JP2000159829A - Catalyst for olefin polymerization and production of polyolefin using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for producing a homogeneous polyolefin having a high mol.wt. and narrow mol.wt. distribution and composition distribution by using a transition metal compound and an activating cocatalyst and/or an organometallic compound. SOLUTION: A transition metal compound of formula I or II is used. In the formulas, M is a transition metal of the group 3-6; n is 3-6; L1 and L2 are each a group of formula III, IV, or V [a is 1 or 2 in formula I and is 0 or 1 in formula II; (R1)a and (R2)a are each H, a hydrocarbon group, a heteroatom- containing hydrocarbon group, or a (heteroatom-containing) hydrocarbon-group- containing silyl group; b is 0 or 1; and (R1)b, (R2)b, and R3 are each the same as (R1)a or (R2)a or they form a ring] provided that at least either L1 or L2 is a group of formula III or IV and that a group of formula V is a monovalent anion; X is H, halogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group, substituted amino, or substituted alkoxy; 1 is an integer of 2 or higher; and L3 is a group of formula VI [R4 and R5 are each the same as (R1)b, (R2)b, or R3; and m is 1-10].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization using a novel transition metal compound and a method for producing a polyolefin using the same.

[0002]

2. Description of the Related Art Until now, the heterogeneous Ziegler catalyst mainly comprising titanium chloride or chromium oxide has been mainly used for polymerization of olefins.

Recently, however, homogeneous catalysts for producing polyolefins using transition metal compounds or organic transition metal compounds have been actively studied, and many reports have been made on the possibility of complex catalysts, especially soluble complex catalysts.

[0004] Most of these are organic transition metal compounds having two or more cyclopentadienyl derivatives collectively referred to as metallocene compounds as substituents, and include bis (cyclopentadienyl) zirconium dichloride and bis (substituted cycloalkyl). Typical compounds include (pentadienyl) zirconium dichloride (Japanese Patent Application Laid-Open No. 58-1983).
No. 19309). The complex catalyst according to the prior art has a limit in copolymerizability, and a complex catalyst having higher copolymerizability has been demanded. As a complex catalyst with dramatically improved copolymerizability, a complex having a constrained geometric structure in which a cyclopentadienyl derivative and an amide ligand are cross-linked with a silyl atom has been reported. There was a problem (Japanese Unexamined Patent Publication No. 3-163088).

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has an object to provide a novel structure which has not been found in a wide variety of olefin polymerization technical fields. An object of the present invention is to provide a catalyst for olefin polymerization and to produce and develop a new catalyst in this technical field, and to provide a method for producing a polyolefin more economically using the catalyst.

[0006]

That is, the present invention provides:
(A) The following general formula (1)

[0007]

Embedded image

(Where M is the periodic table 3, 4, 5, or 6
A transition metal of the group 3, wherein n represents a formal oxidation number of M 3 to 6
Is an integer. L ¹ and L ² may be the same or different from each other, and the following general formulas (2), (3) ((2) and (3) contain at least one nitrogen atom at the benzene ring site) or (4 ), At least one of L ¹ and L ² is (2) or (3), and the formula (4) is always a monovalent anion. Xs may be the same or different, and each represents a hydrogen atom, a halogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, a substituted amino group, or a substituted alkoxy group, and l is an integer of n-2 or more.

[0009]

Embedded image

[0010]

Embedded image

[0011]

Embedded image

Here, (R ¹ ) a or (R ² ) a may be the same or different, and a may be the same integer or different and may be 1 or 2, and the formula (2) or (3) )
A represents 1 when represents a monovalent anion, and a represents 2 when the formula (2) or (3) is neutral. (R ¹ ) a
Alternatively, (R ² ) a is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. Also, (R ¹ )
b and (R ² ) b may be the same or different, and b may be the same integer or different and are 0 or 1, and (R
¹ ) b, (R ² ) b or R ³ is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, or forms them A ring may be formed via an atom. )) Or (A ′) L
General formula (5) in which ¹ and L ² are linked by a substituent L ³ represented by the formula (6)

[0013]

Embedded image

[0014]

Embedded image

(Where M is the periodic table 3, 4, 5, or 6
A transition metal of the group 3, wherein n represents a formal oxidation number of M 3 to 6
Is an integer. L ¹ and L ² may be the same or different from each other, and the following general formulas (2), (3) ((2) and (3) contain at least one nitrogen atom at the benzene ring site) or (4 ), At least one of L ¹ and L ² is (2) or (3), and the formula (4) is always a monovalent anion. Xs may be the same or different, and each represents a hydrogen atom, a halogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, a substituted amino group, or a substituted alkoxy group, and l is an integer of n-2 or more.

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

Here, (R ¹ ) a or (R ² ) a may be the same or different, and a may be the same integer or different and may be 0 or 1, and may be represented by the formula (2) or (3) )
When a represents a monovalent anion, a is 0, and when the formula (2) or (3) is neutral, a is 1. R ⁴ and R ⁵ may be the same or different, and represent a hydrocarbon group, a hetero atom-containing hydrocarbon group, a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, or an atom forming them. And a ring may be formed through the ring. m is an integer of 1 to 10. A) a transition metal compound represented by
The present invention relates to an olefin polymerization catalyst comprising (B) an activating co-catalyst and / or (C) an organometallic compound, and a method for producing a polyolefin, wherein olefin polymerization is carried out using the catalyst. is there.

Hereinafter, the present invention will be described in detail.

(A) used in the present invention,
(A ′) L ¹ and L ² in the transition metal compound are represented by the formula (2):
(3) or (4), and at least one of L ¹ and L ² is (2) or (3).

In the formula (2), the main skeleton is a fluorene ring,
Contains at least one nitrogen atom at the benzene ring site.
(R ¹ ) a may be the same or different, and a may be the same integer or different and may be 0, 1 or 2, and when the transition metal compound is represented by the formula (1), A represents 1 when represents a monovalent anion, and a represents 2 when the formula (2) is neutral. When the transition metal compound is represented by the formula (5), a is 0 when the formula (2) represents a monovalent anion, and 1 when the formula (2) is neutral.
(R ¹ ) a is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. (R ¹ ) b may be the same or different, b may be the same integer or different and may be 0 or 1, and (R ¹ ) b may be hydrogen, a hydrocarbon group,
A heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group,
(R ¹ ) b forms a ring via the atoms forming them. As a preferable example in the formula (2), 1
Azafluorene group, 2-methyl-1-azafluorene group, 2,7-dimethyl-1-azafluorene group, 2-t
-Butyl-1-azafluorene group, 2,7-di-t-butyl-1-azafluorene group, 2-azafluorene group,
3-methyl-2-azafluorene group, 3,6-dimethyl-1-azafluorene group, 3-tert-butyl-2-azafluorene group, 3,6-di-tert-butyl-2-azafluorene group, 3-azafluorene group, 2-methyl-3-azafluorene group, 2,7-dimethyl-3-azafluorene group, 2-t-butyl-3-azafluorene group, 2,7-
Di-t-butyl-3-azafluorene group, 4-azafluorene group, 3-methyl-4-azafluorene group, 3,6
-Dimethyl-4-azafluorene group, 3-t-butyl-
4-azafluorene group, 3,6-di-t-butyl-4-
Azafluorene group, 1,5-diazafluorene group, 2-
Methyl-1,5-diazafluorene group, 2,7-dimethyl-1,5-diazafluorene group, 1,6-diazafluorene group, 1,7-diazafluorene group, 1,8-diaza Fluorene group, 2,5-diazafluorene group, 2,6
A diazafluorene group, a 2,7-diazafluorene group,
2,8-diazafluorene group, 3,5-diazafluorene group, 3,6-diazafluorene group, 3,7-diazafluorene group, 3,8-diazafluorene group, 4,5-dia Zafluorene group, 4,6-diazafluorene group, 4,
7-diazafluorene group, 4,8-diazafluorene group, 1,2,5-triazafluorene group, 1,2,6-
Triazafluorene group, 1,2,7-triazafluorene group, 1,2,8-triazafluorene group, 1,3,5
-Triazafluorene group, 1,3,6-triazafluorene group, 1,3,7-triazafluorene group, 1,3
8-triazafluorene group, 1,4,5-triazafluorene group, 1,4,6-triazafluorene group, 1,
4,7-triazafluorene group, 1,4,8-triazafluorene group, 2,3,5-triazafluorene group,
2,3,6-triazafluorene group, 2,3,7-triazafluorene group, 2,3,8-triazafluorene group, 2,4,5-triazafluorene group, 2, 4,6-
Triazafluorene group, 2,4,7-triazafluorene group, 2,4,8-triazafluorene group, 3,4,5
-Triazafluorene group, 3,4,6-triazafluorene group, 3,4,7-triazafluorene group, 3,4
8-triazafluorene group, 1,2,5,6-tetraazafluorene group, 1,2,5,7-tetraazafluorene group, 1,2,5,8-tetraazafluorene group,
1,2,6,7-tetraazafluorene group, 1,2,2
6,8-tetraazafluorene group, 1,2,7,8-tetraazafluorene group, 1-azafluorenyl group, 2-
Methyl-1-azafluorenyl group, 2,7-dimethyl-
1-azafluorenyl group, 2-t-butyl-1-azafluorenyl group, 2,7-di-t-butyl-1-azafluorenyl group, 2-azafluorenyl group, 3-azafluorenyl group, 4-azafluorenyl group, 1,5- Diazafluorenyl group, 2-methyl-1,5-diazafluorenyl group, 2,7-dimethyl-1,5-diazafluorenyl group, 1,6-diazafluorenyl group, 1,7-diazafluorenyl group, 1,8-diazafluorenyl group, 2,5
-Diazafluorenyl group, 2,6-diazafluorenyl group, 2,7-diazafluorenyl group, 2,8-diazafluorenyl group, 3,5-diazafluorenyl Groups 3,6
-Diazafluorenyl group, 3,7-diazafluorenyl group, 3,8-diazafluorenyl group, 4,5-diazafluorenyl group, 2-methyl-4,5-dia Zafluorenyl group, 2,7-dimethyl-4,5-diazafluorenyl group, 2,7-di-t-butyl-4,5-diazafluorenyl group, 4,6-diaza A fluorenyl group, a 4,7-diazafluorenyl group, a 4,8-diazafluorenyl group,
1,2,5-triazafluorenyl group, 1,2,6-triazafluorenyl group, 1,2,7-triazafluorenyl group, 1,2,8-triazafluorenyl Group, 1,
3,5-triazafluorenyl group, 1,3,6-triazafluorenyl group, 1,3,7-triazafluorenyl group, 1,3,8-triazafluorenyl group, 1,4,5
-A triazafluorenyl group, a 1,4,6-triazafluorenyl group, a 1,4,7-triazafluorenyl group,
1,4,8-triazafluorenyl group, 2,3,5-triazafluorenyl group, 2,3,6-triazafluorenyl group, 2,3,7-triazafluorenyl group Group, 2,
3,8-triazafluorenyl group, 2,4,5-triazafluorenyl group, 2,4,6-triazafluorenyl group, 2,4,7-triazafluorenyl group, 2,4,8
-A triazafluorenyl group, a 3,4,5-triazafluorenyl group, a 3,4,6-triazafluorenyl group,
3,4,7-triazafluorenyl group, 3,4,8-triazafluorenyl group, 1,2,5,6-tetraazafluorenyl group, 1,2,5,7-tetra An azafluorenyl group, a 1,2,5,8-tetraazafluorenyl group,
1,2,6,7-tetraazafluorenyl group, 1,2,2
6,8-tetraazafluorenyl group, 1,2,7,8-
Examples include, but are not limited to, a tetraazafluorenyl group.

In the formula (3), the main skeleton is an indene ring, and at least one nitrogen atom is contained in a benzene ring site.
(R ² ) a may be the same or different, a may be the same integer or different and may be 0, 1 or 2, and when the transition metal compound is represented by the formula (1), the formula (3) A represents 1 when represents a monovalent anion, and a represents 2 when the formula (3) is neutral. When the transition metal compound is represented by the formula (5), a is 0 when the formula (3) represents a monovalent anion, and 1 when the formula (3) is neutral.
(R ² ) a is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. (R ² ) b may be the same or different, b may be the same integer or different and may be 0 or 1, and (R ² ) b may be hydrogen, a hydrocarbon group,
A heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group,
(R ² ) b forms a ring via the atoms forming them. As a preferable example in the formula (3), 4
-Pyringin group, 7-methyl-4-pyringin group, 7-
t-butyl-4-pyringin group, 2,7-dimethyl-4
-Pyringin group, 5-pyringin group, 6-pyringin group, 7-pyringin group, 4,5-diazaindene group, 2
-Methyl-4,5-diazaindene group, 2-t-butyl-4,5-diazaindene group, 4,6-diazaindene group, 4,7-diazaindene group, 5,6-diazaindene group, 4-pyrindinyl group, 7 -Methyl-4-pyridinyl group, 7-t-butyl-4-pyridinyl group, 2,7
-Dimethyl-4-pyridinyl group, 2,7-t-butyl-4-pyridinyl group, 5-pyridinyl group, 6-pyridinyl group, 7-pyridinyl group, 4,5-diazaindenyl group, 4,6-diazaindenyl group, Examples thereof include a 4,7-diazaindenyl group and a 5,6-diazaindenyl group, but are not limited thereto.

