenyl) phosphoniumtetra (phenyl) And triarylphosphonium salts such as boron and tri (dimethylphenyl) phosphoniumtetra (phenyl) boron.

Further, ionic compounds containing a boron atom include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate,
Ferrocenium tetra (pentafluorophenyl) borate can also be mentioned.

Further, examples of the ionic compound containing a boron atom include the following compounds. (In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Salts of anions, for example, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (N-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate and the like.

Examples of borane compounds, carborane complex compounds, and salts of carborane anions include decaborane (1
4), 7,8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride-7,8-
Dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 6-carbadecaborate (1
4), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium
7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (1
2), tri (n-butyl) ammonium dodeca hydride-8-methyl 7,9-dicarboundecaborate, tri (n-butyl
Butyl) ammonium undecahydride 8-ethyl-
7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-8-allyl-7, 9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carbaundecaborate and the like.

Examples of the carborane compound and carborane salt include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl -1,3-dicarbanonaborane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,3-dimethyl-1,3-dicarbanona borane and the like.

Further, examples of the ionic compound containing a boron atom include the following salts of metal carboranes and metal borane anions. (In the ionic compounds listed below, the counter ion is tri (n-butyl)
Ammonium, but not limited thereto. For example, tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (I
II), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Decahydride-7,8-dicarboundecaborate) cubate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal) Boundecaborate) Nickelate (IV) etc.

Further, examples of the ionic compound containing a boron atom include the following compounds. Triphenylcarbenium tetrakis {(2,3,5,6-tetrafluoro-4-triisopropylsilyl) phenyl} borate, N, N-dimethylanilinium tetrakis {(2,3,5,
6-tetrafluoro-4-triisopropylsilyl) phenyl} borate, triphenylcarbeniumtetrakis {(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl} borate, N, N-dimethyl Anilinium tetrakis {(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl} borate, triphenylcarbenium bis (octafluorobiphenylene) borate,
N, N-dimethylanilinium bis (octafluorobiphenylene) borate, triphenylcarbenium bis (octafluoro-1,1'-spiro) biboronol, N, N-dimethylanilinium bis (octafluoro-1,1'-) Spiro) biboronol and the like.

The ionized ionic compound as described above is
Two or more kinds can be used in combination. The olefin polymerization catalyst according to the present invention may further contain the following (C) an organoaluminum compound in addition to the above components, if necessary.

The organoaluminum compound (C) optionally used in the present invention can be represented by, for example, the following general formula (IV). During ^{_{R a n AlX 3-n ...}} (IV) ( wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
3. In the above formula (IV), ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkylaluminums such as trioctylaluminum and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride; diethylaluminum chloride; diisopropylaluminum chloride; diisobutylaluminum chloride; dialkylaluminum halides such as dimethylaluminum bromide; methyl Alkyl aluminum sesquihalides such as aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum Alkylaluminum dihalides such as dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the organoaluminum compound (C), a compound represented by the following formula (V) can be used. During ^{_{R a n AlY 3-n ...}} (V) ( wherein, R ^a is as defined above, Y is -OR ^b group, -
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
a iR ^f ₃ group or -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., ^Re is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g are a methyl group,
And an ethyl group. Specific examples of such an organoaluminum compound include the following compounds. _{^{(I) R a n Al (}} OR b) compounds represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide. _{^{(Ii) R a n Al (}} OSiR c 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C 2 H 5)
₃ ) etc. _{^{(Iii) R a n Al (}} OAlR d 2) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OAl (C
_{2 H 5) 2), (} iso-C 4 H 9) 2 Al (OAl (iso-C 4 H
₉ ) ₂ ) etc. _{^{(Iv) R a n Al (}} NR e 2) compounds represented by _3-n,
For example, (CH ₃ ) ₂ Al (N (C ₂ H ₅ ) ₂ ), (C
_{2 H 5) 2 Al (NH} (CH 3)), (CH 3) 2 Al (N
H (C ₂ H ₅ )), (C ₂ H ₅ ) ₂ Al [N (Si (C
_{H 3) 3) 2],} (iso-C 4 H 9) 2 Al [N (Si (C
Such as H _{3) 3) 2]. ^{(V) R a n Al (}} SiR f 3) a compound represented by _3-n, e.g., _{(iso-C 4 H 9)} 2 Al (Si (CH 3) 3)
Such.

In the present invention, among these, ^Ra ₃ A
1, R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAl
R ^d ₂ ) An organoaluminum compound represented by _3-n can be mentioned as a preferred example, and a compound in which ^Ra is an isoalkyl group and n = 2 is particularly preferable. These organoaluminum compounds can be used in combination of two or more.

In the olefin polymerization catalyst according to the present invention, the component (A-1) and the component (B-1) and / or the component (B-2) or, if necessary, the component (C) are further added. For the preliminary contact, each component is dissolved or suspended in an inert solvent and then stirred and mixed. After dissolving or suspending any of the components, a method of adding the remaining components therein and stirring the mixture is exemplified. Further, the contacted mixture is directly supplied to the polymerization system. In addition, a solvent may be partially removed from the mixture or a solvent may be added as necessary.

The pre-contact temperature is usually -50 to 100
C., preferably at a temperature of -20 to 50C.
The proportion of each component used is adjusted according to the proportion of each component in the polymerization system described below. The preliminary contact time is usually 10 minutes or more, especially 10 minutes to 24 hours, preferably about 25 minutes to 10 hours.

The catalyst for olefin polymerization according to the present invention comprises the above component (A-1), component (B-1) and / or component (B-
2) Alternatively, the catalyst may be a solid catalyst supported on a particulate carrier after the component (C) is further preliminarily contacted as required.

The olefin polymerization catalyst is a prepolymerized catalyst comprising the solid catalyst, an olefin polymer produced by polymerization in the presence of the solid catalyst, and, if necessary, the component (C). It may be.

The particulate carrier used for the solid catalyst and the prepolymerized catalyst is an inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 200 μm.
It is a granular or particulate solid of μm.

Among them, a porous oxide is preferable as the inorganic carrier. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Z
rO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, Ba
O, ThO ₂ or the like, or a mixture thereof, for example, Si
O ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , S
iO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO _2-
MgO and the like can be exemplified. Among them, Si
It is preferable that the main component be at least one component selected from the group consisting of O ₂ and Al ₂ O ₃ .

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

The properties of such a fine particle carrier differ depending on the kind and production method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g,
It is desirable that the pore volume is 0.3 to 2.5 cm ³ / g. The fine particle carrier may be 100 to 100 as necessary.
It is used by firing at a temperature of 0 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
Granular or particulate solids of organic compounds having a size of 0 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers formed mainly of α-olefins having 2 to 14 carbon atoms, such as pentene, and polymers or copolymers formed mainly of vinylcyclohexane or styrene.

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention. In the method for producing an olefin polymer according to the present invention, the transition metal compound (A-1) and the organic aluminum oxy compound and / or the ionized ionic compound (B) as described above, An olefin is homopolymerized or two or more olefins are copolymerized in the presence of an olefin polymerization catalyst formed by pre-contacting with an aluminum compound (C).

The olefin used in the present invention includes:
Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-
Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,
Examples thereof include a chain or branched α-olefin having 3 to 20 carbon atoms such as 1-octadecene.

Further, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
Olefins having an aliphatic or aromatic ring such as a, 5,8,8a-octahydronaphthalene, styrene, and vinylcyclohexane are also included.

In addition to olefin, butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene,
Linear or cyclic dienes such as 5-ethylidene-2-norbornene, 7-methyl-1,6-octadiene, 6,10-dimethyl-1,5,
Linear or cyclic trienes such as 9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 6,10,14-trimethyl
Copolymerization of various polyenes such as linear or cyclic tetraenes such as -1,5,9,13-pentadecatetraene and 5,9,13-trimethyl-1,4,8,12-tetradecatetraene It can also be done.

In the (co) polymerization of an olefin, the above transition metal compound (A-1) is usually used in an amount of about 0.00005-0.
It is used in an amount of 1 mmol, preferably about 0.0001-0.05 mmol.

The organoaluminum oxy compound (B-1) is
The aluminum atom is usually used in an amount of about 1 to 10,000 mol, preferably 10 to 50,000 mol, per 1 mol of the transition metal atom.
It is used in an amount such that it becomes 00 mol.

The ionized ionic compound (B-2) is used in an amount such that the boron atom is usually about 0.5 to 20 mol, preferably 1 to 10 mol, per 1 mol of the transition metal atom. Used.

Further, the organoaluminum compound (C) is
Usually, about 0 to 200 mol, preferably about 0 to 100 mol, more preferably about 5 to 100 mol, per 1 mol of aluminum atom in the organic aluminum oxy compound (B-1).
It is used as needed in a molar amount. Also,
Usually, 0 to 1000 mol, preferably about 0 to 500 mol, per mol of boron in the ionized ionic compound (B-2).
Mole, more preferably about 5-500 moles, as needed.

The (co) polymerization of the olefin can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, gas phase polymerization method and high pressure method. In the liquid phase polymerization method, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, Inert hydrocarbon media such as aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane can be used. Further, the olefin itself can be used as the solvent. These may be used in combination.

The polymerization temperature in the (co) polymerization of the olefin is usually from -50 to 100 when the suspension polymerization method is carried out.
° C, preferably in the range of 0 to 90 ° C. When performing the solution polymerization method, it is usually 0 to 300 ° C,
The temperature is preferably in the range of 20 to 250 ° C., and when performing the gas phase polymerization method, the polymerization temperature is usually 0 to 250 ° C.
It is desirable to be in the range of 120 ° C, preferably 20 to 100 ° C. When performing the high-pressure method, the polymerization temperature is usually 50 to 1000 ° C, preferably 100 to 500 ° C.
Is preferably within the range. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / c.
m ² , and in the case of the high pressure method, usually 100 to 100
10,000 kg / cm ² , preferably 500 to 5000
kg / cm ² . The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, the copolymerization can be performed in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure. Since the present invention uses (A-1) a transition metal compound having an indenyl group having a specific substituent at a specific position as a ligand, the transition metal catalyst component has such a substituent. An olefin (co) polymer having a large molecular weight and an olefin copolymer having a high comonomer content can be obtained as compared with an olefin polymerization catalyst containing a transition metal compound as a catalyst component.

The melt flow rate (MFR) of the first olefin polymer of the present invention obtained by the above production method is usually 0.01 to 200 g / 10 min, preferably 0.03 to 100 g / 10 min. Min, the intrinsic viscosity [η] is usually in the range of 0.5 to 6.0 dl / g, preferably 1.0 to 4.0 dl / g, and the density is usually in the range of 0.85 to 0.4 dl / g. 95 g / cm ³ , preferably 0.86 to
It is in the range of 0.94 g / cm ³ .

Further, the olefin polymer obtained by the above-mentioned production method has a feature that the molecular weight distribution and the composition distribution are narrow. In the present invention, the molecular weight distribution (Mw / Mn) is measured as follows using GPC-150C manufactured by Millipore.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., and the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
T (Takeda Pharmaceutical) 0.025% by weight, 1.0 ml /
The sample concentration is set to 0.1% by weight, the sample injection amount is set to 500 microliters, and a differential refractometer is used as a detector. Standard polystyrene has a molecular weight Mw <1.
For 000 and Mw> 4 × 10 ⁶ , use a product of Tosoh Corporation, and for 1000 <Mw <4 × 10 ⁶ , use a product of Pressure Chemical Company.

The first method for producing an olefin polymer according to the present invention is particularly preferably used for producing an ethylene polymer and a propylene polymer. When producing an ethylene-based polymer, ethylene is homopolymerized in the presence of the olefin polymerization catalyst, or ethylene is copolymerized with an α-olefin having 3 to 20 carbon atoms.
In the present specification, the ethylene-based polymer means an ethylene homopolymer and an ethylene / α-olefin copolymer.

