JPH09176221A - Catalyst for olefin polymerization and production of olefin polymer by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular-weight olefin polymer in high activity at a general reaction temperature by using a catalyst for olefin polymerization comprising a specified transition metal complex (A) and an organoaluminum compound (B) or a cyclic or linear aluminoxane (C). SOLUTION: Component A is represented by formula I [wherein M<1> and M<2> are each a group 4 transition metal atom; Cp<1> to Cp<4> are each a cyclopentadienyl-skeleton-carrying group; Cp<1> and Cp<2> or Cp<3> and Cp<4> are bridged through a bridging group having 1-20 nonhyydrogen atoms; L<1> and L<2> are each a 15 or 16 group atom; R is a 1-20C covalent bond group; X<1> and X<2> are each H, a halogen, a 1-20C (halo)hydrocarbon group, a 1-20C alkoxyl, a 1-20C aryloxy or a 2-20C disubstituted amino]]. Component B is represented by the formula: E<1> a AlZ3-a . Component C is a cyclic aluminoxane represented by the formula: -Al(E<2> )-O-}b or a linear aluminoxane represented by the formula: E<3> [Al(E<3> )-O-]c AlE<3> 2 . In the three formulas, E<1> to E<3> are each a 1-8C hydrocarbon group; Z is H or a halogen; (a) is 0-3; and (b) and (c) are each a number of 1 or greater.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metallocene catalyst for olefin polymerization. More specifically, the two transition metal atoms coordinated by the cyclopentadienyl group are
The present invention relates to an olefin polymerization catalyst containing a complex linked by a covalent bond group containing a group 16 atom, and a method for producing an olefin polymer using the same.

[0002]

2. Description of the Related Art Many reports have already been made on a method for producing an olefin polymer using a metallocene complex. For example, in JP-A-58-19309,
A method for producing a polyolefin using a metallocene complex and an aluminoxane has been reported. In that report, when olefin polymerization was carried out in a system using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane, there was a problem that the molecular weight of the obtained olefin polymer was low.

Several types of metallocene complexes having two or more transition metal atoms are already known. For example, Journal of Organometallic Chemistry, 4
Volume 60 (1993) pp. 191-195 describes the synthesis of metallocene complexes having two zirconium atoms and the olefin polymerization using the same. However, the molecular weight of the olefin polymer was still low.

[0004]

In view of such circumstances, the present invention provides two transitions which give a high activity, high molecular weight olefin polymer at the reaction temperatures commonly used in industrial processes for olefin polymerization. An object is to provide an olefin polymerization catalyst containing a metallocene complex having a metal atom, and a method for producing an olefin polymer using the same.

[0005]

[Means for Solving the Problems] In order to achieve the above-mentioned objects, the present invention has conducted extensive studies on transition metal complexes and olefin polymerization catalysts. As a result, the first two transition metal atoms coordinated by the cyclopentadienyl group
The present invention has been completed by discovering a catalyst for olefin polymerization containing a complex linked by a covalent bond group containing atoms of groups 5 and 16.

That is, the present invention is directed to an olefin polymerization catalyst comprising a transition metal complex represented by the following general formula [I] and the following compound (A), and an olefin polymerization comprising the catalyst further containing the following compound (B). And a method for producing an olefin polymer using these catalysts.

Embedded image(Where M¹, M^TwoIs transition gold of Group 4 of the Periodic Table of the Elements
Represents a genus atom, which may be the same or different, Cp
¹, Cp^Two, Cp^Three, Cp^FourIs cyclopentadienyl bone
Represents a group having a case and may be the same or different.
Yes. Cp¹And Cp^Two, Cp^ThreeAnd Cp^FourAre each non-water
It may be crosslinked with a crosslinking group having 1 to 20 elementary atoms.
L¹, L^TwoIs a group 15 or 16 atom, a transition metal atom and R
Is a covalent linking group that connects
May be. R is a covalent bond group having 1 to 20 carbon atoms
is there. X¹, X^TwoIs hydrogen atom, halogen atom, carbon atom
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
Hydrocarbon group, alkoxy group having 1 to 20 carbon atoms,
Aryloxy group having 1 to 20 carbon atoms or the number of carbon atoms
2 to 20 disubstituted amino groups, which may be the same or different.
May be. ) (A) Any of the following compounds (A1) to (A3)
Or a mixture of two or three of them. (A1) General formula E¹ _aAlZ_3-aOrganic Al
Minium compound (A2) General formula {-Al (E^Two) -O-｝_bIndicated by
Structured cyclic aluminoxane (A3) General formula E^Three｛-Al (E^Three) -O-｝_cAl
E^Three _TwoA linear aluminoxane having the structure¹~ E^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms
And all E¹, All E ^TwoAnd all E^ThreeAre the same
Or they may be different. Z is a hydrogen atom or halogen
Represents an atom, all Z being the same or different
good. a is a number from 0 to 3, and b and c are integers of 1 or more.
You. ) (B) Reacts with a transition metal compound to form an ionic complex
Compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