Formula (4) is a cyclopentadienyl derivative of a monovalent anion and a substituted cyclopentadienyl derivative of a monovalent anion. R ³ may be the same or different, and R ³ is hydrogen or carbon It is a hydrogen group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, or R ³ forms a ring via the atoms forming them. Preferred examples of the formula (4) include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, and a pentamethylcyclopentadienyl Group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, t-butylcyclopentadienyl group, methylethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl Group, methylindenyl group, benzoindenyl group, t-butylindenyl group,
Trimethylsilylindenyl group, dimethylaminoindenyl group, methoxyindenyl group, methylfluorenyl group, 2,7-dimethylfluorenyl group, 2,7-di (t
-Butyl) fluorenyl group, 2-methoxyfluorenyl group, 4-methoxyfluorenyl group, 2,7-dimethoxyfluorenyl group, 2-dimethylaminofluorenyl group,
Examples thereof include a 4-dimethylaminofluorenyl group and a 2,7-dimethylaminofluorenyl group, but are not limited thereto.

(R ¹ ) a, (R ² ) a, (R ¹ ) b,
Preferred examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group of (R ² ) b or R ³ include a methyl group, an ethyl group,
Isopropyl group, n-propyl group, n-butyl group, se
c-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, trimethylsilylmethyl group, alkyl group such as dimethylphenylsilylmethyl group, benzyl group, methoxybenzyl group, aralkyl group such as dimethylaminobenzyl group, phenyl group, o -Tolyl group, m-tolyl group,
p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group, m-butyl Phenyl group, p-butylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-
Butyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-dimethylaminophenyl group, m-dimethylaminophenyl group, p-dimethylaminophenyl group, 2,6-dimethylphenyl Group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6-di (n-butyl) phenyl group, 2,6-di (t-butyl) Phenyl group, 2,6-di (sec-butyl) phenyl group, 2,6-diphenylphenyl group, 2,
6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group,
2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group,
2,4,6-tri (n-butyl) phenyl group,
6-tri (t-butyl) phenyl group, 2,4,6-tri (sec-butyl) phenyl group, 2,4,6-triphenylphenyl group, 2,4,6-trimethoxyphenyl group, 2, 4,6-tri (dimethylamino) phenyl group,
An aryl group such as a 2,4,6-trifluorophenyl group can be mentioned. Examples of the silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group as a substituent include a trimethylsilyl group, a triethylsilyl group, and a triethylsilyl group. Examples thereof include an isopropylsilyl group, a tributylsilyl group, a triphenylsilyl group, a dimethylmethoxysilyl group, and a dimethylphenylsilyl group. Further, in addition to the substituents described above, each of (R ¹ ) b, (R ² ) b or R ³ may form a ring, and the cycloalkadienyl moiety may form an indenyl skeleton or a fluorenyl skeleton.

A crosslinking group for crosslinking L ¹ and L ² in the general formula (5)
L ³ is represented by the following general formula (6),

[0027]

Embedded image

[0028] R ⁴ and R ⁵ may be the same or different, hydrocarbon group, or a silyl group having a hetero atom-containing hydrocarbon group or a hydrocarbon group or a hetero atom-containing hydrocarbon group, or R ^4, And R ⁵ form a ring via the atoms forming them. Where m is 1
Is an integer of 10 to 10. Examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and trimethylsilyl. Alkyl group such as methyl group, dimethylphenylsilylmethyl group, aralkyl group such as benzyl group, methoxybenzyl group, dimethylaminobenzyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethyl Phenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group , O- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- t- butyl) phenyl group, o- methoxyphenyl group, m- methoxyphenyl group, p- methoxyphenyl group, o- dimethylaminophenyl group, m- dimethylaminophenyl group, p
-Dimethylaminophenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group,
2,6-di (n-butyl) phenyl group, 2,6-di (t
-Butyl) phenyl group, 2,6-di (sec-butyl)
Phenyl group, 2,6-diphenylphenyl group, 2,6-
Dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group, 2,
4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-tripropylphenyl group,
2,4,6-tri (isopropyl) phenyl group, 2,
4,6-tri (n-butyl) phenyl group, 2,4,6-
Tri (t-butyl) phenyl group, 2,4,6-tri (s
ec-butyl) phenyl group, 2,4,6-triphenylphenyl group, 2,4,6-trimethoxyphenyl group,
2,4,6-tri (dimethylamino) phenyl group, 2,
An aryl group such as a 4,6-trifluorophenyl group can be mentioned. Examples of the silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group as a substituent include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group. Group, tributylsilyl group, triphenylsilyl group, dimethylmethoxysilyl group, dimethylphenylsilyl group and the like. Examples of the general formula (6) include methylene, ethylene, ethylidene, propylidene, isopropylidene, benzylidene, methylphenylmethylene, diphenylmethylene, dimethylsilanediyl, methylphenylsilanediyl, diphenyl Examples thereof include a silanediyl group, a dimethylgermyl group, a methylphenylgermyl group, a diphenylgermyl group, a phenylene group, a methylimino group, a phenylimino group, a methylphosphino group, and a phenylphosphino group.

M is a transition metal belonging to Group 3, 4, 5, or 6 of the periodic table, and specifically includes a scandium atom, a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, and a molybdenum atom. Atom, or a tungsten atom, preferably a titanium atom, a zirconium atom, or a hafnium atom. Xs may be the same or different from each other;
A halogen, a hydrocarbon, a hetero atom-containing hydrocarbon, or an alkoxy group or an amino group having a hydrocarbon or a hetero atom-containing hydrocarbon group; examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group include a methyl group and an ethyl group; Isopropyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, trimethylsilylmethyl group, dimethylphenylsilylmethyl group and other alkyl groups, benzyl group, methoxybenzyl group Aralkyl groups such as dimethylaminobenzyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl Group, m-isopropylphenyl group, p-isopropylphenyl , O- butylphenyl group, m- butylphenyl group, p- butylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p
-(T-butyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-dimethylaminophenyl group, m-dimethylaminophenyl group, p-dimethylaminophenyl group, 2, 6
-Dimethylphenyl group, 2,6-diethylphenyl group,
2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6-di (n-butyl) phenyl group,
2,6-di (t-butyl) phenyl group, 2,6-di (s
ec-butyl) phenyl group, 2,6-diphenylphenyl group, 2,6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group, 2,4,6-trimethyl Phenyl group, 2,
4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group, 2,4,6-tri (n-butyl) phenyl group, 2,4 , 6-tri (t-butyl) phenyl group, 2,
4,6-tri (sec-butyl) phenyl group, 2,4
Aryl groups such as a 6-triphenylphenyl group, a 2,4,6-trimethoxyphenyl group, a 2,4,6-tri (dimethylamino) phenyl group, and a 2,4,6-trifluorophenyl group may be mentioned. Examples of the alkoxy group and the amino group include those having the above-described hydrocarbon group or heteroatom-containing hydrocarbon group as a substituent.