Here, as the α-olefin having 3 to 20 carbon atoms, the above-mentioned α-olefin other than ethylene having 2 to 2 carbon atoms is preferable.
Α-olefin of 0. Among these,
Propylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Further, ethylene and a compound having 3 to 20 carbon atoms.
And the same polyenes as described above can be copolymerized with the α-olefin. The polymerization conditions for producing the ethylene-based polymer are the same as described above.

The first ethylene polymer of the present invention obtained by the above method has an ethylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 6/45.
It is in the range of 0/40 to 100/5.

The MFR is usually 0.01 to 200 g / 10
Min, preferably in the range of 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 5.0 dl / g,
Preferably in the range of 1.0~4.0dl / g, density is generally 0.85~0.95g / cm ^3, preferably in the range of 0.86~0.94g / cm ^3.

When producing a propylene-based polymer,
Propylene is homopolymerized in the presence of the olefin polymerization catalyst, or propylene is copolymerized with an α-olefin other than propylene. In the present specification, the propylene-based polymer means a propylene homopolymer and a propylene / α-olefin copolymer.

Here, as the α-olefin other than propylene, the above-mentioned α-olefin having 2 to 20 carbon atoms other than propylene can be mentioned. Among them, ethylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Propylene and α other than propylene
-The same polyenes as described above can be copolymerized with the olefin. The polymerization conditions for producing the propylene-based polymer are the same as described above.

The first propylene polymer of the present invention obtained by the above method has a propylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 60/40 to 100/5. Range.

The MFR is usually 0.01 to 200 g / 10
Min, preferably in the range of 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 6.0 dl / g,
Preferably in the range of 1.0~4.0dl / g, density is generally 0.85~0.95g / cm ^3, preferably in the range of 0.86~0.94g / cm ^3.

Further, among the propylene-based polymers, the propylene homopolymer usually has an mr / (mm + rr) value of 0.7 in the dyad distribution measured by ¹³ C-NMR.
To 1.3, preferably 0.8 to 1.2.

Here, the values of mr, mm and rr in the dyad distribution measured by ¹³ C-NMR were obtained as follows. That is, 50 to 70 mg of a sample is
Completely in an MR sample tube (5 mmφ) in a solvent containing about 0.5 ml of hexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene as a lock solvent. After dissolving,
It was measured at 120 ° C. by a complete proton decoupling method.
The measurement conditions were a flip angle of 45 ° and a pulse interval of 3.
4T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) is selected. Since T ₁ of the methylene group and the methine group is shorter than that of the methyl group, the recovery of the magnetization is 99% or more under this condition. The chemical shift was set at 21.59 ppm for the methyl group in the third unit of five propylene units in which the head-to-tail bond and the direction of methyl branching were the same.

In the spectrum relating to the methyl carbon region (19 to 23 ppm), the peak region is represented by the first region (21.1 to 2 ppm).
1.9 ppm), the second region (20.3 to 21.0 pp)
m) and the third region (19.5 to 20.3 ppm). Each peak in the spectrum is described in the literature (Po
lymer, 30 (1989) 1350).

Here, mr, mm and rr are propylene units 3 bonded by head-to-tail represented by the following formulas, respectively.
Indicates a chain.

[0166]

Embedded image

Further, the propylene-based polymer obtained by the above-described production method has a feature that the molecular weight distribution and the composition distribution are narrow. Next, the second method for producing an olefin polymer and the olefin polymer according to the present invention will be described.

The second method for producing an olefin polymer according to the present invention comprises: (A-2) a transition metal compound of Group IVB of the periodic table represented by the following general formula (II): -1) an organic aluminum oxy compound, and / or
Or (B-2) an olefin polymer obtained by pre-contacting a compound which forms an ion pair by reacting with the transition metal compound (A-2), or (C) an organoaluminum compound if necessary. Olefin is homopolymerized in the presence of a catalyst for use, or two or more olefins are copolymerized.

First, the olefin polymerization catalyst used in the present invention will be described. In the present invention, a transition metal compound represented by the following general formula (II) is used as the transition metal compound (A-2).

[0170]

Embedded image

In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium.
R ⁶ may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms. Groups, silicon-containing groups, oxygen-containing groups,
It is a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Specifically, examples of the halogen atom and the alkyl group having 1 to 10 carbon atoms include those similar to R ¹ in the general formula (I). it can, the silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group include those similar to R ² in the formula (I).

The aryl group having 6 to 10 carbon atoms includes phenyl, α- or β-naphthyl, and the alkenyl group having 2 to 10 carbon atoms includes vinyl, propenyl, cyclohexenyl and the like. No.

The above alkyl group and alkenyl group may be substituted with halogen. Among them, R ⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, and in particular, a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl, phenyl, α- An aryl group such as naphthyl and β-naphthyl or a hydrogen atom is preferable.

R ⁷ may be the same as or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, 7 to 4 carbon atoms
0 arylalkyl group, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Specifically, there can be mentioned those similar to R ² in the general formula (I).

The above-mentioned alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen.

Of these, R ⁷ is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or methyl, ethyl, n-propyl, i-propyl, n-butyl, tert.
-Butyl is preferably a hydrocarbon group having 1 to 4 carbon atoms.

Further, R ⁶ and R ⁷ may be the same or different from each other. One of R ⁸ and R ⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom or a carbon atom having the same number as 1 to R ² in the general formula (I). 10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups and phosphorus-containing groups.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, pentyl and the like. Among them, it is preferable that one of R ⁸ and R ⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl, and the other is a hydrogen atom.

[0179] X ¹ and X ² may be the same or different from each other, X ¹ in the general formula (I) and X
² the same hydrogen atom, halogen atom, 1 to carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, sulfur-containing groups or nitrogen-containing groups, or conjugated diene residues formed from X ¹ and X ² .

Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and divalent silicon-containing, similar to Y in the general formula (I). Group, 2
Divalent germanium containing group, divalent tin containing group, -O-,
-CO -, - S -, - SO -, - SO 2 -, - NR
^{5 -, - P (R 5} ) -, - P (O) (R 5) -, - BR
⁵ -or -AlR ^5- wherein R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Among these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and is preferably a divalent silicon-containing group. More preferably, alkyl silylene,
Particularly preferred is alkylarylsilylene or arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (II) are shown below. Ethylene (2-methyl-1-
Indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-1-indenyl) (9-
Fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-1-indenyl) (9-fluorenyl)
Zirconium dichloride, methylphenylsilylene (2-
Methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (3-methyl-1-indenyl) (9
-Fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-1-indenyl) (9-fluorenyl)
Zirconium dichloride, diphenylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride,
Ethylene (2-methyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-1-indenyl) (2,7-di-tert
-Butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-1-indenyl) (2,7-di-
tert-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-phenyl) 1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-phenyl-1-indenyl) ) (9-Fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-phenyl-1-indenyl) (2, 7-di-t
ert-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl -Four-
Phenyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4-phenyl-1-indenyl) (2,7-di
-tert-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4-naphthyl-1-indenyl)
(9-Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl ) Zirconium dichloride, methylphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl
-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9-
Fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-naphthyl-1-indenyl) (2,7-di-t
ert-butyl-9-fluorenyl) zirconium dichloride, diphenylsilylene (2-methyl-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (2- Methyl-4-naphthyl-1-indenyl) (2,7-di-tert-butyl-9
-Fluorenyl) zirconium dichloride and the like.

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can also be used. The transition metal compound (A-2) as described above may be used in combination of two or more.

Examples of the organoaluminum oxy compound (B-1) used in the present invention include the same ones as the above-mentioned organoaluminum oxy compound, and form an ion pair by reacting with the transition metal compound (A-2). Examples of the compound (B-2) include the same compounds as those that react with the transition metal compound (A-1) to form an ion pair.

As the organoaluminum compound (C) optionally used, the same organoaluminum compounds as described above can be used. The method of preliminary contact of each component is
The same method as in the case of the olefin polymerization catalyst can be employed.

The olefin polymerization catalyst used in the second process for producing an olefin polymer according to the present invention comprises the component (A-2), component (B-1) and / or component (B-2). Alternatively, if necessary, the solid catalyst may be preliminarily brought into contact with the component (C) and then supported on a fine particle carrier.

The catalyst for olefin polymerization is a prepolymer comprising the solid catalyst, an olefin polymer produced by prepolymerization in the presence of the solid catalyst, and, if necessary, the component (C). It may be a catalyst.

Examples of the fine-particle carrier used for the solid catalyst and the prepolymerization catalyst include those similar to the fine-particle carrier described above. FIG. 2 shows a process for preparing an olefin polymerization catalyst used in the second method for producing an olefin polymer according to the present invention.

In the second method for producing an olefin polymer according to the present invention, the above transition metal compound (A-2)
Olefin homopolymerization in the presence of an olefin polymerization catalyst obtained by pre-contacting an organoaluminum oxy compound and / or an ionized ionic compound (B) or, if necessary, an organoaluminum compound (C) Or copolymerize two or more olefins.

The olefin used in the present invention includes:
Examples thereof include the same as the chain or branched olefin used in the first method for producing an olefin polymer and the olefin having an aliphatic ring or an aromatic ring.

Further, together with the olefin, a polyene similar to the polyene used in the first method for producing an olefin polymer can be copolymerized. When the olefin is (co) polymerized, the above transition metal compound (A
-2) is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms, per liter of polymerization volume.

The organic aluminum oxy compound (B-1) is
The aluminum atom is usually used in an amount of about 1 to 10,000 mol, preferably 10 to 50,000 mol, per 1 mol of the transition metal atom.
It is used in an amount such that it becomes 00 mol.

The ionized ionic compound (B-2) is used in an amount such that the boron atom is usually about 0.5 to 20 mol, preferably 1 to 10 mol, per 1 mol of the transition metal atom. Used.

Further, the organoaluminum compound (C) is
Usually, about 0 to 200 mol, preferably about 0 to 100 mol, more preferably about 5 to 100 mol, per 1 mol of aluminum atom in the organic aluminum oxy compound (B-1).
It is used as needed in a molar amount. Also,
Usually, 0 to 1000 mol, preferably about 0 to 500 mol, per mol of boron in the ionized ionic compound (B-2).
Mole, more preferably about 5-500 moles, as needed.

The (co) polymerization of the olefin can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, gas phase polymerization method and high pressure method. In the liquid phase polymerization method, the first
As the inert hydrocarbon medium used in the method for producing an olefin polymer described above, the same one can be used as the polymerization medium. Further, the olefin itself can be used as the solvent. These may be used in combination.

The polymerization temperature in the (co) polymerization of the olefin is usually -50 to 100 when the suspension polymerization method is carried out.
° C, preferably in the range of 0 to 90 ° C. When performing the solution polymerization method, it is usually 0 to 250 ° C,
The temperature is preferably in the range of 20 to 200 ° C., and when performing the gas phase polymerization method, the polymerization temperature is usually 0 to 200 ° C.
It is desirable to be in the range of 120 ° C, preferably 20 to 100 ° C. When performing the high-pressure method, the polymerization temperature is usually 50 to 1000 ° C., preferably 100 to 500 ° C.
It is desirable to be in the range of ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² .
cm ² , and in the case of the high pressure method, the polymerization pressure is:
Usually, 100 to 10,000 kg / cm ² , preferably 5
It is under the condition of 00 to 5000 kg / cm ² . The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, the copolymerization can be performed in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature and the polymerization pressure. In the present invention, as the transition metal catalyst component, a transition metal compound (A-2) having an indenyl group having a specific substituent at a specific position as a ligand is used. An olefin (co) polymer having a large molecular weight and an olefin copolymer having a high comonomer content can be obtained as compared with an olefin polymerization catalyst containing a transition metal compound as a catalyst component.