For a specific transition metal compound, M is di-
When ruconium and X are chlorine, the general formula (2)
The number of nitrogen atoms at the benzene ring site represented by (3) is 1
Or 2 is exemplified as (cyclopentadiene
Nyl) (1-azafluorene) zirconium trichlora
Id, (cyclopentadienyl) (2-methyl-1-a
Zafluorene) zirconium trichloride, (cyclo
Pentadienyl) (2,7-dimethyl-1-azafluor
(Len) zirconium trichloride, (cyclopentadi
Enyl) (2-azafluorene) zirconium trichloride
Ride, (cyclopentadienyl) (3-azafluore
N) zirconium trichloride, (cyclopentadie)
Nyl) (4-azafluorene) zirconium trichlora
Id, (methylcyclopentadienyl) (1-azaflu
(Olen) zirconium trichloride, (methylcyclo
Pentadienyl) (2-azafluorene) zirconium
Trichloride, (methylcyclopentadienyl) (3
-Azafluorene) zirconium trichloride,
Tylcyclopentadienyl) (4-azafluorene) di
Ruconium trichloride, (pentamethylcyclopen
Tadienyl) (1-azafluorene) zirconium tri
Chloride, (pentamethylcyclopentadienyl)
(2-azafluorene) zirconium trichloride,
(Pentamethylcyclopentadienyl) (3-azaful
(Olen) zirconium trichloride, (pentamethyl
Cyclopentadienyl) (4-azafluorene) zirco
Trichloride, (indenyl) (1-azaflu
Olen) zirconium trichloride, (indenyl)
(2-azafluorene) zirconium trichloride,
(Indenyl) (3-azafluorene) zirconiumdi
Chloride, (indenyl) (4-azafluorene) di
Ruconium trichloride, (fluorenyl) (1-A
Zafluorene) zirconium trichloride, (fluor
(Renyl) (2-azafluorene) zirconium trichloride
Ride, (fluorenyl) (3-azafluorene) silyl
Conium trichloride, (fluorenyl) (4-aza
(Fluorene) zirconium dichloride, (cyclopen
Tadienyl) (4-pyringin) zirconium triclo
Ride, (cyclopentadienyl) (7-methyl-4-
Pyringin) zirconium trichloride, (cyclope
Antadienyl) (2,7-dimethyl-4-pyringin)
Zirconium trichloride, (cyclopentadienyl
Le) (5-pyringin) zirconium trichloride,
(Cyclopentadienyl) (6-pyringin) zirconi
Trichloride, (cyclopentadienyl) (7-
Pyringin) zirconium trichloride, (methyl
Clopentadienyl) (4-pyringin) zirconium
Trichloride, (methylcyclopentadienyl) (5
-Pyringin) zirconium trichloride, (methyl
Cyclopentadienyl) (6-pyringin) zirconium
Mutrichloride, (methylcyclopentadienyl)
(7-pyringin) zirconium trichloride,
N-methylcyclopentadienyl) (4-pyringin)
Zirconium trichloride, (pentamethylcyclope
Nantadienyl) (5-pyringin) zirconium tric
Chloride, (pentamethylcyclopentadienyl) (6
-Pyringin) zirconium trichloride, (pentane
Methylcyclopentadienyl) (7-pyringin) zyl
Conium trichloride, (indenyl) (4-pyrine
Gin) zirconium trichloride, (indenyl)
(5-pyringin) zirconium trichloride, (a
Ndenyl) (6-pyringin) zirconium trichlora
Id, (indenyl) (7-pyringin) zirconium
Trichloride, (fluorenyl) (4-pyringin)
Zirconium trichloride, (fluorenyl) (5-
Pyringin) zirconium trichloride, (fluor
Nyl) (6-pyringin) zirconium trichlori
Do, (fluorenyl) (7-pyringin) zirconium
Trichloride, (cyclopentadienyl) (1,5-
Diazafluorene) zirconium trichloride,
Clopentadienyl) (1,6-diazafluorene) di
Ruconium trichloride, (cyclopentadienyl)
(1,7-diazafluorene) zirconium trichlora
Id, (cyclopentadienyl) (1,8-diazaful
Olen) zirconium trichloride, (cyclopentane
Dienyl) (2,5-diazafluorene) zirconium
Trichloride, (cyclopentadienyl) (2,6-
Diazafluorene) zirconium trichloride,
Clopentadienyl) (2,7-diazafluorene) di
Ruconium trichloride, (cyclopentadienyl)
(2,8-diazafluorene) zirconium trichlora
Id, (cyclopentadienyl) (3,5-diazaful
Olen) zirconium trichloride, (cyclopentane
Dienyl) (3,6-diazafluorene) zirconium
Trichloride, (cyclopentadienyl) (3,7-
Diazafluorene) zirconium trichloride,
Clopentadienyl) (3,8-diazafluorene) di
Ruconium trichloride, (cyclopentadienyl)
(4,5-diazafluorene) zirconium trichlora
Id, (cyclopentadienyl) (4,6-diazaful
Olen) zirconium trichloride, (cyclopentane
Dienyl) (4,7-diazafluorene) zirconium
Trichloride, (cyclopentadienyl) (4,8-
Diazafluorene) zirconium trichloride,
Tylcyclopentadienyl) (1,5-diazafluore
N) zirconium trichloride, (methylcyclopen
Tadienyl) (1,6-diazafluorene) zirconium
Mutrichloride, (methylcyclopentadienyl)
(1,7-diazafluorene) zirconium trichlora
Id, (methylcyclopentadienyl) (1,8-dia
Zafluorene) zirconium trichloride, (methyl
Cyclopentadienyl) (2,5-diazafluorene)
Zirconium trichloride, (methylcyclopentadi
Enyl) (2,6-diazafluorene) zirconium oxide
Rechloride, (methylcyclopentadienyl) (2,
7-diazafluorene) zirconium trichloride,
(Methylcyclopentadienyl) (2,8-diazaful
(Olen) zirconium trichloride, (methylcyclo
Pentadienyl) (3,5-diazafluorene) zirco
Trichloride, (methylcyclopentadienyl
(3) (3,6-diazafluorene) zirconium tric
Chloride, (methylcyclopentadienyl) (3,7-
Diazafluorene) zirconium trichloride,
Tylcyclopentadienyl) (3,8-diazafluore
N) zirconium trichloride, (methylcyclopen
Tadienyl) (4,5-diazafluorene) zirconium
Mutrichloride, (methylcyclopentadienyl)
(4,6-diazafluorene) zirconium trichlora
Id, (methylcyclopentadienyl) (4,7-dia
Zafluorene) zirconium trichloride, (methyl
Cyclopentadienyl) (4,8-diazafluorene)
Zirconium trichloride, (pentamethylcyclope
Antadienyl) (1,5-diazafluorene) zirconi
Trichloride, (pentamethylcyclopentadie
Nyl) (1,6-diazafluorene) zirconium tri
Chloride, (pentamethylcyclopentadienyl)
(1,7-diazafluorene) zirconium trichlora
Id, (pentapentamethylcyclopentadienyl)
(1,8-diazafluorene) zirconium trichlora
Id, (pentamethylcyclopentadienyl) (2.5
-Diazafluorene) zirconium trichloride,
(Pentamethylcyclopentadienyl) (2,6-dia
Zafluorene) zirconium trichloride, (penta
Methylcyclopentadienyl) (2,7-diazafluor
Len) zirconium trichloride,
Clopentadienyl) (2,8-diazafluorene) di
Ruconium trichloride, (pentamethylcyclopen
Tadienyl) (3,5-diazafluorene) zirconium
Mutrichloride, (pentamethylcyclopentadieni
(3) (3,6-diazafluorene) zirconium tric
Loride, (pentamethylcyclopentadienyl)
(3,7-diazafluorene) zirconium trichlora
Id, (pentamethylcyclopentadienyl) (3,8
-Diazafluorene) zirconium trichloride,
(Pentamethylcyclopentadienyl) (4,5-dia
Zafluorene) zirconium trichloride, (penta
Methylcyclopentadienyl) (4,6-diazafluor
Len) zirconium trichloride,
Clopentadienyl) (4,7-diazafluorene) di
Ruconium trichloride, (pentamethylcyclopen
Tadienyl) (4,8-diazafluorene) zirconium
Mutrichloride, (indenyl) (1,5-diazaf)
(Fluorene) zirconium trichloride, (indeni
) (1,6-diazafluorene) zirconium tric
Loride, (indenyl) (1,7-diazafluore)
N) zirconium trichloride, (indenyl)
(1,8-diazafluorene) zirconium trichlora
Id, (indenyl) (2,5-diazafluorene) di
Ruconium trichloride, (indenyl) (2,6-
Diazafluorene) zirconium trichloride, (a
Ndenyl) (2,7-diazafluorene) zirconium
Trichloride, (indenyl) (2,8-diazaful
Olen) zirconium trichloride, (indenyl)
(3,5-diazafluorene) zirconium trichlora
Id, (indenyl) (3,6-diazafluorene) di
Ruconium trichloride, (indenyl) (3,7-
Diazafluorene) zirconium trichloride, (a
Ndenyl) (3,8-diazafluorene) zirconium
Trichloride, (indenyl) (4,5-diazaful
Olen) zirconium dichloride, (indenyl)
(4,6-diazafluorene) zirconium trichlora
Id, (indenyl) (4,7-diazafluorene) di
Ruconium trichloride, (indenyl) (4,8-
Diazafluorene) zirconium trichloride,
Fluorenyl) (1,5-diazafluorene) zirconium
Mutrichloride, (fluorenyl) (1,6-diaza
(Fluorene) zirconium trichloride, (fluorene)
Nyl) (1,7-diazafluorene) zirconium dik
Loride, (fluorenyl) (1,8-diazafluore
N) zirconium trichloride, (fluorenyl)
(2,5-diazafluorene) zirconium trichlora
Id, (fluorenyl) (2,6-diazafluorenyl
Le) zirconium trichloride, (fluorenyl)
(2,7-diazafluorene) zirconium trichlora
Id, (fluorenyl) (2,8-diazafluorene)
Zirconium trichloride, (fluorenyl) (3,
5-diazafluorene) zirconium trichloride,
(Fluorenyl) (3,6-diazafluorene) zirco
Trichloride, (fluorenyl) (3,7-di
Azafluorene) zirconium trichloride, (full
Orenyl) (3,8-diazafluorene) zirconium
Trichloride, (fluorenyl) (4,5-diazaf
(Fluorene) zirconium trichloride, (fluorenyl)
Le) (4,6-diazafluorene) zirconium tric
Loride, (fluorenyl) (4,7-diazafluore
N) zirconium trichloride, (fluorenyl)
(4,8-diazafluorene) zirconium trichlora
Id, (cyclopentadienyl) (1-azafluorenyl)
Le) zirconium dichloride, (cyclopentadienyl)
) (2-Methyl-1-azafluorenyl) zirconium
Mudichloride, (cyclopentadienyl) (2,7-
Dimethyl-1-azafluorenyl) zirconium dichloro
Ride, (cyclopentadienyl) (2-azafluore
Nil) zirconium dichloride, (cyclopentadie
Nyl) (3-azafluorenyl) zirconium dichlora
Id, (cyclopentadienyl) (4-azafluorenyl)
Le) zirconium dichloride, (methylcyclopentane
Dienyl) (1-azafluorenyl) zirconium dik
Chloride, (methylcyclopentadienyl) (2-aza
Fluorenyl) zirconium dichloride,
Clopentadienyl) (3-azafluorenyl) zirco
Ium dichloride, (methylcyclopentadienyl)
(4-azafluorenyl) zirconium dichloride,
(Pentamethylcyclopentadienyl) (1-azaful
(Oenyl) zirconium dichloride, (pentamethyl
Cyclopentadienyl) (2-azafluorenyl) zyl
Conium dichloride, (pentamethylcyclopentadi
Enyl) (3-azafluorenyl) zirconium dichloride
Ride, (pentamethylcyclopentadienyl) (4-
Azafluorenyl) zirconium dichloride,
Denenyl) (1-azafluorenyl) zirconium dichloride
Ride, (indenyl) (2-azafluorenyl) sill
Conium dichloride, (indenyl) (3-azaflu
(Oenyl) zirconium dichloride, (indenyl)
(4-azafluorenyl) zirconium dichloride,
(Fluorenyl) (1-azafluorenyl) zirconium
Mudichloride, (fluorenyl) (2-azafluore
Nil) zirconium dichloride, (fluorenyl)
(3-azafluorenyl) zirconium dichloride,
(Fluorenyl) (4-azafluorenyl) zirconium
Mudichloride, (cyclopentadienyl) (4-pyri
Nandinyl) zirconium dichloride, (cyclopentane
Dienyl) (7-methyl-4-pyridinyl) zirconi
Um dichloride, (cyclopentadienyl) (2,7
-Dimethyl-4-pyrindinyl) zirconium dichlora
Id, (cyclopentadienyl) (5-pyridinyl)
Zirconium dichloride, (cyclopentadienyl)
(6-pyridinyl) zirconium dichloride,
Clopentadienyl) (7-pyridinyl) zirconium
Mudichloride, (methylcyclopentadienyl) (4
-Pyridinyl) zirconium dichloride, (methyl
Cyclopentadienyl) (5-pyridinyl) zirconi
Um dichloride, (methylcyclopentadienyl)
(6-pyrindinyl) zirconium dichloride,
Tylcyclopentadienyl) (7-pyridinyl) zyl
Conium dichloride, (pentamethylcyclopentadi
Enyl) (4-pyridinyl) zirconium dichlorai
Do, (pentamethylcyclopentadienyl) (5-pyri
Nandinyl) zirconium dichloride, (pentamethyl
Cyclopentadienyl) (6-pyridinyl) zirconi
Um dichloride, (pentamethylcyclopentadienyl
Le) (7-pyridinyl) zirconium dichloride,
(Indenyl) (4-pyridinyl) zirconium dik
Loride, (indenyl) (5-pyridinyl) zirco
Ium dichloride, (indenyl) (6-pyridinini
Le) zirconium dichloride, (indenyl) (7-
Pyrindinyl) zirconium dichloride,
Nyl) (4-pyridinyl) zirconium dichlorai
Do, (fluorenyl) (5-pyridinyl) zirconium
Mudichloride, (fluorenyl) (6-pyridinini
Le) zirconium dichloride, (fluorenyl) (7
-Pyridinyl) zirconium dichloride, (cyclo
Pentadienyl) (1,5-diazafluorenyl) zyl
Conium dichloride, (cyclopentadienyl)
(1,6-diazafluorenyl) zirconium dichlora
Id, (cyclopentadienyl) (1,7-diazaful
(Oenyl) zirconium dichloride, (cyclopentane
Dienyl) (1,8-diazafluorenyl) zirconium
Mudichloride, (cyclopentadienyl) (2,5-
Diazafluorenyl) zirconium dichloride,
Clopentadienyl) (2,6-diazafluorenyl)
Zirconium dichloride, (cyclopentadienyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, (cyclopentadienyl) (2,8-diazaful
(Oenyl) zirconium dichloride, (cyclopentane
Dienyl) (3,5-diazafluorenyl) zirconium
Mudichloride, (cyclopentadienyl) (3,6-
Diazafluorenyl) zirconium dichloride,
Clopentadienyl) (3,7-diazafluorenyl)
Zirconium dichloride, (cyclopentadienyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, (cyclopentadienyl) (4,5-diazaful
(Oenyl) zirconium dichloride, (cyclopentane
Dienyl) (2-methyl-4,5-diazafluorenyl
Le) zirconium dichloride, (cyclopentadienyl)
) (2,7-dimethyl-4,5-diazafluorenyl)
Le) zirconium dichloride, (cyclopentadienyl)
) (4,6-diazafluorenyl) zirconium dik
Chloride, (cyclopentadienyl) (4,7-diaza
Fluorenyl) zirconium dichloride, (cyclope
Antadienyl) (4,8-diazafluorenyl) zirco
Ium dichloride, (methylcyclopentadienyl)
(1,5-diazafluorenyl) zirconium dichlora
Id, (methylcyclopentadienyl) (1,6-dia
Zafluorenyl) zirconium dichloride, (methyl
Cyclopentadienyl) (1,7-diazafluorenyl)
Le) zirconium dichloride, (methylcyclopentane
Dienyl) (1,8-diazafluorenyl) zirconium
Mudichloride, (methylcyclopentadienyl)
(2,5-diazafluorenyl) zirconium dichlora
Id, (methylcyclopentadienyl) (2,6-dia
Zafluorenyl) zirconium dichloride, (methyl
Cyclopentadienyl) (2,7-diazafluorenyl)
Le) zirconium dichloride, (methylcyclopentane
Dienyl) (2,8-diazafluorenyl) zirconium
Mudichloride, (methylcyclopentadienyl)
(3,5-diazafluorenyl) zirconium dichlora
Id, (methylcyclopentadienyl) (3,6-dia
Zafluorenyl) zirconium dichloride, (methyl
Cyclopentadienyl) (3,7-diazafluorenyl)
Le) zirconium dichloride, (methylcyclopentane
Dienyl) (3,8-diazafluorenyl) zirconium
Mudichloride, (methylcyclopentadienyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, (methylcyclopentadienyl) (4,6-dia
Zafluorenyl) zirconium dichloride, (methyl
Cyclopentadienyl) (4,7-diazafluorenyl)
Le) zirconium dichloride, (methylcyclopentane
Dienyl) (4,8-diazafluorenyl) zirconium
Mudichloride, (pentamethylcyclopentadienyl
) (1,5-diazafluorenyl) zirconium dik
Loride, (pentamethylcyclopentadienyl)
(1,6-diazafluorenyl) zirconium dichlora
Id, (pentamethylcyclopentadienyl) (1,7
-Diazafluorenyl) zirconium dichloride,
(Pentapentamethylcyclopentadienyl) (1,8
-Diazafluorenyl) zirconium dichloride,
(Pentamethylcyclopentadienyl) (2,5-dia
Zafluorenyl) zirconium dichloride, (penta
Methylcyclopentadienyl) (2,6-diazafluor
(Renyl) zirconium dichloride, (pentamethyl
Clopentadienyl) (2,7-diazafluorenyl)
Zirconium dichloride, (pentamethylcyclopen
Tadienyl) (2,8-diazafluorenyl) zirconi
Um dichloride, (pentamethylcyclopentadienyl
Le) (3,5-diazafluorenyl) zirconium dik
Loride, (pentamethylcyclopentadienyl)
(3,6-diazafluorenyl) zirconium dichlora
Id, (pentamethylcyclopentadienyl) (3,7
-Diazafluorenyl) zirconium dichloride,
(Pentamethylcyclopentadienyl) (3,8-dia
Zafluorenyl) zirconium dichloride, (penta
Methylcyclopentadienyl) (4,5-diazafluor
(Renyl) zirconium dichloride, (pentamethyl
Clopentadienyl) (4,6-diazafluorenyl)
Zirconium dichloride, (pentamethylcyclopen
Tadienyl) (4,7-diazafluorenyl) zirconi
Um dichloride, (pentamethylcyclopentadienyl
Le) (4,8-diazafluorenyl) zirconium dik
Loride, (indenyl) (1,5-diazafluorenyl)
Le) zirconium dichloride, (indenyl) (1,
6-diazafluorenyl) zirconium dichloride,
(Indenyl) (1,7-diazafluorenyl) zirco
Ium dichloride, (indenyl) (1,8-diaza)
Fluorenyl) zirconium dichloride, (indenyl
Le) (2,5-diazafluorenyl) zirconium dik
Loride, (indenyl) (2,6-diazafluorenyl
Le) zirconium dichloride, (indenyl) (2,
7-diazafluorenyl) zirconium dichloride,
(Indenyl) (2,8-diazafluorenyl) zirco
Ium dichloride, (indenyl) (3,5-diaza
Fluorenyl) zirconium dichloride, (indenyl
(3) (3,6-diazafluorenyl) zirconium dik
Loride, (indenyl) (3,7-diazafluorenyl)
Le) zirconium dichloride, (indenyl) (3,
8-diazafluorenyl) zirconium dichloride,
(Indenyl) (4,5-diazafluorenyl) zirco
Ium dichloride, (indenyl) (4,6-diaza
Fluorenyl) zirconium dichloride, (indenyl
) (4,7-diazafluorenyl) zirconium dik
Loride, (indenyl) (4,8-diazafluorenyl)
Le) zirconium dichloride, (fluorenyl)
(1,5-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (1,6-diazafluorenyl)
Le) zirconium dichloride, (fluorenyl)
(1,7-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (1,8-diazafluorenyl)
Le) zirconium dichloride, (fluorenyl)
(2,5-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (2,6-diazafluorenyl
Le) zirconium dichloride, (fluorenyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (2,8-diazafluorenyl)
Le) zirconium dichloride, (fluorenyl)
(3,5-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (3,6-diazafluorenyl
Le) zirconium dichloride, (fluorenyl)