The MFR of the second olefin polymer of the present invention obtained by the above production method is usually 0.0
1 to 200 g / 10 min, preferably 0.03 to 100 g /
In the range of 10 minutes, the intrinsic viscosity [η] is usually 0.5 to
6.0 dl / g, preferably in the range of 1.0 to 4.0 dl / g, and the density is usually 0.85 to 0.95 g / cm.
³ , preferably in the range of 0.86 to 0.94 g / cm ³ .

Further, the olefin polymer obtained by the above-mentioned production method has a feature that the molecular weight distribution and the composition distribution are narrow. The second method for producing an olefin polymer according to the present invention is preferably used particularly for producing an ethylene polymer and a propylene polymer.

In the case of producing an ethylene polymer, ethylene is homopolymerized in the presence of the olefin polymerization catalyst or ethylene is copolymerized with an α-olefin having 3 to 20 carbon atoms.

Here, as the α-olefin having 3 to 20 carbon atoms, other than ethylene having 2 to 2 carbon atoms other than ethylene,
Α-olefin of 0. Among these,
Propylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Also, ethylene and a compound having 3 to 20 carbon atoms
And the same polyenes as described above can be copolymerized with the α-olefin. The polymerization conditions for producing the ethylene-based polymer are the same as described above.

The second ethylene polymer of the present invention obtained by the above method has an ethylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 6/45.
It is in the range of 0/40 to 100/5.

The MFR is usually 0.01 to 200 g / 10
Min, preferably in the range of 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 5.0 dl / g,
Preferably in the range of 1.0~4.0dl / g, density is generally 0.85~0.95g / cm ^3, preferably in the range of 0.86~0.94g / cm ^3.

When producing a propylene-based polymer,
Propylene is homopolymerized in the presence of the olefin polymerization catalyst, or propylene is copolymerized with an α-olefin other than propylene.

The α-olefins other than propylene include the α-olefins having 2 to 20 carbon atoms other than propylene. Among them, ethylene, 1-butene, 1-hexene, 1-octene and the like are preferably used.

Propylene and α other than propylene
-The same polyenes as described above can be copolymerized with the olefin. The polymerization conditions for producing the propylene-based polymer are the same as described above.

The second propylene-based polymer of the present invention obtained by the above method has a propylene / α-olefin component ratio of usually 55/45 to 100/2, preferably 60/40 to 100/5. Range.

MFR is usually 0.01 to 200 g / 10
Min, preferably in the range of 0.03 to 100 g / 10 min, and the intrinsic viscosity [η] is usually 0.5 to 6.0 dl / g,
Preferably in the range of 1.0~4.0dl / g, density is generally 0.85~0.95g / cm ^3, preferably in the range of 0.86~0.94g / cm ^3.

[0210] Among the propylene-based polymers, the propylene homopolymer usually has an mr / (mm + rr) value of 0.7 in the dyad distribution measured by ¹³ C-NMR.
To 1.3, preferably 0.8 to 1.2.

Further, the propylene-based polymer obtained by the above-described production method has a feature that the molecular weight distribution and the composition distribution are narrow.

[0212]

The catalyst for olefin polymerization according to the present invention comprises:
An olefin (co) polymer having a high molecular weight can be obtained, and an olefin copolymer having a high comonomer content can be obtained even when the comonomer content is low. Further, in the polymerization using a polyene together with an olefin, an olefin copolymer having a high polyene content can be obtained even when the use ratio of the polyene is small.

In the first method for producing an olefin polymer according to the present invention, an olefin (co) polymer having a high molecular weight can be obtained, and an olefin polymer having a high comonomer content can be obtained even when the comonomer content is low. can get. Further, in the polymerization using a polyene together with an olefin, an olefin polymer having a high polyene content can be obtained even when the use ratio of the polyene is small.

The first olefin polymer according to the present invention comprises:
The molecular weight distribution is narrow, and when the olefin polymer is a copolymer, the molecular weight distribution and the composition distribution are narrow. According to the second method for producing an olefin polymer according to the present invention, an olefin (co) polymer having a high molecular weight can be obtained, and an olefin polymer having a high comonomer content can be obtained even when the use ratio of a comonomer is small. . Further, in the polymerization using a polyene together with an olefin, an olefin polymer having a high polyene content can be obtained even when the use ratio of the polyene is small.

The second olefin polymer according to the present invention comprises:
The molecular weight distribution is narrow, and when the olefin polymer is a copolymer, the molecular weight distribution and the composition distribution are narrow.

[0216]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0219]

[Production Example 1] [Synthesis of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] Reactor having an inner volume of 100 ml Was charged with 5.5 ml (20 mmol) of diethyl ether and 2,7-di-t-butyl-9-fluorene under ice cooling.
Hexane solution of n-butyllithium (1.67 mmol /
12.0 ml) was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 10 hours to obtain a mixed solution A.

In a reactor having an inner volume of 200 ml, 40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were added.
(320 mmol) and then the mixture A under ice-cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After distilling off diethyl ether and dimethyldichlorosilane under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. After methylene chloride was distilled off from the obtained methylene chloride solution under reduced pressure, the pressure was reduced by a vacuum pump and the solvent was further distilled off to obtain an orange viscous oil.

In a reactor having an inner volume of 100 ml, 50 ml of diethyl ether and 3.6 of 2-methyl-4,5-benzoindene were placed.
After adding 0 g (20 mmol), n-butyllithium hexane solution (1.67 mmol / ml) 1 was added under ice cooling.
2.0 ml was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 13 hours to obtain a mixed solution B.

After putting 40 ml of a diethyl ether solution of the orange viscous oil obtained in the above reaction into a reactor having an inner volume of 200 ml, the above mixed solution B was added dropwise over 30 minutes under ice-cooling, and the mixture was added at room temperature. The mixture was further stirred for one day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, and the ether layer was washed with water and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution; n-hexane) to obtain the desired product [dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7 -Di-t-butyl-9-fluorene)] was obtained as a pale yellow amorphous solid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) −0.4 (s, 3H), −0.3 (d, J = 3.6H)
z, 3H), 1.23-1.60 (m, 18H), 2.
29 to 2.40 (br.s, 3H), 3.80 to 3.9
4 (m, 1H), 4.17 to 4.31 (m, 1H),
7.29-8.34 (m, 13H).

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-butyl) obtained above were added.
After adding 1.50 g (3.2 mmol) of fluorene), a solution of n-butyllithium in hexane (1.6 ml) was added under ice cooling.
(7 mmol / ml) was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes.
The resulting dark yellow slurry solution was cooled to −60 ° C., and 0.75 g (3.2 mmol) of zirconium tetrachloride was added little by little. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

The produced solid was filtered with a glass filter. The obtained solid was washed by adding 10 ml of diethyl ether, and then filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered with a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2-methyl-4,5- Benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] 0.
84 g were obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.26 (s, 9H), 1.35 (s, 9H), 1.4
4 (s, 3H), 1.54 (s, 3H), 2.37
(S, 3H), 7.01-8.02 (m, 13H).

[0225]

[Production Example 2] [Synthesis of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride] In a reactor having an inner volume of 100 ml, 50 ml of diethyl ether and 3.32 g of fluorene were placed. (20 mmol), 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes under ice cooling, and the mixture was stirred at room temperature for another 10 hours. I got

In a reactor having an inner volume of 200 ml, 40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were added.
(320 mmol) and the mixture C under ice-cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After distilling off diethyl ether and dimethyldichlorosilane under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. After methylene chloride was distilled off from the obtained methylene chloride solution under reduced pressure, the pressure was reduced by a vacuum pump and the solvent was further distilled off to obtain an orange viscous oil.

In a reactor having an internal volume of 100 ml, diethyl ether (50 ml) and 2-methyl-4,5-benzoindene (3.8) were added.
After charging 9 g (20 mmol), 1-hexane solution of n-butyllithium (1.67 mmol / ml) was added under ice cooling.
2.0 ml was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 13 hours to obtain a mixed solution D.

After putting 40 ml of a diethyl ether solution of the orange viscous oil obtained in the above reaction into a reactor having an inner volume of 200 ml, the mixture D was added dropwise over 30 minutes under ice-cooling, and the mixture was added at room temperature. The mixture was further stirred for one day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, and the ether layer was washed with water and dried over anhydrous magnesium sulfate. After concentrating the ether layer, the desired product [dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorene) is separated and purified by silica gel column chromatography (developing solution: n-hexane). )] 3.88 g (yield; 48%) was obtained as a slightly yellow amorphous solid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) −0.4 (s, 3H), −0.3 (d, J = 3.6H)
z, 3H), 2.29 to 2.40 (br.s, 3H),
3.94 (br.s, 1H), 4.26 (br.s, 1H)
H), 7.09-8.31 (m, 15H) In a reactor having an inner volume of 100 ml, diethyl ether 50 was added.
1.30 g of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorene) obtained above.
(3.2 mmol) and then 3.8 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) under ice-cooling.
ml for 10 minutes and 30 minutes under reflux at room temperature for 1 hour.
The reaction was continued for another minute. The resulting dark yellow slurry solution was cooled to -60 ° C and 0.75 g of zirconium tetrachloride
(3.2 mmol) was added in small portions. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

The produced solid was filtered with a glass filter. The obtained solid was washed by adding 10 ml of diethyl ether, and then filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered with a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2-methyl-4,5- 0.96 g of [benzo-1-indenyl) (9-fluorenyl) zirconium dichloride] was obtained as an orange powder.

[0231] Data of the NMR spectrum of the compound obtained are described below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.44 (s, 3H), 1.54 (s, 3H), 2.3
7 (s, 3H), 6.99 to 8.00 (m, 15H)

[0232]

[Production Example 3] [Synthesis of dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride] A reactor was charged with 50 ml of diethyl ether and 5.57 g (20 mmol) of 2,7-di-t-butyl-9-fluorene, and then n-butyllithium hexane solution (1.67 mmol) under ice-cooling. / Ml) was added dropwise over 10 minutes and stirred at room temperature for another 10 hours to obtain a mixture E.

In a reactor having an internal volume of 200 ml, 40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were added.
(320 mmol) and then the mixture E under ice-cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After distilling off diethyl ether and dimethyldichlorosilane under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. After methylene chloride was distilled off from the obtained methylene chloride solution under reduced pressure, the pressure was reduced by a vacuum pump and the solvent was further distilled off to obtain an orange viscous oil.

50 ml of diethyl ether and 3.88 g (20 mmol) of 2,6-dimethyl-4,5-benzoindene were put into a reactor having an inner volume of 100 ml, and then a hexane solution of n-butyllithium was added under ice cooling. (1.67 mmol / m
l) 12.0 ml was added dropwise over 10 minutes, and an additional 1
The mixture was stirred for 3 hours to obtain a mixed solution F.

After putting 40 ml of a diethyl ether solution of the orange viscous oil obtained in the above reaction into a reactor having an inner volume of 200 ml, the mixture F was added dropwise over 30 minutes under ice-cooling, and the mixture was stirred at room temperature. The mixture was further stirred for one day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, and the ether layer was washed with water and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution: n-hexane) to obtain the desired product [dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2 , 7-di-t-butyl-9-fluorene)] 4.8 g
(Yield; 45%) was obtained as a slightly yellow amorphous solid.

In a reactor having an internal volume of 100 ml, diethyl ether (50 ml) and the dimethylsilylene (2,6-
After adding 1.69 g (3.2 mmol) of dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorene), n-butyllithium was added under ice cooling. 3.8 ml of a hexane solution (1.67 mmol / ml) was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes. The resulting dark yellow slurry solution was cooled to -60 ° C and 0.75 g (3.2 mmol) of zirconium tetrachloride.
Was added little by little. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

The produced solid was filtered with a glass filter. The obtained solid was washed by adding 10 ml of diethyl ether, and then filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated with a glass filter to obtain the desired product [dimethylsilylene (2,6-dimethyl-4, 5-benzo-1-indenyl) (2,7-di-t
-Butyl-9-fluorenyl) zirconium dichloride]
1.02 g was obtained as an orange powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 1.24 (s, 9H), 1.35 (s, 9H), 1.4
3 (s, 3H), 1.56 (s, 3H), 2.36
(S, 3H), 2.50 (s, 3H), 7.01-8.
02 (m, 12H)

[0239]

[Production Example 4] [Synthesis of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride ] Internal volume is 100
50 ml of diethyl ether, 2,7-di-t
After charging 5.57 g (20 mmol) of -butyl-9-fluorene, 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes under ice-cooling, and the mixture was added at room temperature. The mixture was further stirred for 10 hours to obtain a mixed solution G.

In a reactor having an internal volume of 200 ml, 40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were added.
(320 mmol) and then the mixture G under ice-cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After distilling off diethyl ether and dimethyldichlorosilane under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. After methylene chloride was distilled off from the obtained methylene chloride solution under reduced pressure, the pressure was reduced by a vacuum pump and the solvent was further distilled off to obtain an orange viscous oil.

A reactor having an internal volume of 100 ml was charged with 50 ml of diethyl ether and 4.16 g (20 mmol) of 2,7-dimethyl-4,5- (2-methyl-benzo) indene.
Under ice cooling, 12.0 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 13 hours to obtain a mixed solution H.

After putting 40 ml of the orange viscous oil diethyl ether solution obtained by the above reaction into a reactor having an inner volume of 200 ml, the mixture H was added dropwise over 30 minutes under ice-cooling, and the mixture was stirred at room temperature. The mixture was further stirred for one day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, and the ether layer was washed with water and dried over anhydrous magnesium sulfate. After concentrating the ether layer, the desired product [dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo)-] was separated and purified by silica gel column chromatography (developing solution: n-hexane). 5.2 g (yield; 48%) of 1-indenyl) (2,7-di-t-butyl-9-fluorene) was obtained as a pale yellow amorphous solid.

In a reactor having an inner volume of 100 ml, diethyl ether (50 ml) and the dimethylsilylene (2,7-
Dimethyl-4,5- (2-methyl-benzo) -1-indenyl)
1.73 g of (2,7-di-t-butyl-9-fluorene) (3.2
Mmol), 3.8 ml of a hexane solution of n-butyllithium (1.67 mmol / ml) was added under ice cooling.
The mixture was added dropwise over 0 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 30 minutes. The obtained dark yellow slurry solution was used for -6.
After cooling to 0 ° C., 0.75 g of zirconium tetrachloride (3.2
Mmol) was added in small portions. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

The produced solid was filtered with a glass filter. The obtained solid was washed by adding 10 ml of diethyl ether, and then filtered under reduced pressure. The obtained solid was washed with 40 ml of methylene chloride, filtered through a glass filter, and the solid precipitated by concentrating the methylene chloride solution was separated through a glass filter to obtain the desired product [dimethylsilylene (2,7-dimethyl-4, 0.94 g of 5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was obtained as an orange powder.

The NMR spectrum data of the obtained compound is shown below. ¹ H-NMR (δ value, CDCl ₃ , 90 MHz) 0.69 (s, 9H), 1.36 (s, 9H), 1.5
6 (s, 3H), 1.69 (s, 3H), 2.24
(S, 3H), 2.47 (s, 3H), 2.57 (s,
3H), 6.71 to 8.40 (m, 11H)

[0246]

[Production Example 5] [Synthesis of dimethylsilylene ( 2-n-propyl-4- (9-phenanthryl) -1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride 1 liter The four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. Fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added thereto, and a hexane solution of n-butyllithium (30 mmol) was added dropwise at −10 ° C. with stirring over 30 minutes. After dropping, slowly warm to room temperature slowly,
Stirred at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a solution of dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) with stirring at −10 ° C. over 1 hour, and the mixture was naturally heated and stirred overnight. Transfer the solution to a glass filter (G-
5) Pressure filtration to remove lithium chloride, remove solvent and unreacted dichlorodimethylsilane in the filtrate under reduced pressure, reslurry with dehydrated hexane (100 ml), and pressurize with a glass filter (G-5). Filtration gave a white powder (3.30 g, 43% yield).

The following shows the NMR spectrum data of the obtained compound. ¹ H-NMR (CDCl ₃ ); 7.2 to 8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (2-n-propyl-4- (9-phenanthryl) -1-i
Synthesis of Ndenyl) (9-fluorenyl) silane A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. This is 2-n-
Propyl-4- (9-phenanthryl) indene (1.60
g, 4.78 mmol) and dehydrated ether (20 ml) were added, and a hexane solution of n-butyllithium (5.02 mmol) was added dropwise at −40 ° C. with stirring. After the dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 7 hours, the white slurry changed to a yellow slurry and a brown slurry, and then became a yellow slurry. Dehydrated ether (30m
l) was added thereto, and the mixture was stirred at 0 ° C. with stirring to obtain dimethyl (9-fluorenyl) silane chloride (1.24 g,
5.02 mmol) and stirred at room temperature overnight. The reaction liquid became a yellow slurry. Thereafter, N-methyl-2-pyrrolidone (0.1 g) was added, and the mixture was further stirred for 3 hours to change to an orange solution. This is ether (100m
l), a saturated aqueous ammonium chloride solution (100 ml) was added, and the mixture was transferred to a separatory funnel to separate an organic layer. The organic layer was washed with a saturated aqueous ammonium chloride solution, water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was removed (yellow oil) and purified by column chromatography (solvent: hexane) to give a white oil. When this was depressurized with a vacuum pump, it was foamed and solidified to give a white powder (2.02 g, yield 76%).
%).

The NMR spectrum data of the obtained compound are shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 7.0~9.
0 (m, 20H), 6.2 (d, 1H), 4.3 (d,
1H), 3.9 (br, 1H), 2.1 to 2.5 (t,
2H), 1.0-1.6 (br, 2H), 0.6-1.
0 (t, 3H), -0.2 to -0.4 (d, 6H) dimethylsilylene (2-n-propyl-4- (9-phenanthrene)
Le) -1-indenyl) (9-fluorenyl) zirconium
Synthesis of dichloride A 50 ml Schlenk bottle was equipped with a dropping funnel, and was sufficiently purged with nitrogen and dried. Then, dimethyl (2-n-propyl-4- (9-phenanthryl) -1-indenyl) (9-fluorenyl) silane (0.80 g, 1.44) synthesized above was added thereto.
mmol) and dehydrated ether (20 ml).
Hexane solution of n-butyllithium (3.0
2 mmol) was added dropwise. After the dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 8 hours, the yellow solution became a brown slurry via a bright yellow slurry. This was again stirred at −78 ° C. while stirring zirconium tetrachloride (0.33
5 g, 1.44 mmol) was added, and after the dropwise addition, the temperature was slowly raised to room temperature. Stirring at room temperature overnight resulted in a red slurry. The mixture was filtered under pressure through a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, and the slurry was reslurried with dehydrated hexane (25 ml).
5), and the desired metallocene is mixed with a red powder (39).
7 mg, 39% yield).

[0249]

[Production Example 6] [Synthesis of ethylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] reflux tube, thermometer,
In a 200 ml four-necked flask equipped with a dropping funnel, 2-methylindene (4.5 g, 34.6 mmol) and dehydrated ether (50 ml) were placed, and a hexane solution of n-butyllithium (1.61 mol / Liter, 23.7
ml, 38.1 mmol) was added dropwise over 1 hour and then allowed to warm to room temperature over 6 hours. The reaction became a yellow-orange slurry.

Subsequently, 1,2-dibromoethane (3
2.5 g, 0.173 mol), dehydrated ether (100
ml), and the entire reaction mass was added by pipette at 0 ° C. over 1 hour, followed by stirring at room temperature for 15 hours. The obtained yellow transparent solution was poured into 300 ml of water to separate an ether layer, and the aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting yellow-brown oil was purified by column chromatography (silica gel 300 g, developed with hexane) to give the target product [3- (2-bromoethyl) -2 as a yellow-white transparent liquid.
-Methylindene] was obtained (yield 76%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.8 to 2.6 (m, 2H), 1.93 (s, 3H),
2.8 to 3.2 (m, 2H), 3.3 (br, 1H),
6.32 (s, 1H), 6.6-7.4 (m, 4H).

A 300 equipped with a reflux tube, thermometer and dropping funnel
fluorene (2.11 g, 1
2.7 mmol) and dehydrated ether (60 ml).
At 0 ° C., a hexane solution of n-butyllithium (1.61 mol)
1 / liter, 8.7 ml, 14.0 mmol) was added dropwise over 1 hour and then refluxed for 2 hours. The reaction became dark red clear. This was cooled to -78 ° C (yellow slurry) and 3- (2-bromoethyl) -2-methylindene (3
g, 12.7 mmol) in dehydrated ether (20 ml) was added dropwise over 1 hour, and then the mixture was naturally warmed to room temperature and stirred for 15 hours. The reaction gradually became a yellow slurry.

The reaction product was poured into a saturated aqueous solution of ammonium chloride (300 ml) to separate the ether layer. The aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow powder was reslurried with hexane (200 ml) and filtered, and the target substance of white powder [1- (9-fluorenyl) -2- (2-methyl-1-indenyl) ethane was removed. ] To 2.
50 g was obtained (yield 61%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.3 to 1.9 (m, 4H), 1.92 (s, 3H),
3.12 (br, 1H), 3.88 (br, 1H),
6.48 (s, 1H), 7.0 to 7.9 (m, 12
H).

A 300 equipped with a reflux tube, thermometer and dropping funnel
1- (9-Fluorenyl) -2- (2-
Methyl-1-indenyl) ethane (1.0 g, 3.10 m
mol) and dehydrated ether (100 ml).
Hexane solution of n-butyl lithium (1.61 mol
/ Liter, 4.04 ml, 6.51 mmol) in 30
Then, the temperature was naturally raised to 0 ° C. over 5 hours, and the mixture was stirred at 0 ° C. for 3 hours. The reaction became a yellow slurry.

The reaction was then cooled to -78 ° C and zirconium tetrachloride (0.760 g, 3.26 mmol) was added over 15 minutes. After that, the temperature naturally rises to room temperature,
Stir for 12 hours. Obtained reactant (orange yellow slurry)
Was filtered with a glass filter (G-5), and the residue was washed with dehydrated ether (100 ml). The orange solid remaining on the filter was washed with dehydrated dichloromethane (300 ml), filtered, and the solvent in the filtrate was distilled off to obtain a red-orange solid (1.
20 g) were obtained. This solid was washed with dehydrated dichloromethane (100 ml) and filtered to give a red-orange powder of the desired product [ethylene (9-fluorenyl) (2-methyl-1-
Indenyl) zirconium dichloride] is 0.650
g (43% yield).

The following shows the NMR spectrum data of the obtained compound. _{^{1 H-NMR (CDCl 3,}} 90MHz) 2.20 (s, 3H), 3.8~4.4 (m, 4H),
6.24 (s, 1H), 6.9 to 8.0 (m, 12
H).

[0258]

[Production Example 7] [Dimethylsilylene (9-fluorenyl) (2-methyl-1-
Synthesis of indenyl) zirconium dichloride] A reactor having an inner volume of 100 ml was charged with 20 ml of diethyl ether and 3.3 g (20 mmol) of fluorene, and then, under ice-cooling, a hexane solution of n-butyllithium (1.61 mmol). / Ml) was added dropwise over 10 minutes and stirred at room temperature for another 10 hours to obtain a mixture I.