(3,7-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (3,8-diazafluorenyl)
Le) zirconium dichloride, (fluorenyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (4,6-diazafluorenyl
Le) zirconium dichloride, (fluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, (fluorenyl) (4,8-diazafluorenyl
B) zirconium dichloride, bis (1-azafluo)
(Renyl) zirconium dichloride, bis (2-azaph)
Fluorenyl) zirconium dichloride, bis (3-A
Zafluorenyl) zirconium dichloride, bis (4
-Azafluorenyl) zirconium dichloride, bis
(4-pyrindinyl) zirconium dichloride, bis
(5-pyrindinyl) zirconium dichloride, bis
(6-pyrindinyl) zirconium dichloride, bis
(7-pyridinyl) zirconium dichloride, (1
-Azafluorenyl) (2-azafluorenyl) zirco
Ium dichloride, (1-azafluorenyl) (3-
(Azafluorenyl) zirconium dichloride, (1-
Azafluorenyl) (4-azafluorenyl) zirconi
Um dichloride, (2-azafluorenyl) (3-a
(Zafluorenyl) zirconium dichloride, (2-A
Zafluorenyl) (4-azafluorenyl) zirconium
Mudichloride, (3-azafluorenyl) (4-aza
Fluorenyl) zirconium dichloride, (4-pyri)
Nandinyl) (5-pyridinyl) zirconium dichlora
Id, (4-pyrindinyl) (6-pyrindinyl) zyl
Conium dichloride, (4-pyrindinyl) (7-
(Phosphinyl) zirconium dichloride, (5-pyrine
Dinyl) (6-pyridinyl) zirconium dichlorai
, (5-pyridinyl) (7-pyridinyl) zirco
Ium dichloride, (6-pyrindinyl) (7-pyri
Ndinyl) zirconium dichloride, bis (1,5-
Diazafluorenyl) zirconium dichloride,
(1,5-diazafluorenyl) (1,6-diazafull)
(Oenyl) zirconium dichloride, (1,5-dia
Zafluorenyl) (1,7-diazafluorenyl) zyl
Conium dichloride, (1,5-diazafluoreni
Le) (1,8-diazafluorenyl) zirconium dik
Loride, (1,5-diazafluorenyl) (2,5-
Diazafluorenyl) zirconium dichloride,
(1,5-diazafluorenyl) (2.6-diazafluor
(Oenyl) zirconium dichloride, (1,5-dia
Zafluorenyl) (2,7-diazafluorenyl) zyl
Conium dichloride, (1,5-diazafluoreni
) (2,8-diazafluorenyl) zirconium dik
Loride, (1,5-diazafluorenyl) (3,5-
Diazafluorenyl) zirconium dichloride,
(1,5-diazafluorenyl) (3,6-diazafull
(Oenyl) zirconium dichloride, (1,5-dia
Zafluorenyl) (3,7-diazafluorenyl) zyl
Conium dichloride, (1,5-diazafluoreni
Le) (3,8-diazafluorenyl) zirconium dik
Loride, (1,5-diazafluorenyl) (4,5-
Diazafluorenyl) zirconium dichloride,
(1,5-diazafluorenyl) (4,6-diazafluor
(Oenyl) zirconium dichloride, (1,5-dia
Zafluorenyl) (4,7-diazafluorenyl) zyl
Conium dichloride, (1,5-diazafluoreni
Le) (4,8-diazafluorenyl) zirconium dik
Loride, bis (1,6-diazafluorenyl) zirco
Ium dichloride, (1,6-diazafluorenyl)
(1,7-diazafluorenyl) zirconium dichlora
Id, (1,6-diazafluorenyl) (1,8-dia
Zafluorenyl) zirconium dichloride, (1,6
-Diazafluorenyl) (2,5-diazafluorenyl
Le) zirconium dichloride, (1,6-diazaful)
(Oenyl) (2.6-diazafluorenyl) zirconium
Mudichloride, (1,6-diazafluorenyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, (1,6-diazafluorenyl) (2,8-dia
Zafluorenyl) zirconium dichloride, (1,6
-Diazafluorenyl) (3,5-diazafluorenyl
Le) zirconium dichloride, (1,6-diazaful)
Olenyl) (3,6-diazafluorenyl) zirconium
Mudichloride, (1,6-diazafluorenyl)
(3,7-diazafluorenyl) zirconium dichlora
Id, (1,6-diazafluorenyl) (3,8-dia
Zafluorenyl) zirconium dichloride, (1,6
-Diazafluorenyl) (4,5-diazafluorenyl)
Le) zirconium dichloride, (1,6-diazaful)
(Olenyl) (4,6-diazafluorenyl) zirconium
Mudichloride, (1,6-diazafluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, (1,6-diazafluorenyl) (4,8-dia
Zafluorenyl) zirconium dichloride, bis
(1,7-diazafluorenyl) zirconium dichlora
Id, (1,7-diazafluorenyl) (1,8-dia
(Zafluorenyl) zirconium dichloride, (1,7
-Diazafluorenyl) (2,5-diazafluorenyl
Le) zirconium dichloride, (1,7-diazaful)
(Oenyl) (2.6-diazafluorenyl) zirconium
Mudichloride, (1,7-diazafluorenyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, (1,7-diazafluorenyl) (2,8-dia
(Zafluorenyl) zirconium dichloride, (1,7
-Diazafluorenyl) (3,5-diazafluorenyl
Le) zirconium dichloride, (1,7-diazaful)
Olenyl) (3,6-diazafluorenyl) zirconium
Mudichloride, (1,7-diazafluorenyl)
(3,7-diazafluorenyl) zirconium dichlora
Id, (1,7-diazafluorenyl) (3,8-dia
(Zafluorenyl) zirconium dichloride, (1,7
-Diazafluorenyl) (4,5-diazafluorenyl)
Le) zirconium dichloride, (1,7-diazaful)
(Olenyl) (4,6-diazafluorenyl) zirconium
Mudichloride, (1,7-diazafluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, (1,7-diazafluorenyl) (4,8-dia
Zafluorenyl) zirconium dichloride, bis
(1,8-diazafluorenyl) zirconium dichlora
Id, (1,8-diazafluorenyl) (2,5-dia
(Zafluorenyl) zirconium dichloride, (1,8
-Diazafluorenyl) (2.6-diazafluorenyl)
Le) zirconium dichloride, (1,8-diazaful)
Olenyl) (2,7-diazafluorenyl) zirconium
Mudichloride, (1,8-diazafluorenyl)
(2,8-diazafluorenyl) zirconium dichlora
Id, (1,8-diazafluorenyl) (3,5-dia
(Zafluorenyl) zirconium dichloride, (1,8
-Diazafluorenyl) (3,6-diazafluorenyl
Le) zirconium dichloride, (1,8-diazaful)
Olenyl) (3,7-diazafluorenyl) zirconium
Mudichloride, (1,8-diazafluorenyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, (1,8-diazafluorenyl) (4,5-dia
(Zafluorenyl) zirconium dichloride, (1,8
-Diazafluorenyl) (4,6-diazafluorenyl)
Le) zirconium dichloride, (1,8-diazaful)
(Olenyl) (4,7-diazafluorenyl) zirconium
Mudichloride, (1,8-diazafluorenyl)
(4,8-diazafluorenyl) zirconium dichlora
Id, bis (2,5-diazafluorenyl) zirconium
Mudichloride, (2,5-diazafluorenyl)
(2.6-diazafluorenyl) zirconium dichlora
Id, (2,5-diazafluorenyl) (2,7-dia
Zafluorenyl) zirconium dichloride, (2,5
-Diazafluorenyl) (2,8-diazafluorenyl)
Le) zirconium dichloride, (2,5-diazaful)
Olenyl) (3,5-diazafluorenyl) zirconium
Mudichloride, (2,5-diazafluorenyl)
(3,6-diazafluorenyl) zirconium dichlora
Id, (2,5-diazafluorenyl) (3,7-dia
Zafluorenyl) zirconium dichloride, (2,5
-Diazafluorenyl) (3,8-diazafluorenyl)
Le) zirconium dichloride, (2,5-diazaful)
Olenyl) (4,5-diazafluorenyl) zirconium
Mudichloride, (2,5-diazafluorenyl)
(4,6-diazafluorenyl) zirconium dichlora
Id, (2,5-diazafluorenyl) (4,7-dia
Zafluorenyl) zirconium dichloride, (2,5
-Diazafluorenyl) (4,8-diazafluorenyl)
B) zirconium dichloride, bis (2,6-diaza)
Fluorenyl) zirconium dichloride, (2,6-
Diazafluorenyl) (2,7-diazafluorenyl)
Zirconium dichloride, (2,6-diazafluore
Nyl) (2,8-diazafluorenyl) zirconiumdi
Chloride, (2,6-diazafluorenyl) (3,5
-Diazafluorenyl) zirconium dichloride,
(2,6-diazafluorenyl)
(Oenyl) zirconium dichloride, (2,6-dia
Zafluorenyl) (3,7-diazafluorenyl) zyl
Conium dichloride, (2,6-diazafluoreni
Le) (3,8-diazafluorenyl) zirconium dik
Loride, (2,6-diazafluorenyl) (4,5-
Diazafluorenyl) zirconium dichloride,
(2,6-diazafluorenyl)
(Oenyl) zirconium dichloride, (2,6-dia
Zafluorenyl) (4,7-diazafluorenyl) zyl
Conium dichloride, (2,6-diazafluoreni
Le) (4,8-diazafluorenyl) zirconium dik
Loride, bis (2,7-diazafluorenyl) zirco
Ium dichloride, (2,7-diazafluorenyl)
(2,8-diazafluorenyl) zirconium dichlora
Id, (2,7-diazafluorenyl) (3,5-dia
(Zafluorenyl) zirconium dichloride, (2,7
-Diazafluorenyl) (3,6-diazafluorenyl
Le) zirconium dichloride, (2,7-diazaful)
Olenyl) (3,7-diazafluorenyl) zirconium
Mudichloride, (2,7-diazafluorenyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, (2,7-diazafluorenyl) (4,5-dia
(Zafluorenyl) zirconium dichloride, (2,7
-Diazafluorenyl) (4,6-diazafluorenyl)
Le) zirconium dichloride, (2,7-diazaful)
(Olenyl) (4,7-diazafluorenyl) zirconium
Mudichloride, (2,7-diazafluorenyl)
(4,8-diazafluorenyl) zirconium dichlora
Id, bis (2,8-diazafluorenyl) zirconium
Mudichloride, (2,8-diazafluorenyl)
(3,5-diazafluorenyl) zirconium dichlora
Id, (2,8-diazafluorenyl) (3,6-dia
Zafluorenyl) zirconium dichloride, (2,8
-Diazafluorenyl) (3,7-diazafluorenyl)
Le) zirconium dichloride, (2,8-diazaful)
Olenyl) (3,8-diazafluorenyl) zirconium
Mudichloride, (2,8-diazafluorenyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, (2,8-diazafluorenyl) (4,6-dia
Zafluorenyl) zirconium dichloride, (2,8
-Diazafluorenyl) (4,7-diazafluorenyl)
Le) zirconium dichloride, (2,8-diazaful)
Orenyl) (4,8-diazafluorenyl) zirconium
Mudichloride, bis (3,5-diazafluorenyl)
Zirconium dichloride, (3,5-diazafluore
Nyl) (3,6-diazafluorenyl) zirconiumdi
Chloride, (3,5-diazafluorenyl) (3,7
-Diazafluorenyl) zirconium dichloride,
(3,5-diazafluorenyl) (3,8-diazafull)
(Oenyl) zirconium dichloride, (3,5-dia)
Zafluorenyl) (4,5-diazafluorenyl) zyl
Conium dichloride, (3,5-diazafluoreni
) (4,6-diazafluorenyl) zirconium dik
Loride, (3,5-diazafluorenyl) (4,7-
Diazafluorenyl) zirconium dichloride,
(3,5-diazafluorenyl) (4,8-diazafull)
Olenyl) zirconium dichloride, bis (3,6-
Diazafluorenyl) zirconium dichloride,
(3,6-diazafluorenyl) (3,7-diazafull)
(Oenyl) zirconium dichloride, (3,6-dia)
Zafluorenyl) (3,8-diazafluorenyl) zyl
Conium dichloride, (3,6-diazafluoreni
Le) (4,5-diazafluorenyl) zirconium dik
Loride, (3,6-diazafluorenyl) (4,6-
Diazafluorenyl) zirconium dichloride,
(3,6-diazafluorenyl) (4,7-diazafluor
(Oenyl) zirconium dichloride, (3,6-dia)
Zafluorenyl) (4,8-diazafluorenyl) zyl
Conium dichloride, bis (3,7-diazafluore
Nyl) zirconium dichloride, (3,7-diazaf)
Luorenyl) (3,8-diazafluorenyl) zirconi
Um dichloride, (3,7-diazafluorenyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, (3,7-diazafluorenyl) (4,6-dia
Zafluorenyl) zirconium dichloride, (3,7
-Diazafluorenyl) (4,7-diazafluorenyl)
Le) zirconium dichloride, (3,7-diazaful)
Orenyl) (4,8-diazafluorenyl) zirconium
Mudichloride, bis (3,8-diazafluorenyl)
Zirconium dichloride, (3,8-diazafluore
Nyl) (4,5-diazafluorenyl) zirconiumdi
Chloride, (3,8-diazafluorenyl) (4,6
-Diazafluorenyl) zirconium dichloride,
(3,8-diazafluorenyl) (4,7-diazafluor
(Oenyl) zirconium dichloride, (3,8-dia)
Zafluorenyl) (4,8-diazafluorenyl) zyl
Conium dichloride, bis (4,5-diazafluore
Nyl) zirconium dichloride, (4,5-diazaf)
Luorenyl) (4,6-diazafluorenyl) zirconi
Um dichloride, (4,5-diazafluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, (4,5-diazafluorenyl) (4,8-diaza
Fluorenyl) zirconium dichloride, bis (4
6-diazafluorenyl) zirconium dichloride,
(4,6-diazafluorenyl) (4,7-diazafull)
(Oenyl) zirconium dichloride, (4,6-dia
Zafluorenyl) (4,8-diazafluorenyl) zyl
Conium dichloride, bis (4,7-diazafluore
Nyl) zirconium dichloride, (4,7-diazaf
Luorenyl) (4,8-diazafluorenyl) zirconi
Um dichloride, bis (4,8-diazafluoreni)
G) zirconium dichloride, dimethylsilanediyl
(Cyclopentadienyl) (1-azafluorenyl) di
Ruconium dichloride, dimethylsilanediyl
Lopentadienyl) (2-methyl-1-azafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(Cyclopentadienyl) (2-azafluorenyl) di
Ruconium dichloride, dimethylsilanediyl
Lopentadienyl) (3-azafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (cyclopen
Tadienyl) (4-azafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (tetramethylcyclyl)
Lopentadienyl) (1-azafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (tetramethyl
Rucyclopentadienyl) (2-azafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (tetra
Lamethylcyclopentadienyl) (3-azafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(Tetramethylcyclopentadienyl) (4-azafur
Oenyl) zirconium dichloride, dimethylsilane
Diyl (indenyl) (1-azafluorenyl) zirco
Dichloride, dimethylsilanediyl (indeni
Le) (2-azafluorenyl) zirconium dichlori
, Dimethylsilanediyl (indenyl) (3-azaf
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (indenyl) (4-azafluorenyl) sill
Conium dichloride, dimethylsilanediyl (fluoro
(Renyl) (1-azafluorenyl) zirconium dichloride
Ride, dimethylsilanediyl (fluorenyl) (2-
Azafluorenyl) zirconium dichloride, dimethi
Lusilanediyl (fluorenyl) (3-azafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(Fluorenyl) (4-azafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (cyclopentane
Dienyl) (4-pyridinyl) zirconium dichlora
Id, dimethylsilanediyl (cyclopentadienyl)
(5-pyrindinyl) zirconium dichloride, dime
Tylsilanediyl (cyclopentadienyl) (6-pyri
Ndinyl) zirconium dichloride, dimethylsilane
Diyl (cyclopentadienyl) (7-pyridinyl)
Zirconium dichloride, dimethylsilanediyl (Te
Tramethylcyclopentadienyl) (4-pyrindini
G) zirconium dichloride, dimethylsilanediyl
(Tetramethylcyclopentadienyl) (5-azayne
Denenyl) zirconium dichloride, dimethylsilanedi
Yl (tetramethylcyclopentadienyl) (6-pyri
Ndinyl) zirconium dichloride, dimethylsilane
Diyl (tetramethylcyclopentadienyl) (7-pi
(Phosphinyl) zirconium dichloride, dimethylsila
Ndiyl (indenyl) (4-pyridinyl) zirconi
Um dichloride, dimethylsilanediyl (indeni
Le) (5-pyrindinyl) zirconium dichloride,
Dimethylsilanediyl (indenyl) (6-pyrindini
G) zirconium dichloride, dimethylsilanediyl
(Indenyl) (7-pyridinyl) zirconium dik
Chloride, dimethylsilanediyl (fluorenyl) (4
-Pyridinyl) zirconium dichloride, dimethyl
Silanediyl (fluorenyl) (5-pyridinyl) di
Ruconium dichloride, dimethylsilanediyl (full
Olenyl) (6-pyridinyl) zirconium dichlora
And dimethylsilanediyl (fluorenyl) (7-pi
(Phosphinyl) zirconium dichloride, dimethylsila
And diyl (cyclopentadienyl) (1,5-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (1,6-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (1,7-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (1,8-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
And diyl (cyclopentadienyl) (2,5-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (2,6-diazaf
Fluorenyl) zirconium dichloride, dimethylsila
Diyl (cyclopentadienyl) (2,7-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
And diyl (cyclopentadienyl) (2,8-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
And diyl (cyclopentadienyl) (3,5-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (3,6-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (3,7-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
Ndiyl (cyclopentadienyl) (3,8-diazaf)
Fluorenyl) zirconium dichloride, dimethylsila
And diyl (cyclopentadienyl) (4,5-diazaf
Fluorenyl) zirconium dichloride, dimethylsila
N-diyl (cyclopentadienyl) (2-methyl-4,
5-diazafluorenyl) zirconium dichloride,
Dimethylsilanediyl (cyclopentadienyl) (2,
7-dimethyl-4,5-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (cyclopen
Tadienyl) (4,6-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (cyclopen
Tadienyl) (4,7-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (cyclopen
Tadienyl) (4,8-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (tetramethyl
Rucyclopentadienyl) (1,5-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(Tetramethylcyclopentadienyl) (1,6-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (tetramethylcyclopentadienyl)
(1,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (tetrapentamethylcyclyl)
Lopentadienyl) (1,8-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (tetra
Lamethylcyclopentadienyl) (2,5-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (tetramethylcyclopentadienyl) (2,6
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (tetramethylcyclopentadienyl
Le) (2,7-diazafluorenyl) zirconium dik
Chloride, dimethylsilanediyl (tetramethylcyclo
Pentadienyl) (2,8-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (tetra
Methylcyclopentadienyl) (3,5-diazafluor
Renyl) zirconium dichloride, dimethylsilanedi
Yl (tetramethylcyclopentadienyl) (3,6-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (tetramethylcyclopentadienyl
) (3,7-diazafluorenyl) zirconium dik
Chloride, dimethylsilanediyl (tetramethylcyclo
Pentadienyl) (3,8-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (tetra
Methylcyclopentadienyl) (4,5-diazafluor
Renyl) zirconium dichloride, dimethylsilanedi
Yl (tetramethylcyclopentadienyl) (4,6-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (tetramethylcyclopentadienyl
) (4,7-diazafluorenyl) zirconium dik
Chloride, dimethylsilanediyl (tetramethylcyclo
Pentadienyl) (4,8-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (indene