In a reactor having an internal volume of 200 ml, 40 ml of diethyl ether and 41.2 g of dimethyldichlorosilane were added.
(320 mmol) and the mixture I under ice cooling.
Was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1 hour. After distilling off diethyl ether and dimethyldichlorosilane under reduced pressure, 100 ml of methylene chloride was added and stirred, and solids were removed using a glass filter. After methylene chloride was distilled off from the obtained methylene chloride solution under reduced pressure, the pressure was reduced by a vacuum pump and the solvent was further distilled off to obtain 5.0 g of an orange oil.

In a reactor having an internal volume of 100 ml, 40 ml of diethyl ether and 2.18 g of 2-methylindene (16.
8 mmol) and 10.4 ml of a hexane solution of n-butyllithium (1.61 mmol / ml) under ice-cooling.
Was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 13 hours to obtain a mixed solution J.

A reactor having an inner volume of 200 ml was charged with a solution of 5.0 g of the orange oil obtained in the above reaction in 40 ml of diethyl ether, and the mixture J was added under ice cooling to 1.5 ml.
The mixture was added dropwise over time and stirred at room temperature for another day. The obtained reaction solution was poured into a saturated aqueous solution of ammonium chloride, and the ether layer was washed with water and dried over anhydrous magnesium sulfate. After concentrating the ether layer, it was separated and purified by silica gel column chromatography (developing solution: n-hexane) to obtain the desired product [dimethylsilylene (9-fluorenyl) (2-methyl
1.65 g (yield; 45%) as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) -4.3 (d, 6H), 2.2 (s, 3H), 3.7
(S, 1H), 4.2 (s, 1H), 6.7 (s, 1H)
H), 7.0-8.0 (m, 12H).

In a reactor having an internal volume of 100 ml, 50 ml of diethyl ether and 1.35 g of dimethylsilylene (9-fluorenyl) (2-methyl-1-indene) obtained above.
(3.8 mmol), and then hexane solution of n-butyllithium (1.60 mmol / ml) 4.8 under ice-cooling.
ml was added dropwise over 10 minutes, and the reaction was further continued at room temperature for 1 hour and under reflux for 2 hours. The resulting yellow slurry solution was cooled to −60 ° C. and 0.90 g of zirconium tetrachloride
(3.8 mmol) was added in small portions. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

After refluxing with ether for another 1 hour, the resulting solid was filtered with a glass filter. After the obtained solid was washed with 30 ml of diethyl ether, the diethyl ether solution was filtered under reduced pressure. The obtained solid was washed with 100 ml of n-hexane and then filtered through a glass filter to give 1.58 g of the target substance [dimethylsilylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] in a brick color. Obtained as a powder.

[0265]

[Production Example 8] [Diphenylsilylene (9-fluorenyl) (2-methyl-1
Synthesis of -indenyl) zirconium dichloride] In a reactor having an inner volume of 100 ml, diethyl ether 30 ml,
After charging 3.3 g (20 mmol) of fluorene, 12.4 ml of a hexane solution of n-butyllithium (1.61 mmol / ml) was added dropwise over 10 minutes under ice-cooling, and the mixture was further stirred at room temperature for 10 hours. . The obtained reaction solution was concentrated and solidified under reduced pressure, dried under reduced pressure with a vacuum pump, and a yellow lithium salt was obtained.

In a reactor having an inner volume of 200 ml, n-hexane 150 ml and diphenyldichlorosilane 6.6 g (26
Mmol), and the lithium salt is added thereto under ice-cooling.
After the temperature was raised to room temperature, stirring was further continued for 12 hours. The generated solid is removed using a glass filter,
The obtained filtrate was concentrated. The precipitated solid was filtered through a glass filter to obtain 4.51 g (yield; 59%) of the target product [9- (chlorodiphenylsilyl) fluorene] as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 4.58 (s, 1H), 7.0 to 7.90 (m, 18
H).

In a reactor having an internal volume of 100 ml, 40 ml of diethyl ether and 1.53 g of 2-methylindene (11.
After adding 8 mmol), 7.3 ml of a hexane solution of n-butyllithium (1.61 mmol / ml) was added dropwise over 10 minutes under ice-cooling, and the mixture was further stirred at room temperature for 10 hours to obtain a mixed solution K. Was.

A reactor having an inner volume of 200 ml was charged with 50 ml of diethyl ether, 4.51 g (11.8 mmol) of 9- (chlorodiphenylsilyl) fluorene and 144 mg (1.2 mmol) of copper thiocyanate, and then cooled with ice. The mixture K was added dropwise under 1 hour, and reacted at room temperature for further 15 hours. After the reaction, the precipitated solid was removed with a glass filter. The obtained filtrate was concentrated and solidified, and was reslurried and washed with 30 ml of diethyl ether to obtain the desired product [diphenylsilylene (9-fluorenyl) (2-methyl).
2-indene)] 2.10 g (yield; 37%) as a white powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.98 (s, 3H), 4.42 (s, 1H), 4.9
6 (s, 1H), 6.20 (s, 1H), 6.60-
8.40 (m, 22H).

In a reactor having an inner volume of 100 ml, diethyl ether (50 ml) and the diphenylsilylene (9-
1.50 g of fluorenyl) (2-methyl-1-indene)
(3.15 mmol), and then n-butyllithium hexane solution (1.60 mmol / ml) under ice-cooling.
9 ml was added dropwise over 10 minutes, and 2 hours under reflux at room temperature for 1 hour.
The reaction continued for an additional hour. The obtained yellow slurry solution was cooled to −60 ° C., and 0.73 g of zirconium tetrachloride was used.
(3.15 mmol) was added in small portions. The temperature was allowed to rise to room temperature and stirred at room temperature for another 12 hours.

After refluxing with ether for another 1 hour, the resulting solid was filtered with a glass filter. After the obtained solid was washed with 30 ml of diethyl ether, the diethyl ether solution was filtered under reduced pressure. The obtained solid was washed with 100 ml of n-hexane and then filtered through a glass filter to give 1.80 g of the desired product [diphenylsilylene (9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] in an orange color. Obtained as a powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 2.12 (s, 3H), 6.70 to 8.40 (m, 13
H).

[0274]

[Production Example 9] [Synthesis of ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride] Indene (10) was placed in a 300 ml four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel.
g, 86.1 mmol), dehydrated ether (100 ml)
And a hexane solution of n-butyl lithium (1.61 mol / L, 59 ml, 94.7 mm
ol) was added dropwise over 30 minutes and then allowed to warm to room temperature over 3 hours. The reaction became orange clear.

Next, 1,2-dibromoethane (8-liter) was placed in a 1-liter four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel.
1 g, 0.431 mol), dehydrated ether (150 m
l) was added thereto, and the whole amount of the above reaction product was added dropwise at 0 ° C. over 2 hours, followed by stirring at room temperature for 15 hours. The obtained yellow transparent solution was poured into 300 ml of water to separate an ether layer, and the aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained tan oil was purified by column chromatography (500 g of silica gel, developed with hexane) to obtain 16.36 g of a light green yellow transparent liquid [3- (2-bromoethyl) indene]. (Yield 85%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.8 to 2.6 (m, 2H), 3.40 (t, J = 1.
9Hz, 2H), 3.5-3.8 (m, 1H), 6.4
8 (d, J = 1.6 Hz, 1H), 6.83 (d, J =
1.6 Hz, 1H), 7.1-7.6 (m, 4H).

A 300 equipped with a reflux tube, thermometer and dropping funnel
fluorene (3.72 g, 2
2.4 mmol) and dehydrated ether (100 ml) were added, and a hexane solution of n-butyllithium (1.61) was added at 0 ° C.
mol / liter, 15.3 ml, 24.6 mmol)
Was added dropwise over 1 hour, and then refluxed for 2 hours. The reaction became dark red clear. This was cooled to −78 ° C. (yellow slurry) and 3- (2-bromoethyl) indene (5 g, 2 g)
(2.4 mmol) dissolved in dehydrated ether (50 ml) was added dropwise over 1 hour, and then the mixture was naturally warmed to room temperature and stirred for 15 hours. The reaction gradually became an orange-yellow transparent homogeneous solution. This was poured into a saturated aqueous solution of ammonium chloride (200 ml) to separate the ether layer, the aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow semi-solid was purified by column chromatography (400 g of silica gel, developed with hexane), and the desired product of white powder [1- (9-fluorenyl) -2- (1-indenyl) ethylene 3.42 g (yield 49%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 1.1 to 2.6 (m, 4H), 3.35 (br, 1
H), 3.97 (br, 1H), 6.48 (d, J =
1.6 Hz, 1 H), 6.83 (d, J = 1.6 Hz,
1H), 7.1-8.0 (m, 12H) FD-MS 308 (M ⁺ ) 1- (9-Fluorenyl) -2 in a 100 ml four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel. -(1-indenyl)
Ethylene (1.0 g, 3.24 mmol) and dehydrated ether (50 ml) were added, and a hexane solution of n-butyl lithium (1.61 mol / liter, 4.2 m) was added at -78 ° C.
1, 6.80 mmol) was added dropwise over 1 hour, and then the temperature was spontaneously raised over 5 hours and refluxed for 1 hour. The reaction became an orange-yellow slurry.

The reaction was then cooled to -78 ° C and zirconium tetrachloride (0.792 g, 3.40 mmol) was added over 15 minutes. After that, the temperature naturally rises to room temperature,
Stir for 12 hours. Obtained reactant (orange yellow slurry)
Was filtered with a glass filter (G-5), and the residue was washed with dehydrated ether (50 ml). The orange solid remaining on the filter is washed with dehydrated dichloromethane (150 ml),
After filtration, the solvent of the filtrate was distilled off to obtain a red-orange solid (1.29)
g) was obtained. This solid is dehydrated in hexane (100 m
After reslurrying in 1) and filtering, 0.924 g of a target product of red-orange powder [ethylene (9-fluorenyl) (1-indenyl) zirconium dichloride] was obtained (yield: 61%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) 3.7 to 4.4 (m, 4H), 6.20 (d, J = 0.
8 Hz, 1H), 6.35 (d, J = 0.8 Hz, 1
H), 6.9-8.1 (m, 12H).

[0281]

[Production Example 10] [Dimethylsilylene (9-fluorenyl) (2-methyl-4-
Synthesis of phenyl-1-indenyl) zirconium dichloride] A 100 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel was sufficiently purged with nitrogen and dried. To this, 2-methyl-4-phenylindene (1.50 g, 7.7 g) produced by the method described in JP-A-6-100579.
27 mmol), dehydrated diethyl ether (40 m
l) and stirring at −78 ° C. with n-butyllithium n-
A hexane solution (7.63 mmol) was added dropwise. After the dropwise addition, the solution was allowed to warm to room temperature slowly and then stirred at room temperature overnight. As a result, the slurry concentration became high and stirring became impossible. The dehydrated diethyl ether (1
Dimethylsilylfluorenyl monochloride 1.88 synthesized in Production Example 6 under stirring at 0 ° C.
g (7.27 mmol) was added and stirred at room temperature for 12 hours to obtain a yellow slurry. Diethyl ether (100 ml) and a saturated ammonium chloride aqueous solution (100 ml) were added to the yellow slurry, and the mixture was transferred to a separatory funnel to separate the organic phase. The organic phase was washed with a saturated ammonium chloride aqueous solution, water, and saturated saline in this order. Dry over magnesium sulfate. After removing the solvent, column chromatography (solvent:
n-hexane) to obtain 1.75 g (yield: 56%) of a pale yellow powder.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz) −0.35 (d, 6H), 2.2 (s, 3H), 3.8
(T, 1H), 4.2 (s, 1H), 6.8 (s, 2
H), 6.9-7.9 (m, 16H).