Nyl) (1,5-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (indenyl)
(1,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (indenyl) (1,7-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (indenyl) (1,8-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (indenyl) (2,5-diazafluorenyl)
Zirconium dichloride, dimethylsilanediyl (I
Ndenyl) (2,6-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (indenyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (indenyl) (2,8-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (indenyl) (3,5-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (indenyl) (3,6-diazafluorenyl)
Zirconium dichloride, dimethylsilanediyl (I
Ndenyl) (3,7-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (indenyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (indenyl) (4,5-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (indenyl) (4,6-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (indenyl) (4,7-diazafluorenyl)
Zirconium dichloride, dimethylsilanediyl (I
Ndenyl) (4,8-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (fluoreni
) (1,5-diazafluorenyl) zirconium dik
Loride, dimethylsilanediyl (fluorenyl)
(1,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (fluorenyl) (1,7
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (fluorenyl) (1,8-diaza
Fluorenyl) zirconium dichloride, dimethyl
Landiyl (fluorenyl) (2,5-diazafluore
Nyl) zirconium dichloride, dimethylsilanediyl
Le (fluorenyl) (2,6-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (full
Olenyl) (2,7-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (fluoreni
) (2,8-diazafluorenyl) zirconium dik
Loride, dimethylsilanediyl (fluorenyl)
(3,5-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (fluorenyl) (3,6
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (fluorenyl) (3,7-diaza
Fluorenyl) zirconium dichloride, dimethyl
Landiyl (fluorenyl) (3,8-diazafluore
Nyl) zirconium dichloride, dimethylsilanediyl
Le (fluorenyl) (4,5-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (full
(Olenyl) (4,6-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (fluoreni
) (4,7-diazafluorenyl) zirconium dik
Loride, dimethylsilanediyl (fluorenyl)
(4,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediylbis (1-azafluorene
G) zirconium dichloride, dimethylsilanediyl
Bis (2-azafluorenyl) zirconium dichlorai
De, dimethylsilanediylbis (3-azafluorene)
G) zirconium dichloride, dimethylsilanediyl
Bis (4-azafluorenyl) zirconium dichlorai
Dimethylsilanediylbis (4-pyrindinyl) di
Ruconium dichloride, dimethylsilanediylbis
(5-pyrindinyl) zirconium dichloride, dime
Tylsilanediylbis (6-pyridinyl) zirconium
Mudichloride, dimethylsilanediylbis (7-pyri
Ndinyl) zirconium dichloride, dimethylsilane
Diyl (1-azafluorenyl) (2-azafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1-azafluorenyl) (3-azafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1-
Azafluorenyl) (4-azafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (2-azaf
Luorenyl) (3-azafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (2-azafluore
Nyl) (4-azafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (3-azafluorenyl)
(4-azafluorenyl) zirconium dichloride,
Dimethylsilanediyl (4-pyrindinyl) (5-pyridinyl)
Ndinyl) zirconium dichloride, dimethylsilane
Diyl (4-pyrindinyl) (6-pyrindinyl) diyl
Conium dichloride, dimethylsilanediyl (4-pi
(Lindinyl) (7-pyridinyl) zirconium dichloride
Ride, dimethylsilanediyl (5-pyrindinyl)
(6-pyrindinyl) zirconium dichloride, dime
Tylsilanediyl (5-pyringinyl) (7-pyringe
Nyl) zirconium dichloride, dimethylsilanediyl
(6-pyridinyl) (7-pyridinyl) zirconi
Um dichloride, dimethylsilanediylbis (1,5
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,5-diazafluorenyl)
(1,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,5-diazafluore
Nyl) (1,7-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,5-diazaf
Luorenyl) (1,8-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,5-di
Azafluorenyl) (2,5-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
5-diazafluorenyl) (2.6-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1,5-diazafluorenyl) (2,7-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (1,5-diazafluorenyl) (2,8-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (1,5-diazafluorenyl) (3,5
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,5-diazafluorenyl)
(3,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,5-diazafluore
Nil) (3,7-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,5-diazaf
Luorenyl) (3,8-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,5-di
Azafluorenyl) (4,5-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
5-diazafluorenyl) (4,6-diazafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(1,5-diazafluorenyl) (4,7-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (1,5-diazafluorenyl) (4,8-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediylbis (1,6-diazafluorenyl) silyl
Conium dichloride, dimethylsilanediyl (1,6
-Diazafluorenyl) (1,7-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1,6-diazafluorenyl) (1,8-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (1,6-diazafluorenyl) (2,5-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (1,6-diazafluorenyl) (2.6
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,6-diazafluorenyl)
(2,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,6-diazafluore
Nyl) (2,8-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,6-diazaf
Luorenyl) (3,5-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,6-di
Azafluorenyl) (3,6-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
6-diazafluorenyl) (3,7-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1,6-diazafluorenyl) (3,8-diazafluor)
Renyl) zirconium dichloride, dimethylsilanedi
Yl (1,6-diazafluorenyl) (4,5-diaza
Fluorenyl) zirconium dichloride, dimethyl
Landiyl (1,6-diazafluorenyl) (4,6-
Diazafluorenyl) zirconium dichloride, dime
Tylsilanediyl (1,6-diazafluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,6-diazafluore
Nyl) (4,8-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediylbis (1,7-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (1,7-diazafluorenyl) (1,8
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,7-diazafluorenyl)
(2,5-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,7-diazafluore
Nil) (2.6-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,7-diazaf
Luorenyl) (2,7-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,7-di
Azafluorenyl) (2,8-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
7-diazafluorenyl) (3,5-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1,7-diazafluorenyl) (3,6-diazafull
Oenyl) zirconium dichloride, dimethylsilane
Diyl (1,7-diazafluorenyl) (3,7-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (1,7-diazafluorenyl) (3,8
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,7-diazafluorenyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,7-diazafluore
Nyl) (4,6-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,7-diazaf
Luorenyl) (4,7-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,7-di
Azafluorenyl) (4,8-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediylbis
(1,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,8-diazafluore
Nyl) (2,5-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,8-diazaf
Luorenyl) (2.6-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,8-di
Azafluorenyl) (2,7-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
8-diazafluorenyl) (2,8-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(1,8-diazafluorenyl) (3,5-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (1,8-diazafluorenyl) (3,6-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (1,8-diazafluorenyl) (3,7
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (1,8-diazafluorenyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (1,8-diazafluore
Nyl) (4,5-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (1,8-diazaf
Luorenyl) (4,6-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (1,8-di
Azafluorenyl) (4,7-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (1,
8-diazafluorenyl) (4,8-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
Bis (2,5-diazafluorenyl) zirconium zinc
Chloride, dimethylsilanediyl (2,5-diazaful
(Oenyl) (2.6-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (2,5-dia
Zafluorenyl) (2,7-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (2.5
-Diazafluorenyl) (2,8-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(2,5-diazafluorenyl)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (2,5-diazafluorenyl) (3,6-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (2,5-diazafluorenyl) (3,7
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (2,5-diazafluorenyl)
(3,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (2,5-diazafluore
Nyl) (4,5-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (2,5-diazaf
Luorenyl) (4,6-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (2,5-di
Azafluorenyl) (4,7-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (2,
5-diazafluorenyl) (4,8-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
Bis (2,6-diazafluorenyl) zirconium zinc
Chloride, dimethylsilanediyl (2,6-diazaful
Olenyl) (2,7-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (2,6-dia
Zafluorenyl) (2,8-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (2,6
-Diazafluorenyl) (3,5-diazafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(2,6-diazafluorenyl)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (2,6-diazafluorenyl) (3,7-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (2,6-diazafluorenyl) (3,8
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (2,6-diazafluorenyl)
(4,5-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (2,6-diazafluore
Nyl) (4,6-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (2,6-diazaf
Luorenyl) (4,7-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (2,6-di
Azafluorenyl) (4,8-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediylbis
(2,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (2,7-diazafluore
Nyl) (2,8-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (2,7-diazaf
Luorenyl) (3,5-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (2,7-di
Azafluorenyl) (3,6-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (2,
7-diazafluorenyl) (3,7-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(2,7-diazafluorenyl) (3,8-diazafluor
Oenyl) zirconium dichloride, dimethylsilane
Diyl (2,7-diazafluorenyl) (4,5-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (2,7-diazafluorenyl) (4,6
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (2,7-diazafluorenyl)
(4,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (2,7-diazafluore
Nyl) (4,8-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediylbis (2,8-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (2,8-diazafluorenyl) (3,5
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (2,8-diazafluorenyl)
(3,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (2,8-diazafluore
Nil) (3,7-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (2,8-diazaf
Luorenyl) (3,8-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediyl (2,8-di
Azafluorenyl) (4,5-diazafluorenyl) di
Ruconium dichloride, dimethylsilanediyl (2,
8-diazafluorenyl) (4,6-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(2,8-diazafluorenyl) (4,7-diazafluor
Oenyl) zirconium dichloride, dimethylsilane
Diyl (2,8-diazafluorenyl) (4,8-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediylbis (3,5-diazafluorenyl) silyl
Conium dichloride, dimethylsilanediyl (3,5
-Diazafluorenyl) (3,6-diazafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(3,5-diazafluorenyl) (3,7-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (3,5-diazafluorenyl) (3,8-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (3,5-diazafluorenyl) (4,5
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (3,5-diazafluorenyl)
(4,6-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (3,5-diazafluore
Nyl) (4,7-diazafluorenyl) zirconiumdi
Chloride, dimethylsilanediyl (3,5-diazaf
Luorenyl) (4,8-diazafluorenyl) zirconi
Um dichloride, dimethylsilanediylbis (3,6
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (3,6-diazafluorenyl)
(3,7-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediyl (3,6-diazafluore
Nyl) (3,8-azafluorenyl) zirconium dik
Chloride, dimethylsilanediyl (3,6-diazaful
Orenyl) (4,5-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (3,6-dia
Zafluorenyl) (4,6-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (3,6
-Diazafluorenyl) (4,7-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(3,6-diazafluorenyl) (4,8-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diylbis (3,7-diazafluorenyl) zirconium
Mudichloride, dimethylsilanediyl (3,7-dia
Zafluorenyl) (3,8-diazafluorenyl) zyl
Conium dichloride, dimethylsilanediyl (3,7
-Diazafluorenyl) (4,5-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(3,7-diazafluorenyl) (4,6-diazafull)
Oenyl) zirconium dichloride, dimethylsilane
Diyl (3,7-diazafluorenyl) (4,7-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (3,7-diazafluorenyl) (4,8
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediylbis (3,8-diazafluorenyl)
G) zirconium dichloride, dimethylsilanediyl
(3,8-diazafluorenyl) (4,5-diazafluor
Oenyl) zirconium dichloride, dimethylsilane
Diyl (3,8-diazafluorenyl) (4,6-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (3,8-diazafluorenyl) (4,7
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (3,8-diazafluorenyl)
(4,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediylbis (4,5-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (4,5-diazafluorenyl) (4,6-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (4,5-diazafluorenyl) (4,7
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediyl (4,5-diazafluorenyl)
(4,8-diazafluorenyl) zirconium dichlora
Id, dimethylsilanediylbis (4,6-diazaful
Oenyl) zirconium dichloride, dimethylsilane
Diyl (4,6-diazafluorenyl) (4,7-dia
Zafluorenyl) zirconium dichloride, dimethyl
Silanediyl (4,6-diazafluorenyl) (4,8
-Diazafluorenyl) zirconium dichloride, di
Methylsilanediylbis (4,7-diazafluorenyl
G) zirconium dichloride, dimethylsilanediyl
(4,7-diazafluorenyl) (4,8-diazafluor
Oenyl) zirconium dichloride, dimethylsilane
Diylbis (4,8-diazafluorenyl) zirconium
Modichloride and the like. Also, expressed by equation (1)
The transition metal compound (A) includes L ¹ , L ^Two But (2)
Is (3), when (2) and (3) are three or more
It may contain a nitrogen atom. In addition, the central metal
Is a transition metal of group 3, 4, 5, or 6 of the periodic table, preferably
Scandium atom, titanium atom, hafnium
Compounds substituted with atoms, vanadium atoms, and chromium atoms
Things are fine. Also preferably, chlorine of the above complex
Group substituted with alkyl group, fluorine, bromine or iodine
Dimethylsilanediyl group which is a crosslinking group of the above-mentioned complex
With isopropylidene, diphenylmethylene,
Nylsilanediyl group, a plurality of the above
Examples of complexes formed as clusters
But, of course, the transition by the combination of the claims
The transfer metal compounds (A) and (A ') can be used.
Wear. Here, the transition metal compounds (A) and (A ′)
To further clarify the possible structure,
Only a part of the structure has an oxidation number of 4 of the central metal, and
Examples of the case where X is chlorine are shown below.
However, the present invention is not limited to this.

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

The (B) activating co-catalyst used as a component of the catalyst for olefin polymerization in the present invention includes:
Protonic acid represented by the following general formula (7), general formula (8)
An ionized ionic compound represented by the general formula (9), a Lewis acid compound represented by the general formula (10), [HL ⁴ ] [E (Ar) ₄ ] (7) [GL ⁵ _o ] [E (Ar) ₄ ] (8) [D] [E (Ar) ₄ ] (9) E (Ar) ₃ (10) (where H is a proton and E is a boron atom or aluminum L ⁴ is a Lewis base such as tetrahydrofuran, diethyl ether, pyridine, dimethylamine, tetramethylethylenediamine, trimethylphosphine, etc., L ⁵ is a Lewis base exemplified for L ⁴ or a substituted or unsubstituted cyclopentadienyl group. G is a lithium, iron and silver atom, D is a carbonium cation or a tropylium cation, Ar may be the same or different from each other, Aryl, aralkyl, aryl or aralkyl substituted with halogen, hydrocarbon or heteroatom-containing hydrocarbon, aryl substituted with silyl having hydrocarbon or heteroatom-containing hydrocarbon or An aralkyl group, preferably an aryl group, an aryl group substituted with a halogen, a hydrocarbon group or a hetero atom-containing hydrocarbon group, or an aryl group substituted with a silyl group having a hydrocarbon or a hetero atom-containing hydrocarbon group. .
o is 0, 1 or 2. Aluminoxane, clay mineral, magnesium chloride compound, sulfonate, carboxylic acid derivative, surface-treated solid oxide or solid halide, and the solid surface is a cation component, and the counter anion component of the ionic compound is Solid components that have been placed.

Specific examples of the protonic acid represented by the general formula (7) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) ) Borate, hydronium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, tri (n-
Butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, Tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentane) Fluorophenyl) aluminate and the like,
It is not limited to these. As the ionized ionic compound represented by the general formula (8), specifically, lithium tetrakis (pentafluorophenyl) borate,
Lithium salt such as lithium tetrakis (pentafluorophenyl) aluminate or an ether complex thereof, ferrocenium salt such as ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis (pentane) Examples thereof include silver salts such as (fluorophenyl) borate and silver tetrakis (pentafluorphenyl) aluminate, but are not limited thereto. Specific examples of the Lewis acid represented by the general formula (9) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, and tropylium tetrakis Examples thereof include (pentafluorophenyl) aluminate, but are not limited thereto. As specific examples of the Lewis acidic compound represented by the general formula (10), tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4) , 5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like. It is possible, but not limited to these.

On the other hand, when the activation co-catalyst (B), which is a component of the catalyst for olefin polymerization of the present invention, is aluminoxane, the aluminoxane is represented by the following general formula (1)
1), (12) or more than one aluminum atom, R ⁶
It is represented by a compound containing a cluster structure composed of a group and an oxygen atom.

[0037]

Embedded image

(In the formula, R ⁶ may be the same or different, and is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and q is 2 to 60.) Further, the aluminoxane described above. May contain a monomer such as trialkylaluminum, a dimer and an oligomer, but can be used without any problem. This aluminoxane can be generally obtained by reacting an organic aluminum compound and water in an organic solvent or an organic aluminum compound and a salt or oxide hydrate in an organic solvent, and is produced by a known method. Can be used.

In the general formulas (11) and (12),
When R ⁶ is a hydrocarbon group, specific examples include a methyl group,
Examples thereof include a hydrocarbon group having 1 to 20 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a t-butyl group.

When the activating cocatalyst (B), which is a component of the olefin polymerization catalyst of the present invention, is magnesium chloride,
Magnesium chloride is adjusted by a known method,
(A), (A ') There is no particular limitation on the amount used per transition metal compound. Further, magnesium chloride can be generated in the system during polymerization or catalyst preparation using organoaluminum halide, organomagnesium, or the like, and used for polymerization.

When the activating polymerization catalyst (B), which is a component of the catalyst for olefin polymerization of the present invention, is a clay mineral, all of natural clay minerals and clay minerals having a cation exchange ability obtained by artificial synthesis are used. It is possible to use a clay mineral chemically treated by introducing an ionic substance or compound between the layers. As clay minerals, naturally occurring kaolinite,
Kaolin-based minerals such as dickite and halloysite; smectite-based minerals such as montmorillonite, hectorite, beidellite, saponite, teniolite, and sauconite; mica-based minerals such as muscovite, paragonite, and illite;
Vermiculite family; brittle mica-based minerals such as margarite and clintonite; curdstone-based minerals such as dombasite, coucheite, clinochlore; and artificially synthesized clay minerals such as sepiolite-palygorskite, preferably smectite-based Minerals or mica-based minerals include, but are not limited to. Examples of the acid used for the chemical treatment include Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. As the alkali, sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferably used. Compounds used in the salt treatment include ionic halides such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron chloride, and ammonium chloride; sulfates such as sodium sulfate, potassium sulfate, aluminum sulfate, and ammonium sulfate; Carbonates such as potassium carbonate, sodium carbonate and calcium carbonate; inorganic salts such as phosphates such as sodium phosphate, potassium phosphate, aluminum phosphate and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate and citric acid Organic acid salts such as sodium acid salt and sodium tartrate can be exemplified.

The organic compounds used to form the organic complex of the clay mineral include onium salts, trityl chloride,
Examples thereof include compounds that generate carbon cations such as tropylium bromide and complex compounds that generate metal complex cations such as ferrocenium salts. Examples of the inorganic compound used for forming the inorganic composite include metal hydroxides that generate hydroxide cations such as aluminum hydroxide, zirconium hydroxide, and chromium hydroxide.

Among the clay minerals used in the present invention, a modified clay compound which is a clay mineral-organic ion complex in which a metal ion, which is an exchangeable cation present in the clay mineral, is exchanged for a specific organic cation component. It is. As the organic cation to be introduced into the modified clay compound, specifically, butylammonium, butylmethylammonium, dibutylammonium, dimethylbutylammonium, tributylammonium, hexylammonium, hexylmethylammonium, dihexylammonium, dimethylhexylammonium, trihexylammonium Octyl ammonium, octyl methyl ammonium, dioctyl ammonium, dimethyl octyl ammonium, trioctyl ammonium, octadecyl ammonium, octadecyl methyl ammonium, dioctadecyl ammonium, dioctadecyl methyl ammonium, oleyl ammonium, oleyl methyl ammonium, oleyl dimethyl ammonium, dioleyl ammonium, The Aliphatic ammonium cations such as rail methylammonium, anilinium, N- methyl anilinium, N, N- dimethylanilinium, N
-Ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N,
Examples thereof include aromatic ammonium cations such as 2,4,6-pentamethylanilinium and oxonium ions such as dimethyloxonium and diethyloxonium, but are not limited thereto.