A 50 ml reactor equipped with a dropping funnel was sufficiently purged with nitrogen and dried. To this, dimethylsilylene (9-fluorenyl) (2-methyl, 4-phenyl-1-indene) (0.80 g, 1.87 mmol) synthesized above,
Add dehydrated diethyl ether (20 ml) and at -78 ° C
n-butyllithium n-hexane solution (3.93 mmol)
l) was added dropwise. After the dropwise addition, the temperature of the solution was slowly raised to room temperature. Next, after stirring at room temperature for 12 hours,
Under stirring with zirconium tetrachloride (0.435 g, 1.8
7 mmol) was added dropwise, and after the addition, the temperature was spontaneously raised to room temperature. Next, after stirring at room temperature for 8 hours, the obtained red slurry was filtered with a glass filter, and the obtained solid was quickly washed with dry dichloromethane. The solvent of the obtained filtrate was removed, and the slurry was reslurried with 40 ml of dehydrated hexane.
0 mg was obtained as a red powder (yield: 51%).

[0284]

[Production Example 11] [Synthesis of ethylene (2,7-di-t-butyl-9-fluorenyl) (2-methyl-1-indenyl) zirconium dichloride] Production of 2,7-di-t-butyl-9-fluorene In a 100 ml four-necked flask equipped with a synthetic reflux tube, a thermometer, and a dropping funnel, fluorene (3.4 g, 20.5 mmol
l), 2,6-di-t-butyl-p-cresol (4.4 g, 2
0.0 mmol) and nitromethane (30 ml).
Under stirring in a water bath (10 ° C.), anhydrous aluminum chloride (4
g) dissolved in nitromethane (6 ml) was added dropwise (dropping time was 1 hour, the reaction solution gradually became purple hetero). After stirring for 3 hours, the reaction solution was put into 300 ml of ice water, transferred to a separating funnel, and after separating the organic layer, the aqueous layer was extracted with ether (200 ml × 3) and the organic layers were combined. Ether and nitromethane were completely distilled off using an evaporator and an oil pump, and the residue was washed with ether (20%).
0 ml) and 10% aqueous sodium hydroxide solution (1
After washing with 50 ml × 3), it was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained white-yellow powder was recrystallized from methanol to give the target product (3.5 yellow needle-like crystals).
g, yield 63%).

The NMR spectrum data of the obtained compound is shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 1.38
(S, 18H), 3.86 (s, 2H), 7.2-7.
Synthesis of 8 (m, 6H) 3- (2-bromoethyl) -2-methylindene 2-methylindene (4.5 g, 34.6 mm) was placed in a 200 ml four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel.
ol) and dehydrated ether (50 ml).
A hexane solution of n-butyllithium (1.61 mol / L, 23.7 ml, 38.1 mmol) was added dropwise over 1 hour, and then the temperature was naturally raised to room temperature over 6 hours. The reaction became a yellow-orange slurry.

Next, 1,2-dibromoethane (3.times.) Was placed in a 500 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel.
2.5 g, 0.173 mol), dehydrated ether (100
ml), and the total amount of the anion slurry prepared above was reduced to 0%.
C. over 1 hour, followed by stirring at room temperature for 15 hours. Transfer the obtained yellow transparent solution to 300 ml of water,
The ether layer was separated, and the aqueous layer was extracted with ether (100 ml).
× 3) and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained tan oil was purified by column chromatography (solvent: hexane) to obtain the target product (6.25 g, yield 76%) as a yellow-white transparent liquid.

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ , 90 MHz); 1.8 to 2.
6 (m, 2H), 1.93 (s, 3H), 2.8-3.
2 (m, 2H), 3.3 (br, 1H), 6.32
(S, 1H), 6.6-7.4 (m, 4H) 1- (2,7-di-t-butyl-9-fluorenyl) -2- (2-methyl-
Synthesis of 1-indenyl) ethylene In a 100 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 2,7-di-t-butylfluorene (1.18 g,
4.22 mmol) and dehydrated ether (30 ml) were added thereto, and a hexane solution of n-butyl lithium (1.67) was added at 0 ° C.
mol / liter, 2.8 ml, 4.64 mmol) was added dropwise over 1 hour, followed by stirring at room temperature for 7 hours. The reaction became red-orange and transparent. This was cooled to −78 ° C. (yellow-orange slurry), and 3- (2-bromoethyl) -2-methylindene (1 g, 4.22 mmol) dissolved in dehydrated ether (10 ml) was added dropwise over 30 minutes. ,
Thereafter, the mixture was naturally heated to room temperature and stirred for 15 hours. The reaction gradually became a yellow slurry. This was transferred to a saturated aqueous ammonium chloride solution (200 ml), the ether layer was separated, the aqueous layer was extracted with ether (100 ml × 2), and the organic layers were combined and dried over anhydrous magnesium sulfate.
The solvent was distilled off, and the obtained white-yellow powder was washed with hexane (1
00ml) and filtered to give the desired product as a white powder (1.70 g, 93% yield).

The NMR spectrum data of the obtained compound is shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 1.3~1.
9 (m, 4H), 1.40 (s, 18H), 1.91
(Br, 3H), 3.08 (br, 1H), 3.85
(Br, 1H), 6.48 (br, 1H), 7.0 to 7.0
7.9 (m, 10H) ethylene (2,7-di-t-butyl-9-fluorenyl) (2-methyl
Synthesis of l-1-indenyl) zirconium dichloride In a 300 ml four-necked flask equipped with a reflux tube, a thermometer and a dropping funnel, 1- (2,7-di-t-butyl-9-fluorenyl) -2-
(2-methyl-1-indenyl) ethylene (0.5 g, 1.
15 mmol) and dehydrated ether (50 ml).
At 78 ° C., a hexane solution of n-butyllithium (1.67 m
ol / liter, 1.45 ml, 2.42 mmol) was added dropwise over 30 minutes, and then the temperature was naturally raised to room temperature over 15 hours. The reaction became an orange-yellow slurry.

The reaction was then cooled to -78 ° C. and zirconium tetrachloride (0.282 g, 1.21 mmol) was added over 15 minutes. After that, the temperature naturally rises to room temperature,
Stir for 12 hours. Obtained reactant (orange yellow slurry)
Was filtered under pressure through a glass filter (G-5), and the residue was washed with dehydrated ether (20 ml × 2). The solvent of the filtrate was distilled off with an oil pump to obtain a red-orange solid, and the solid was washed with dehydrated hexane (10 ml × 2) to obtain the desired red-orange powder (0.300 g, yield 44%). Was.

The following shows the NMR spectrum data of the obtained compound. ¹ H-NMR (CDCl ₃ , 90 MHz): 1.2 to 1.
4 (m, 18H), 2.20 (s, 3H), 3.6-
4.2 (m, 4H), 6.10 (s, 1H), 6.8 to
7.8 (m, 10H)

[0291]

[Production Example 12] [Synthesis of dimethylsilylene (3-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride A 1-liter four-necked flask was equipped with a reflux tube and a thermometer. The vessel was equipped with a dropping funnel and was sufficiently purged with nitrogen and dried. Fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added thereto, and a hexane solution of n-butyllithium (30 mmol) was added dropwise at −10 ° C. with stirring over 30 minutes. After dropping, slowly warm to room temperature slowly,
Stirred at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a solution of dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) with stirring at −10 ° C. over 1 hour, and the mixture was naturally heated and stirred overnight. Transfer the solution to a glass filter (G-
5) Pressure filtration to remove lithium chloride, remove solvent and unreacted dichlorodimethylsilane in the filtrate under reduced pressure, reslurry with dehydrated hexane (100 ml), and pressurize with a glass filter (G-5). Filtration gave a white powder (3.30 g, 43% yield).

The following shows the NMR spectrum data of the obtained compound. ¹ H-NMR (CDCl ₃ ); 7.2 to 8.0 (m, 8
H) 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (1-indenyl) (9-fluorenyl) silane
A 200 ml four-neck flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. Indene (3.00 g, 25.8 mmol) and dehydrated ether (40 ml) were added thereto, and a hexane solution of n-butyllithium (25.8 mmol) was added dropwise at 0 ° C. while stirring. After the dropwise addition, the temperature was slowly raised to room temperature. 2 at room temperature
Stirred for hours. The reaction solution became an orange solution. 0 again
While stirring at ℃, dimethyl (9-fluorenyl) silane chloride synthesized above (6.69 g, 25.8 mmol)
l) was added, and after the dropwise addition, the temperature was slowly raised to room temperature. Stirring at room temperature for 2 hours resulted in a yellow slurry. Ether (100 ml) and a saturated aqueous ammonium chloride solution (100 ml) were added thereto, and the mixture was transferred to a separatory funnel to separate the organic layer. The aqueous layer was extracted with ether (100 ml × 3), and the organic layers were combined. Washed and dried over anhydrous magnesium sulfate. After removing the solvent, the residue was purified by column chromatography (solvent: hexane) to give a white powder (4.70).
g, yield 54%).

The NMR spectrum data of the obtained compound is shown below. ¹ H-NMR (CDCl ₃ ); 7.2 to 8.0 (m, 12
H), 6.9 (m, 1H), 6.3 (dd, 1H),
4.1 (s, 1H), 3.6 (t, 1H), -0.2
(S, 3H), -0.4 (s, 3H) dimethyl (3-methyl-1-indenyl) (9-fluorenyl
B) Synthesis of silane A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. The dimethyl (1-indenyl) (9-fluorenyl) silane (2.00 g, 5.91 mmol) and the dehydrated ether (50 ml) synthesized above were added thereto, and n-butyllithium hexane solution was stirred at -40 ° C. (6.21 mmol) were added dropwise. After the dropwise addition, the temperature was slowly raised to room temperature. Stirring overnight led to a yellow solution. This was again stirred at −40 ° C. with methyl iodide (3.78 g, 26.
6 mmol) was added, and after the dropwise addition, the temperature was slowly raised naturally to room temperature. Stirred at room temperature for one day. The reaction solution became an orange solution. Ether (100 ml) and a saturated aqueous ammonium chloride solution (100 ml) were added, and the mixture was transferred to a separatory funnel to separate an organic layer, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was removed and the product was purified by column chromatography (solvent: hexane) to obtain two isomers (one is a colorless transparent liquid and the other is a yellow liquid) (total 1.85 g, 89% yield). Was.

The following shows the NMR spectrum data of the obtained compound. ¹ H-NMR (CDCl ₃ ); two isomers (A: B = 4:
1) Isomer A 7.2-8.0 (m, 12H), 6.5 (d, 1H),
4.1 (s, 1H), 3.6 (dd, 1H), 1.2
(D, 3H), 0.1 (d, 6H), isomer B 7.2-8.0 (m, 12H), 6.1 (d, 1H),
4.0 (s, 1H), 3.6 (dd, 1H), 2.1
(S, 3H), -0.3 (d, 6H) dimethylsilylene (3-methyl-1-indenyl) (9-fur
Synthesis of (Oenyl) Zirconium Dichloride A 50 ml Schlenk bottle was equipped with a dropping funnel, and was sufficiently purged with nitrogen and dried. To this, dimethyl (3-methyl-1-indenyl) (9-fluorenyl) silane (0.80 g, 2.27 mmol) synthesized above and dehydrated ether (2
0 ml), and a hexane solution of n-butyllithium (4.76 mmol) was added dropwise at −78 ° C. with stirring. After the dropwise addition, the temperature was slowly raised to room temperature. After stirring overnight, the yellow solution became a red solution. -78 again
C., while stirring, zirconium tetrachloride (0.53 g, 2.2
7 mmol) was added, and after the dropwise addition, the temperature was slowly raised to room temperature. Stirred at room temperature overnight. The reaction liquid became a red slurry. The mixture was filtered under pressure through a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, and the slurry was reslurried with dehydrated hexane (25 ml).
Filtration under pressure was performed in 5) to give the desired metallocene as an orange powder (330 mg, yield 28%).