When the activating cocatalyst (B), which is a component of the catalyst for olefin polymerization of the present invention, is a sulfonate,
For example, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, calcium bis (trifluoromethanesulfonate), barium bis (trifluoromethanesulfonate), titanium tris (trifluoromethanesulfonate), tetrakis (trifluoromethane) Sulfonate) titanium, tetrakis (trifluoromethanesulfonate) zirconium, tetrakis (trifluoromethanesulfonate) hafnium, pentakis (trifluoromethanesulfonate) niobium,
Pentakis (trifluoromethanesulfonate) tantalum, tris (trifluoromethanesulfonate) iron, silver trifluoromethanesulfonate, tris (trifluoromethanesulfonate) boron, tris (trifluoromethanesulfonate) aluminum, tris (trifluoromethanesulfonate) gallium , Tetrakis (trifluoromethanesulfonate) tin, lithium pentafluorobenzenesulfonate, sodium pentafluorobenzenesulfonate, potassium pentafluorobenzenesulfonate, magnesium bis (pentafluorobenzenesulfonate) magnesium, bis (pentafluorobenzenesulfonate) calcium , Bis (pentafluorobenzenesulfonate) barium, tris (pentafluorobenzenesulfonate) G) titanium, tetrakis (pentafluorobenzenesulfonate) zirconium, tetrakis (pentafluorobenzenesulfonate) hafnium, pentakis (pentafluorobenzenesulfonate) niobium, pentakis (pentafluorobenzenesulfonate) tantalum, tris (pentafluorobenzenesulfonate) Nate) iron, silver pentafluorobenzenesulfonate, tris (pentafluorobenzenesulfonate)
Boron, tris (pentafluorobenzenesulfonate) aluminum, tris (pentafluorobenzenesulfonate) gallium, tetrakis (pentafluorobenzenesulfonate) tin, bis (trifluoromethanesulfonate) magnesium, pentakis (trifluoromethanesulfonate) niobium, Examples thereof include bis (pentafluorobenzenesulfonate) magnesium, tetrakis (pentafluorobenzenesulfonate) titanium, and pentakis (pentafluorobenzenesulfonate) niobium.

When the activating polymerization catalyst (B) which is a component of the catalyst for olefin polymerization of the present invention is a carboxylic acid derivative, for example, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluorobenzoic acid, tetrafluorotoluic acid , 2,4- (trifluoromethyl) benzoic acid,
Pentafluorophenylacetic acid can be exemplified.

When the activating polymerization catalyst (B), which is a component of the olefin polymerization catalyst of the present invention, is a surface-modified solid oxide or solid halide, the above-mentioned organoaluminum compound or aluminum is coated on the solid surface. Noxane-modified or solid surface with 1 to 1 carbon atoms
Modified with an organometallic compound having 30 halogens, particularly a fluorine-substituted hydrocarbon group, and having a metal atom, a Zn atom or a Sn atom of Groups 1, 2, and 13 of the periodic table, such as a trispentafluorophenyl borate derivative Can be used. Here, specific examples of solid oxides include oxides of typical elements such as alumina and silica, oxides of transition metal elements such as titania and zirconia, and silica-
Composite oxides such as alumina and silica-magnesia can be used. Examples of the inorganic halide include a halide of an alkaline earth metal such as magnesium chloride, and a halide of a Group 13 element of the periodic table such as aluminum chloride.
The organometallic compound used for the modification of the solid surface is represented by the general formula (13) WR ⁷ _{s Yt} (13) (where W is a metal atom belonging to Group 1, 2, or 13 of the periodic table;
An atom selected from Zn atom or Sn atom, R ⁷
Is a hydrocarbon group having 1 to 30 carbon atoms, and is a group in which some or all of the hydrogen atoms have been substituted with fluorine. Y is halogen,
It is a hydroxyl group or a hydrocarbon group having 1 to 30 carbon atoms. s
≧ t, and s + t is equal to the oxidation number of the metal atom W. )
It is represented by Examples of the hydrocarbon group having 1 to 30 carbon atoms include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aromatic hydrocarbon group is preferably a phenyl group, a substituted phenyl group such as a tolyl group, or a naphthyl group. As the aliphatic hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decanyl group are preferable, and these hydrocarbon groups are part of hydrogen. Or all must be halogenated. In particular, those that are fluorinated are preferred.

The method for reacting the organometallic compound on the surface of the inorganic oxide or inorganic halide is not particularly limited.

In the case where the activating cocatalyst (B), which is a component of the olefin polymerization catalyst of the present invention, is a solid component in which the solid surface is a cation component and a counter anion component of an ionic compound is coordinated, The compound is represented by the general formula (14) [Cation ⁺ ] [Anion ⁻ ] (14), where [Anion ⁻ ] is an anionic component of an ionic compound, and is a component that reacts with a transition metal compound to become a stable anion. Examples include an organic boron compound anion, an organic aluminum compound anion, an organic phosphorus compound anion, and an organic antimony compound anion. Specifically, tetrakis (pentafluorophenyl) boron, tetrakisphenylboron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (pentafluorophenyl) aluminum, tetrakisphenylaluminum, tetrakis (3,5 -Di (trifluoromethyl) phenyl) aluminum and the like.

[Cation ⁺ ] is a cationic component of the ionic compound, and is characterized by making the solid surface cationic. The solid having a cationic surface is, for example, one of components composed of a cationic group such as an aluminum cation, an oxonium cation, a sulfonium cation, a phosphonium cation, a carbonium cation, a tropylium cation, and a metal cation. Solid components that are partly or wholly chemically bonded to the solid surface are included. Specific examples of the cationic group constituting the cationic solid include tripropylammonium, tributylammonium, N, N-
Dimethylanilinium, N, N, 2,4,5-pentamethylanilinium, pyridinium, diethyloxonium, triphenylsulfonium, trimethylsulfonium, triphenylphosphonium, tri (o-tolyl) phosphonium, triphenylcarbene , Cycloheptatrienium, ferrocenium and the like, but are not limited thereto. These cationic groups may be a part of the components constituting the solid, or may be those immobilized on the surface of the solid by chemical modification.

The (C) organometallic compound used in the present invention is a compound having a metal atom, a Sn atom or a Zn atom belonging to groups 1, 2, and 13 of the periodic table having at least one hydrocarbon group, and is particularly limited. However, for example, compounds represented by the following general formulas (15), (16) or (17) can be mentioned.

(R ⁸ ) ₃ Al (15) (wherein R ⁸ may be the same or different and is substituted with a hydrogen atom, a halogen, a hydrocarbon group, an amino group, an alkoxy group, or a hydrocarbon group. An amino group or an alkoxy group, at least one of which is a hydrocarbon group.) Examples of such a compound include trimethylaluminum,
Examples thereof include triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

(R ⁹ ) ₂ Mg (16) (wherein R ⁹ may be the same or different and is substituted with a hydrogen atom, a halogen, a hydrocarbon group, an amino group, an alkoxy group, or a hydrocarbon group. Represents an amino group or an alkoxy group, at least one of which is a hydrocarbon group.) Examples of such compounds include dimethylmagnesium,
Diethyl magnesium, dibutyl magnesium, ethyl butyl magnesium, methyl magnesium chloride,
Examples thereof include methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, isopropyl magnesium chloride, isopropyl magnesium bromide, butyl magnesium chloride, and butyl magnesium bromide.

R ¹⁰ Li (17) (wherein R ¹⁰ may be the same or different and each is a hydrogen atom or a hydrocarbon group.) Examples of such a compound include methyllithium, ethyllithium and butyllithium. And the like.

Of these, particularly preferred are trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and isobutylaluminum dichloride.

In the preparation of the catalyst, the quantitative ratio of the transition metal compound (A) or (A ') to the activation co-catalyst (B) is (B)
The activating co-catalyst is represented by the general formulas (7), (8), (9), (1)
(A), (A ') a transition metal compound and (B)
The activating co-catalyst is (A, A ′ component) :( B component) = 10:
A molar ratio of 1 to 1: 1000 is preferably used, and a range of 3: 1 to 1: 100 is particularly preferably used. Further, (C) when using the organometallic compound (A),
Although the ratio of the transition metal compound (A ′) to the organometallic compound (C) is not particularly limited, the molar ratio of the (A), (A ′) transition metal compound and the (C) organometallic compound per metal atom is ( A, A 'components): (C component) = 100: 1 to 1:10
It is preferably used in the range of 0000, particularly preferably in the range of 1: 1 to 1: 10000. Considering the viewpoints of catalyst stability and catalyst poison removal, (C) the organometallic compound is (A, A ′ component) :( C component) = 1: 1.
It is particularly preferred to use a molar ratio of １ ： 1: 1000.

When the (B) activating co-catalyst is aluminoxane, (A, A ′) a transition metal compound and (B) a molar ratio per metal atom of the activating co-catalyst (A, A ′ component) :
(B component) = 100: 1 to 1: 1000000 is preferably used, and particularly preferably 1: 1 to 1: 1000000.
Range is used. The ratio of the (A, A ′) transition metal compound to the (C) organometallic compound is not particularly limited,
The molar ratio of (A, A ') transition metal compound to (C) organometallic compound per metal atom is preferably in the range of (A, A' component) :( C component) = 100: 1 to 1: 100,000. It is particularly preferably used in the range of 1: 1 to 1: 10000.

Further, when (B) the activation promoter is a clay mineral, (B)
The amount of the clay mineral of the activating co-catalyst is not particularly limited as long as the amount of the clay mineral is sufficient for the (A, A ') transition metal compound to react. The amount ratio to the mole is preferably from 0.01 to 10000 kg, more preferably from 0.1 to 1000 kg.

(B) When the activating co-catalyst is magnesium chloride, (B) relative to (A, A ') transition metal compound
The amount of magnesium chloride in the activation promoter is (A, A ')
There is no particular limitation as long as the amount of magnesium chloride is sufficient for the transition metal compound to react.
And more preferably 0.1 to 1000 kg.

(B) When the activating co-catalyst is a surface-modified inorganic oxide or inorganic halide or a solid component in which the solid surface is a cationic component and a counter anionic component of an ionic compound is coordinated, A, A ') The ratio of the transition metal compound to the (B) activating co-catalyst is not particularly limited,
(B) The amount ratio of the (A, A ') transition metal compound to the activation promoter is (A, A' component) :( B component) = 0.01
The range is preferably from 1 mmol: 1 kg to 1 mol: 1 kg, more preferably from 0.1 mmol: 1 kg to 1 mol.
0.5 mol: 1 kg, particularly preferably 1 mmol: 1 k
g-0.3 mol: in the range of 1 kg.

In the present invention, the method for preparing the catalyst is not particularly limited, and examples of the preparation method include a method in which a solvent or a monomer inert to each component is used as a solvent and mixed. Also, there is no particular limitation on the order in which the above-mentioned catalyst components are reacted, and there is no particular limitation on the temperature and the processing time for this treatment.

The catalyst for olefin polymerization of the present invention can be used in any of ordinary polymerization methods, that is, slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, bulk polymerization and the like.

In the present specification, the term polymerization is used to mean not only homopolymerization but also copolymerization. The polyolefin produced by these polymerizations includes not only homopolymers but also copolymers. I have.

Further, in the present invention, a method for preliminarily forming polymer particles using the catalyst system described above, further controlling the shape and density of the polyolefin particles, and stably producing a desired polyolefin will be described. ing. Further, the present invention shows a method for preliminarily forming polymer particles on a solid support, controlling the shape and density of polyolefin particles, and stably producing a desired polyolefin.

Using the olefin polymerization catalyst of the present invention,
When a polyolefin is produced in the presence of an olefin polymerization catalyst obtained by prepolymerizing an olefin, the resulting polyolefin has a high bulk density, does not adhere to the reactor wall, etc., and particularly in gas phase polymerization or slurry polymerization. Stable production is realized.

Further, (A, A ′) transition metal compounds,
The (B) activation co-catalyst and / or (C) the organometallic compound may be supported on (D) a solid carrier or the like and used as a solid catalyst for olefin polymerization. The solid support (D) used as a component of the solid catalyst for olefin polymerization is an inorganic or organic compound, and specific examples of the inorganic compound include an inorganic oxide and an inorganic halide. More specifically, as an example of an inorganic oxide,
Examples include oxides of typical elements such as alumina, silica and magnesia, transition metal oxides such as titania and zirconia, and composite oxides such as silica-alumina and silica-magnesia. Examples of inorganic halides include magnesium chloride, aluminum chloride and the like. These compounds usually include, as impurities, salts such as carbonates and sulfates of alkali metals and alkaline earth metals such as potassium carbonate and barium sulfate, and inorganic halides include hydroxides and oxides. The above-mentioned inorganic oxides or inorganic halides can be used in a form containing these impurities, but it is preferable to use beforehand an operation of removing or reducing these impurities. Also, as an organic carrier,
Examples include polyolefins such as polyethylene, polypropylene, and polybutene; polar polymers such as polystyrene, polyethyl methacrylate, polyester, and polyimide; and mixtures of polyolefins and polar polymers. Further, the organic carrier may have a copolymer composition such as an ethylene-vinyl acetate copolymer which is a copolymer of an olefin and a polar monomer.

The shape of the solid carrier (D) used in the present invention is not limited. However, considering the range in which the catalyst shows high activity and is easy to handle in the process, the particle diameter is 0.1 to 1%.
It is preferably in the form of granules or fine particles having a diameter of 000 μm and a pore diameter of 1 to 1000 nm.

The olefin (E) which is a component of the solid catalyst for olefin polymerization obtained by prepolymerization using the catalyst for olefin polymerization or the solid catalyst for olefin polymerization of the present invention is not particularly limited. Α-olefins or cyclic olefins are preferred, and α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene; butadiene, 1,4-hexadiene, 5 -Ethylidene-2
-Norbornene, dicyclopentadiene, 4-methyl-
Conjugated and non-conjugated dienes such as 1,4-hexadiene and 7-methyl-1,6-octadiene; and cyclic olefins such as cyclobutene and cyclopentene. These may be used alone or as a mixture of two or more.

When the prepolymerization is carried out using two or more olefins, they are added sequentially or simultaneously to the reaction system.
Prepolymerization can also be performed.

The prepolymerization method using the olefin polymerization catalyst or the olefin polymerization solid component of the present invention is not particularly limited as long as the olefin polymerization catalyst or the olefin polymerization solid catalyst and the (E) olefin can be polymerized. Although not particularly limited, the reaction temperature is −50 to 100 ° C.,
Preferably -20 to 60 ° C, more preferably -10 to 4
In the temperature range of 0 ° C., the reaction pressure can be carried out under normal pressure or under pressure. When the reaction is carried out in a gaseous phase, it is preferred that the contact be carried out sufficiently under flow conditions, and when the reaction is carried out in a liquid phase, the contact is carried out sufficiently under stirring conditions.

The olefin used for the polymerization in the present invention includes α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene; butadiene, 1,4- Hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-
Conjugated and non-conjugated dienes such as methyl-1,6-octadiene; cyclic olefins such as cyclobutene and cyclopentene; and ethylene and propylene;
Polymerization can be carried out by mixing two or more components such as butene, or three or more components such as ethylene and propylene and styrene, ethylene and 1-hexene and styrene, and ethylene and propylene and ethylidene norbornene.

In the present invention, it is possible to carry out polymerization using two or more kinds of (A, A ') transition metal compounds. In particular, when expanding the molecular weight distribution or the composition distribution, a plurality of (A, A ′) transition metal compounds can be used.

In the present invention, olefin polymerization can be carried out in a gas phase or a liquid phase. In particular, when the olefin polymerization is carried out in a gas phase, an olefin polymer having a uniform particle shape can be produced efficiently and stably. be able to. When the polymerization is performed in the liquid phase, the solvent used may be any commonly used organic solvent, and specific examples include benzene, toluene, xylene, propane, isobutane, pentane, heptane, cyclohexane, gasoline, and the like. And olefin itself such as propylene, 1-butene, 1-hexene and 1-octene can be used as a solvent.

In producing an olefin polymer using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited.
The polymerization temperature is −100 to 300 ° C., and considering the productivity, 2
0 to 300 ° C., particularly preferably 120 to 300 ° C. when the ethylene copolymer is produced by a high pressure method, and −
10 to 260 ° C, 6 for slurry polymerization and gas phase polymerization
It is preferable to carry out in the range of 0 to 120 ° C. The polymerization time varies depending on each process, but is usually performed in the range of 10 seconds to 20 hours, and the polymerization pressure varies depending on the process, but can be performed in the range of normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. Polymerization is batch, semi-continuous,
It is possible to carry out by any method of a continuous type, and it is also possible to carry out in two or more stages by changing the polymerization conditions.
Further, the polyolefin can be separated and recovered from the polymerization solvent by a conventionally known method after completion of the polymerization, and can be obtained by drying.

[0074]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The reactions were all carried out in an atmosphere of an inert gas such as dried or purified nitrogen or argon.
fiction of Laboratory Ch
Purification, drying, or deoxygenation was performed by a known method described in “Electrics 2nd Edition” and the like.

The transition metal compound was identified by NMR (GPX-400 type NMR measuring apparatus manufactured by JEOL Ltd.) and M
The measurement was performed using ASS (QP-1000, manufactured by Shimadzu Corporation, mass spectrometer).

MI (melt index), HLMI
(High Road Melt Index) is ASTM D-
1238, MI is 2.16 kg load, H
LMI was performed with a 21.6 kg load. The N value is H
Represents the ratio of LMI / MI.

Example 1 (Synthesis of (cyclopentadienyl) (4,5-diazafluorene) zirconium trichloride) Under a nitrogen atmosphere, 4,5-diazafluoren-9-one (1.0 g, 5. 50 mmol) was placed in a 100 ml two-necked eggplant flask, and hydrazine monohydrate (4.2 ml,
84 mmol) was added. The mixture was heated at 200 ° C. for 6 hours. After cooling, 30 ml of dichloromethane and 10 ml of water were added, and the mixture was extracted with dichloromethane. After the dichloromethane extract was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained solid was 4,5-diazafluorene having a Rf of 0.45 by column chromatography using ethyl acetate as a solvent (white solid, 0.39 g). ¹ H-NMR and MS
From the spectrum, it was confirmed that the substance was 4,5-diazafluorene.

¹ H-NMR; (solvent: CDCl ₃ , δ (p
pm)) 8.78 (d, J = 4.0 Hz), 7.93
(D, J = 7.7 Hz), 7.35 (dd, J = 4.8)
Hz), 3.92 (s) MASS; 168 (M +) 4,5-diazafluorene (258 mg,
1.54 mmol) in 10 ml of hexane and n
-BuLi hexane solution (1.54 M, 1.0 ml,
1.54 mmol) was added at low temperature. This reaction solution was slowly added at low temperature to a suspension of cyclopentadienyl zirconium trichloride (406 mg, 1.54 mmol) in 10 ml of toluene which was collected in another container. After the temperature of the reaction solution was raised naturally, the soluble part and the insoluble part were separated by filtration. The insoluble portion was vacuum dried to obtain 647 mg of a reddish brown solid.

¹ H-NMR; (solvent: CDCl ₃ , δ (p
pm)) 4.17 (s), 6.89 (s), 7.61
(Dd, J = 4.7 Hz), 8.14 (dd, J = 7.7 Hz).
4 Hz), 8.78 (d, J = 5.4 Hz), 9.52
(D, J = 5.4 Hz) (Preparation of catalyst) (cyclopentadienyl) obtained earlier
4.8 mg of (4,5-diazafluorene) zirconium trichloride was placed in a Schlenk tube, and 1000 ml of toluene was added to methylaluminoxane (MAO).
(Tosoh Akzo Co., Ltd., aluminum content 10.4w
(t%) 11 ml of a solution to which 1.5 ml was dropped was added to obtain a pale purple catalyst solution, and 1 ml of the solution was dropped into toluene to which MAO was added to obtain a catalyst solution (1).

(Polymerization of ethylene) The catalyst solution (1) prepared above was introduced into a 2-liter stainless steel autoclave under a nitrogen atmosphere, and the temperature was raised to 70 ° C. Next, ethylene was introduced into the autoclave, and the ethylene partial pressure was 0.6 MPa.
The polymerization was started under the following conditions. Polymerization temperature 80
C., polymerization was carried out for 60 minutes, and 100 ml of ethanol was injected into the autoclave under pressure to terminate the polymerization. As a result, 23.43 g of polyethylene was obtained. The MI of this polymer was 0.025 g / 10 min, and the N value was 29.

Example 2 (Copolymerization of ethylene and 1-hexene)
The catalyst solution (1) obtained in Example 1 was introduced into 1 l of a stainless steel autoclave, and 1-hexene was further added to 20 l of autoclave.
After introducing ml, the temperature was raised to 70 ° C. Next, ethylene was introduced into the autoclave, and polymerization was started by setting the ethylene partial pressure to 0.6 MPa. The polymerization was carried out for 60 minutes while maintaining the polymerization temperature at 80 ° C., and 100 ml of ethanol was injected into the autoclave to stop the polymerization. as a result,
71.93 g of an ethylene / 1-hexene copolymer was obtained. The MI of this polymer was 0.121 g / 10 min, and the N value was 22.

Example 3 (Synthesis of (cyclopentadienyl) (4,5-diazafluorene) zirconium trichloride)
4,5-diazafluorene (258 mg, 1.54 mm
ol) was suspended in 10 ml of toluene, and the resulting suspension was placed in a separate container.
Slowly added to 0 ml suspension. The reaction solution was dried under vacuum to obtain 660 mg of a white solid.

¹ H-NMR; (solvent: CDCl ₃ , δ (p
pm)) 4.17 (s), 6.89 (s), 7.61
(Dd, J = 4.7 Hz), 8.14 (dd, J = 7.7 Hz).
4 Hz), 8.78 (d, J = 5.4 Hz), 9.52
(D, J = 5.4 Hz) (Polymerization of ethylene) (cyclopentadienyl) (4,5-diazafluorene) zirconium trichloride obtained above was introduced into a 2 l stainless steel autoclave under a nitrogen atmosphere. The temperature was raised to 70 ° C. Next, ethylene was introduced into the autoclave, and the ethylene partial pressure was 0.6 MPa.
The polymerization was started under the following conditions. Polymerization temperature 80
C., polymerization was carried out for 60 minutes, and 100 ml of ethanol was injected into the autoclave under pressure to terminate the polymerization. As a result, 5.86 g of polyethylene was obtained. The MI of this polymer was 0.006 g / 10 min, and the N value was 31.

[0085]

According to the present invention, it is possible to provide an olefin polymerization catalyst comprising a transition metal compound having a novel structure as a main catalyst. A homogeneous polyolefin having a narrow molecular weight distribution and composition distribution can be economically produced.

Continued on the front page F term (reference) 4J028 AA01A AB01A AC00A AC01A AC02A AC08A AC10A AC18A AC20A AC22A AC26A AC28A AC31A AC32A AC37A AC38A AC41A AC42A AC44A BC01B BC05B BC06B BC12B DA06 DB04A EB02 EB04 EB05 EB07 EB09 EB10 EB13 EB16 EB17 EB18 EB21 EC01 EC02 FA01 FA02 FA04 FA06 FA07 GA05 4J100 AA02P AA03P AA03Q AA04P AA16P AA16Q AA17P AA19P AB02 AS02P02 AR03 AS02P

Claims (3)

[Claims] (A) The following general formula (1): (Here, M is a transition metal of Group 3, 4, 5, or 6 of the periodic table, and n is an integer of 3 to 6 representing the formal oxidation number of M. L ¹ and L ² are the same or different. at best, the following general formula (2), (3) ((2) and (3) at least comprises one or more nitrogen atoms in the benzene ring moiety) represented by or (4), of L ^1, L ² At least one is (2) or (3), and formula (4) is always a monovalent anion, X may be the same or different,
A hydrogen atom, a halogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, a substituted amino group or a substituted alkoxy group, and 1 is an integer of n-2 or more. Embedded image Embedded image Embedded image Also, here, (R ¹ ) a or (R ² ) a may be the same or different, a may be the same integer or different and may be 1 or 2, and the formula (2) or (3) may be 1 or 2 A is 1 when it represents a valent anion, and 2 when the formula (2) or (3) is neutral. (R ¹ ) a or (R ² )
a is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. (R ¹ ) b and (R ² ) b may be the same or different, b may be the same integer or different and may be 0 or 1, and (R ¹ ) b, (R ² ) b or R ³ is hydrogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group, or a ring forming an atom forming them; Is also good. ), (B) an activating co-catalyst and / or (C)
An olefin polymerization catalyst comprising an organometallic compound. (A ′) A compound of the general formula (5) wherein L ¹ and L ² are linked by a substituent L ³ represented by the formula (6). Embedded image (Here, M is a transition metal of Group 3, 4, 5, or 6 of the periodic table, and n is an integer of 3 to 6 representing the formal oxidation number of M. L ¹ and L ² are the same or different. at best, the following general formula (2), (3) ((2) and (3) at least comprises one or more nitrogen atoms in the benzene ring moiety) represented by or (4), of L ^1, L ² At least one is (2) or (3), and formula (4) is always a monovalent anion, X may be the same or different,
A hydrogen atom, a halogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, a substituted amino group or a substituted alkoxy group, and 1 is an integer of n-2 or more. Embedded image Embedded image Embedded image Here, (R ¹ ) a or (R ² ) a may be the same or different, and a may be the same integer or different and may be 0 or 1, and the formula (2) or (3) may be 1 A is 0 when it represents a valent anion, and 1 when the formula (2) or (3) is neutral. R ⁴ and R ⁵ may be the same or different, and represent a hydrocarbon group, a hetero atom-containing hydrocarbon group, a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, or an atom forming them. And a ring may be formed through the ring. m is an integer of 1 to 10. ), A catalyst for olefin polymerization, comprising (B) an activating co-catalyst and / or (C) an organometallic compound. 3. A method for producing a polyolefin, comprising homopolymerizing or copolymerizing an olefin using the catalyst for olefin polymerization according to claim 1 or 2.