[0295]

[Production Example 13] [Ethylene (2-methyl-4-phenyl-1-indenyl) (9-
Synthesis of fluorenyl) zirconium dichloride] 3- (2-bromomethyl) -2-methyl-7-phenylindene
A 200 ml four-neck flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. In addition, 2-
Methyl-4-phenylindene (2.50 g, 12.12
mmol) and dehydrated ether (50 ml), and stirred at 0 ° C. under a hexane solution of n-butyllithium (12.73).
mmol) was added dropwise over 30 minutes. After the dropwise addition, the temperature was slowly raised to room temperature, followed by stirring at room temperature for 4 hours. The reaction was a yellow slurry. This was added dropwise to a solution of dibromoethane (5.22 ml, 60.6 mmol) / dehydrated ether (20 ml) with stirring at 0 ° C. over 1 hour, the temperature was allowed to rise naturally, and the mixture was stirred at room temperature overnight. The reaction was a yellow solution. Ether (100 ml) and a saturated aqueous solution of ammonium chloride (100 ml) were added thereto, and the mixture was transferred to a separatory funnel to separate an organic layer. The organic layer was washed with a saturated aqueous solution of ammonium chloride, water and saturated saline, and dried over anhydrous magnesium sulfate. The yellow oil obtained by removing the solvent was purified by column chromatography (solvent: hexane) to obtain a pale yellow oil (3.00 g, yield 79%).

The NMR spectrum data of the obtained compound is shown below. ¹ H-NMR (CDCl ₃ , 90 MHz);
8 (m, 2H), 2.1 (s, 3H), 3.0 to 3.8
(M, 2H), 3.5 (br, 1H), 6.7 (s, 1
H), 7.1-7.8 (m, 8H) 1- (9- Fluorenyl ) -2- (2-methyl-4-phenyl-1-i
Synthesis of Ndenyl) Ethylene A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. To this, fluorene (1.29 g, 7.76 mmol) and dehydrated ether (25 ml) were added, and a hexane solution of n-butyllithium (8.15 mmol) was added dropwise over 30 minutes while stirring at 0 ° C. After the dropwise addition, the temperature was slowly raised to room temperature and stirred at room temperature for 1.5 hours. The reaction liquid became a brown slurry. Thereafter, 3- (2-bromomethyl) is added under stirring at 0 ° C.
2-methyl-7-phenylindene (2.42 g, 7.73
(mmol) / dehydrated ether (40 ml) solution over 1 hour, the mixture was heated naturally, and stirred at room temperature overnight, whereby the reddish purple solution became a dark orange solution. This is ether (100
ml) and a saturated aqueous ammonium chloride solution (100 ml) were added, and the mixture was transferred to a separatory funnel to separate an organic layer. The organic layer was washed with a saturated aqueous ammonium chloride solution, water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was removed and the residue was purified by column chromatography (solvent: hexane) to give an orange oil. When this was depressurized with a vacuum pump, it was foamed and solidified to obtain a pale orange powder (1.10 g, yield: 36%).

The NMR spectrum data of the obtained compound is shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 1.3~1.
9 (m, 4H), 1.91 (br, 3H), 3.08
(Br, 1H), 3.85 (br, 1H), 6.48
(Br, 1H), 7.0-7.9 (m, 10H) ethylene (2-methyl-4-phenyl-1-indenyl) (9-f
Synthesis of fluorenyl) zirconium dichloride A 50 ml Schlenk bottle was equipped with a dropping funnel, and was sufficiently purged with nitrogen and dried. 1- (9-fluorenyl) -2- (2-methyl-4-phenyl-1-indenyl) synthesized above
Ethylene (0.50 g, 1.25 mmol) and dehydrated ether (20 ml) were added, and a hexane solution of n-butyllithium (2.63 mmol) was added dropwise at −78 ° C. with stirring. After the dropwise addition, the temperature was slowly raised to room temperature.
After stirring at room temperature overnight, the yellow-orange solution turned into a brown solution, and then turned into a brown-orange slurry via a dark-orange slurry. Again-
While stirring at 78 ° C., zirconium tetrachloride (0.307 g,
1.31 mmol) was added, and after the dropwise addition, the temperature was slowly raised to room temperature. After stirring overnight at room temperature, the ocher slurry turned into an orange slurry. Glass filter (G-
The mixture was filtered under pressure in 5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, reslurried with dehydrated hexane (30 ml), and filtered through a glass filter (G-5) to obtain the target metallocene as a red-orange powder (320 mg, yield 46%). .

The following shows the NMR spectrum data of the obtained compound. _{^{1 H-NMR (CDCl 3,}} 90MHz); 2.20
(S, 3H), 3.6-4.2 (m, 4H), 6.10
(S, 1H), 6.8-8.0 (m, 16H)

[0299]

[Production Example 14] [Dimethylsilylene (2-methyl-4-i-propyl-7-methyl
Synthesis of -1-indenyl) (9-fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride Let dry. Fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added thereto, and a hexane solution of n-butyllithium (30 mmol) was added dropwise at −10 ° C. with stirring over 30 minutes. After dropping, slowly warm to room temperature slowly,
Stirred at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a solution of dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) with stirring at −10 ° C. over 1 hour, and the mixture was naturally heated and stirred overnight. Transfer the solution to a glass filter (G-
5) Filter under pressure to remove lithium chloride, remove solvent and unreacted dichlorodimethylsilane in the filtrate under reduced pressure, and reslurry with dehydrated hexane (100 ml).
The mixture was filtered under pressure with a glass filter (G-5) to obtain a white powder (3.30 g, yield 43%).

The NMR spectrum data of the obtained compound is shown below. ¹ H-NMR (CDCl ₃ ); 7.2 to 8.0 (m, 8
H), 4.1 (s, 1H), 0.15 (s, 6H) dimethyl (2-methyl-4-i-propyl-7-methyl-1-indene)
Synthesis of nyl) (9-fluorenyl) silane A 100 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel, and was sufficiently purged with nitrogen and dried. To this was added 2-methyl-4-i-propyl-7-methylindene (1.50 g,
8.06 mmol) and dehydrated ether (25 ml) were added, and a hexane solution of n-butyllithium (8.46 mmol) was added dropwise at −78 ° C. with stirring. After the dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature overnight, the colorless solution turned into a white slurry, followed by a light yellow slurry to a yellow slurry. While stirring the reaction solution at 0 ° C., dimethyl (9-fluorenyl) silane chloride (2.06 g, 8.06 mmol) synthesized above was added thereto, and the mixture was stirred at room temperature for 1.5 hours. This is ether (100 ml),
A saturated aqueous ammonium chloride solution (100 ml) was added, the mixture was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution, water and saturated saline, and dried over anhydrous magnesium sulfate. The yellow oil obtained by removing the solvent was purified by column chromatography (solvent: hexane) to obtain a yellow oil (1.50 g, yield 46%).

The NMR spectrum data of the obtained compound is shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 6.6~8.
0 (m, 11H), 4.2 (s, 1H), 3.7 (s,
1H), 2.65 to 3.05 (m, 1H), 2.45
(S, 3H), 2.25 (s, 3H), 1.1-1.3
(D, 6H), -0.35 (d, 6H) dimethylsilylene (2-methyl-4-i-propyl-7-methyl-1)
-Indenyl) (9-fluorenyl) zirconium dichloride
Synthesis of Lido A 50 ml Schlenk bottle was equipped with a dropping funnel, and was sufficiently purged with nitrogen and dried. The dimethyl (2-methyl-4-i-propyl-7-methyl-1-indenyl) (9
-Fluorenyl) silane (0.80 g, 1.96 mmol)
l) and dehydrated ether (20 ml) were added thereto, and n-butyllithium hexane solution (4.11 mm
ol) was added dropwise. After the dropwise addition, the temperature was slowly raised to room temperature. After stirring overnight, the lemon yellow solution became a reddish brown solution via a bright yellow solution. Under stirring at −78 ° C., zirconium tetrachloride (0.456 g, 1.96 mm
ol), and after the addition, the temperature was slowly raised to room temperature. Stirred at room temperature for 8 hours. The reaction liquid became a red slurry. The mixture was filtered under pressure through a glass filter (G-5) to remove ether, and the residue was quickly washed with dehydrated dichloromethane (the residue was lithium chloride). The solvent of the filtrate thus obtained was removed, and dehydrated hexane (30 m
l), and the mixture was filtered through a glass filter (G-4) to obtain the target metallocene as a red powder (50 mg, yield 4%).

[0302]

[Production Example 15] [Dimethylsilylene (2,3-dimethyl-1-indenyl) (9
Synthesis of -Fluorenyl) zirconium dichloride] Synthesis of dimethyl (9-fluorenyl) silane chloride A 1-liter four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel. Fluorene (5.00 g, 30 mmol) and dehydrated ether (100 ml) were added thereto, and a hexane solution of n-butyllithium (30 mmol) was added dropwise at −10 ° C. with stirring over 30 minutes. After dropping, slowly warm to room temperature slowly,
Stirred at room temperature for 4 hours. The reaction liquid became a yellow slurry. This was added dropwise to a solution of dichlorodimethylsilane (18.24 ml, 150 mmol) / dehydrated ether (100 ml) with stirring at −10 ° C. over 1 hour, and the mixture was naturally heated and stirred overnight. Transfer the solution to a glass filter (G-
5) Filter under pressure to remove lithium chloride, remove solvent and unreacted dichlorodimethylsilane in the filtrate under reduced pressure, and reslurry with dehydrated hexane (100 ml).
The mixture was filtered under pressure with a glass filter (G-5) to obtain a white powder (3.30 g, yield 43%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.2 to 8.0 (m, 8
H) 4.1 (s, 1H), 0.15 (s, 6H) Synthesis of 1,2-dimethylindene A 200 ml four-necked flask equipped with a reflux tube, a thermometer, and a dropping funnel was sufficiently purged with nitrogen. And dried. Methylmagnesium bromide (3.0 mol / liter ether solution) (16.9 ml, 50.7 mmol) and dehydrated ether (50 ml) were added thereto, and 2-methyl-1-indanone (3.70 g, 25 .3 mmol) /
Dehydrated ether (20 ml) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, then transferred into ice water, and transferred to a separating funnel to separate an organic layer. The aqueous layer is ether (100m
1 × 3), the organic layers were combined, washed with a saturated aqueous solution of ammonium chloride, water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the solvent, 1,2-dimethyl-1-
Hydroxy-indene was obtained. 30 ml of this
, And 0.1 g of p-toluenesulfonic acid was added, and the mixture was refluxed for 3 hours without water. The organic layer was transferred to a separating funnel and washed with a saturated aqueous ammonium solution, water, and saturated saline,
Dry over anhydrous magnesium sulfate. Remove the solvent,
Purification by column chromatography (solvent: hexane) gave a pale yellow solution (2.70 g (GC 94%), yield 74).
%).

The NMR spectrum data of the obtained compound are shown below. ¹ H-NMR (CDCl ₃ ); 7.1 to 7.6 (m, 4
H), 3.2 (s, 2H), 2.0 (s, 6H) dimethyl (2,3-dimethyl-1-indenyl) (9-fluore
Synthesis of nyl) silane A 200 ml four-necked flask was equipped with a reflux tube, a thermometer, and a dropping funnel. The 1,2-dimethylindene synthesized above (1.60 g, 1
1.09 mmol) and dehydrated ether (40 ml) were added, and a hexane solution of n-butyllithium (11.6 mmol) was added dropwise at 0 ° C. while stirring. After the dropwise addition, the temperature was slowly raised to room temperature. Stirring at room temperature overnight resulted in a milky white slurry. Under stirring at 0 ° C., dimethyl (9-fluorenyl) silane chloride (2.72 g, 10.51 mmol) synthesized above was added, and the mixture was stirred at room temperature for 2 hours. The reaction liquid became a yellow slurry. To this was added N-methyl-2-pyrrolidine (0.1 g), and the mixture was stirred at room temperature for 1.5 hours. This is ether (100m
l), a saturated aqueous ammonium chloride solution (100 ml) was added, and the mixture was transferred to a separatory funnel to separate an organic layer. The organic layer was washed with a saturated aqueous ammonium chloride solution, water and saturated saline, and dried over anhydrous magnesium sulfate. After removing the solvent, the residue was purified by column chromatography (solvent: hexane) to give a yellow powder (1.1
0 g, 27% yield).

The NMR spectrum data of the obtained compound are shown below. _{^{1 H-NMR (CDCl 3,}} 90MHz); 6.7~8.
0 (m, 12H), 4.5 (s, 1H), 3.6 (t,
1H), 2.0 (s, 6H), -0.4 (s, 6H) dimethylsilylene (2,3-dimethyl-1-indenyl) (9-
Synthesis of fluorenyl) zirconium dichloride A 50 ml Schlenk bottle was equipped with a dropping funnel, and was sufficiently purged with nitrogen and dried. The dimethyl (2,3-dimethyl-1-indenyl) (9-fluorenyl) silane (0.80 g, 2.18 mmol) and dehydrated ether (15 ml) synthesized above were added thereto, and the mixture was stirred at -78 ° C for n. A hexane solution of 4.5-butyllithium (4.58 mmol) was added dropwise.
After the dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 8 hours, the pale yellow solution became a yellow slurry via a yellow solution. Again with stirring at −78 ° C., zirconium tetrachloride (0.509 g, 2.18 mmol) was added,
After the dropwise addition, the temperature was slowly raised to room temperature. After stirring at room temperature overnight, the reaction solution became a red slurry. Pressure filtration with a glass filter (G-5) to remove ether,
The filtrate was quickly washed with dehydrated dichloromethane (the filtrate was lithium chloride). The solvent of the filtrate thus obtained was removed, reslurried with dehydrated hexane (30 ml), and filtered through a glass filter (G-5) to obtain the target metallocene as a red powder (427 mg, yield 37%).

[0306]

Example 1 Preparation of Catalyst Solution Dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-) was placed in a glass flask sufficiently purged with nitrogen.
5.8 mg of butyl-9-fluorenyl) zirconium dichloride (compound a) was added, and 1.57 ml of a toluene solution of methylaluminoxane (MAO) (Al; 1.1 mol / l) and 2.76 ml of toluene were added thereto. The mixture was stirred at 23 ° C. for 30 minutes with a magnetic rotor to obtain a catalyst solution.

Polymerization In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 800 ml of hexane and 1-octene 2 were added.
Then, the temperature inside the system was increased to 130 ° C.
Subsequently, 1 mmol of triisobutylaluminum (TIBA) and 0.5 ml of the catalyst solution prepared above (Zr
(0.001 mmol) was injected with ethylene to initiate polymerization. Thereafter, the total pressure was maintained at 30 kg / cm ² -G by continuously supplying only ethylene, and polymerization was carried out at 140 ° C. for 15 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene was purged. The polymer was precipitated by throwing the obtained polymer solution into a large excess of methanol. The polymer is recovered by filtration at 130 ° C.
And dried under reduced pressure overnight. As a result, the MFR was 0.16
g / 10 minutes, and 65.3 g of an ethylene / 1-octene copolymer having a density of 0.892 g / cm ³ was obtained. Table 1 shows the results.

[0308]

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the preliminary contact time between the compound a and MAO was changed to 1 hour. Table 1 shows the results.

[0309]

Example 3 Polymerization was carried out in the same manner as in Example 1 except that the preliminary contact time between compound a and MAO was changed to 2 hours. Table 1 shows the results.

[0310]

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the pre-contact time between compound a and MAO was 1 hour, and the pre-contact temperature was 5 ° C. Table 1 shows the results
Shown in

[0311]

Example 5 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 160 ° C.

[0312]

Example 6 Preparation of Catalyst Solution Aluminoxane (Al concentration = 7.5% by weight, (Me + i-Bu)) was placed in a 200 ml volumetric flask which was sufficiently purged with nitrogen.
/Al)=1.91; Me / i-Bu = 79/21, both in molar ratio). Here, n-decane was charged in a total amount of 200 ml, and the Al concentration was 0.20 m.
ol / liter of aluminoxane solution was obtained. 125 ml of this aluminoxane solution was charged into a 200 ml glass flask sufficiently purged with nitrogen, and nitrogen saturated with water at 23 ° C. was supplied at 3.3 N l / hr for 120 minutes with stirring. Here, nitrogen was supplied to the gas phase of the aluminoxane solution. The aluminoxane in the aluminoxane solution after the treatment was (Me + i-Bu) / Al) = 1.61.

In a glass flask sufficiently purged with nitrogen, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) was placed.
7.0 mg of (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (compound a) was added thereto, and the n-decane solution of aluminoxane prepared as described above (Al;
(0.20 mol / l) and 90 ml of n-hexane were added and stirred at 23 ° C. for 30 minutes with a magnetic rotor to obtain a catalyst solution.

Polymerization was carried out in the same manner as in Example 1 except that the above catalyst solution was used as the catalyst solution. Table 1 shows the results.

[0315]

Example 7 In Example 6, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-) was used in place of compound a. Polymerization was carried out in the same manner as in Example 6 except that butyl-9-fluorenyl) zirconium dichloride (compound b) was used. Table 1 shows the results.

[0316]

Example 8 In Example 6, instead of 1-octene,
Polymerization was carried out in the same manner as in Example 6, except that 4-methyl-1-pentene was used and the polymerization time was 30 minutes. as a result,
The MFR is 0.5 g / 10 min and the density is 0.889 g /
58.3 g of an ethylene / 4-methyl-1-pentene copolymer having a cm ³ was obtained.

[0317]

Example 9 Preparation of Catalyst Solution A glass flask sufficiently purged with nitrogen was charged with 5 m of n-hexane.
l, and 1 ml of a toluene solution of the compound a (Zr
0.001 mmol) and 1 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.002 mmol as B)
Was added and stirred at 23 ° C. for 30 minutes with a magnetic rotator to obtain a catalyst solution.

Polymerization In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 800 ml of hexane and 1-octene 2 were added.
Then, the temperature inside the system was increased to 130 ° C.
Subsequently, triisobutylaluminum (TIBA) 0.1.
Polymerization was initiated by injecting 5 mmol and the catalyst solution prepared above with ethylene. Thereafter, the total pressure is reduced to 30 kg / c by continuously supplying only ethylene.
While maintaining the m ² -G, polymerization was carried out at 140 ° C. for 15 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene was purged. The polymer was precipitated by throwing the obtained polymer solution into a large excess of methanol. The polymer was collected by filtration and dried at 130 ° C. under reduced pressure overnight. As a result, MF
R is 0.53 g / 10 min and density is 0.892 g / c
63.3 g of an ethylene / 1-octene copolymer having an m of ³
Obtained.

[0319]

[Table 1]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 2 is an explanatory view showing a step of preparing an olefin polymerization catalyst used in a second method for producing an olefin polymer according to the present invention.

Claims (9)

[Claims] (A-1) A transition metal compound of Group IVB of the periodic table represented by the following general formula (I): (B) (B-1) an organoaluminum oxy compound, and / or (B) -2) a compound capable of forming an ion pair by reacting with the transition metal compound (A-1) or, if necessary, further preliminarily contacting with (C) an organoaluminum compound. Olefin polymerization catalyst; (Wherein, M is a transition metal atom of Group IVB of the periodic table, R ¹ may be the same or different, and at least one of them is an aryl group having 11 to 20 carbon atoms, An arylalkyl group having 12 to 40 atoms,
An arylalkenyl group having 13 to 40 carbon atoms, an alkylaryl group having 12 to 40 carbon atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ¹ are those together with the carbon atom bonded to the case and to form an aromatic or aliphatic ring [this, the ring formed by R ¹ in the number of carbon atoms from 4 to 20 in all including carbon atoms to which R ¹ is attached is there〕,
The other R ¹ is a hydrogen atom, a halogen atom, a group having 1 carbon atom.
And R ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. An aryl group, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms,
A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and at least two of the groups represented by R ² are, together with the carbon atom to which they are bonded, aromatic, ring or aliphatic ring may form [this case a ring formed by R ² has a number of carbon atoms in all including carbon atoms to which R ² is attached 4-2
0, and the other R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group], R ¹ and R ² may be the same or different from each other, R ³ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, 7 to 4 carbon atoms
0 arylalkyl group, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. X ¹ and X ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen Containing groups, sulfur containing groups or nitrogen containing groups,
Or a conjugated diene residue formed by X ¹ and X ² , Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent halogenated carbon group having 1 to 20 carbon atoms. Hydrogen group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -S
O _2- , -NR ^5- , -P (R ⁵ )-, -P (O) (R
⁵⁾ -, - BR ⁵ - or -AlR ⁵ - [proviso R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms] Is). 2. A method for producing an olefin polymer, comprising homopolymerizing an olefin or copolymerizing two or more olefins in the presence of the olefin polymerization catalyst according to claim 1. 3. The process for producing an olefin polymer according to claim 2, wherein the olefin to be homopolymerized is ethylene, and the two or more olefins are ethylene and an α-olefin having 3 to 20 carbon atoms. 4. An olefin polymer produced by the method for producing an olefin polymer according to claim 2. 5. An ethylene-based polymer produced by the method for producing an olefin polymer according to claim 3. (A-2) a transition metal compound of Group IVB of the periodic table represented by the following general formula (II): (B) (B-1) an organoaluminum oxy compound, and / or (B) -2) In the presence of a catalyst obtained by pre-contacting a compound which forms an ion pair by reacting with the transition metal compound (A-2) or, if necessary, further with (C) an organoaluminum compound A method for producing an olefin polymer, which comprises homopolymerizing an olefin or copolymerizing two or more olefins; (Wherein, M is a transition metal atom of Group IVB of the periodic table, R ⁶ may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom An aryl group having 6 to 10 atoms, an alkenyl group having 2 to 10 carbon atoms, a silicon-containing group, an oxygen-containing group,
A sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ⁷ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 20 aryl groups, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms ,
An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ⁶ and R ⁷ may be the same or different from each other, R ⁸ and R ⁹ are either carbon 1 to 5 atoms
And a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 2 to 1 carbon atoms.
0, an alkenyl group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group; X ¹ and X ² may be the same or different from each other; A hydrocarbon group having 1 to 20 atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group,
Or a conjugated diene residue formed by X ¹ and X ² , Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent halogenated carbon group having 1 to 20 carbon atoms. Hydrogen group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -S
O _2- , -NR ^5- , -P (R ⁵ )-, -P (O) (R
⁵⁾ -, - BR ⁵ - or -AlR ⁵ - [proviso R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms] Is). 7. The method for producing an olefin polymer according to claim 6, wherein the olefin to be homopolymerized is ethylene, and the two or more olefins are ethylene and an α-olefin having 3 to 20 carbon atoms. 8. An olefin polymer produced by the method for producing an olefin polymer according to claim 6. 9. An ethylene-based polymer produced by the method for producing an olefin polymer according to claim 7.