(1) Transition Metal Complex M ¹ and M ² in the transition metal complex represented by the above general formula [I] used in the present invention are the periodic table (I) of the elements.
A transition metal atom of Group 4 of UPAC Inorganic Chemistry Revised Edition 1989), preferably a titanium atom, a zirconium atom, or a hafnium atom.

Cp ¹ , Cp ² , Cp ³ and Cp ⁴ in the transition metal complex represented by the above general formula [I] are groups having a cyclopentadienyl skeleton, for example, cyclopentadienyl and substituted cyclopenta. Dienyl, indenyl,
Substituted indenyl, fluorenyl or substituted fluorenyl. Specific examples include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, normal propylcyclo Pentadienyl group, isopropylcyclopentadienyl group, primary butylcyclopentadienyl group, secondary butylcyclopentadienyl group, tertiary butylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilyl Cyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, ethylindenyl group, normal propylindenyl group, isopropylindenyl group, first
Butylindenyl group, secondary butylindenyl group, tertiary butylindenyl group, phenylindenyl group, trimethylsilylindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl group, ethylfluorene Nyl group, diethyl fluorenyl group, normal propyl fluorenyl group, di-normal propyl fluorenyl group,
Isopropyl fluorenyl group, diisopropyl fluorenyl group, primary butyl fluorenyl group, di primary butyl fluorenyl group, secondary butyl fluorenyl group, di secondary
Butyl fluorenyl group, tertiary butyl fluorenyl group, ditertiary butyl fluorenyl group, phenyl fluorenyl group, diphenyl fluorenyl group, trimethylsilyl fluorenyl group, ditrimethyl silyl fluorenyl group And the like, and preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an indenyl group, a methylindenyl group and a fluorenyl group.

Cp ¹ and Cp ² and Cp ³ and Cp ⁴ may be crosslinked with a crosslinking group having 1 to 20 non-hydrogen atoms. Examples of the bridging group connecting the two Cp rings include an alkylene group having 1 to 20 non-hydrogen atoms and a silylene group.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, dimethylmethylene group,
Examples thereof include a diphenylmethylene group and a tetramethylethylene group. Of these, a methylene group, an ethylene group, a dimethylmethylene group and a diphenylmethylene group are preferable.

Specific examples of the silylene group include a silylene group, a dimethylsilylene group, and a diphenylsilylene group.

L ¹ and L ² in the above-mentioned general formula [I] are covalent bonding groups for connecting the transition metal atom and R with atoms of groups 15 and 16, and they may be the same or different, preferably Is an oxygen atom, a sulfur atom, an imino group, or the like.

When L is an imino group, specific examples thereof include a methylimino group, an ethylimino group, a normal propylimino group, an isopropylimino group, a normal butylimino group, a secondary butylimino group, a tertiary butylimino group and an isobutylimino group. Group, a phenylimino group and the like, and preferably a methylimino group, an isopropylimino group and the like.

R in the above general formula [I] is a covalent bond group having 1 to 20 carbon atoms, and examples thereof include an alkylene group, an arylene group and a silylene group. Preferably,
An alkylene group having 1 to 20 carbon atoms and an arylene group.

Examples of the alkylene group include a linear alkylene group and an alkylene group having a branched chain. Among them, a linear alkylene group having 1 to 10 carbon atoms is preferable, and a specific example is methylene. Group, ethylene group,
Examples thereof include a propylene group, a butylene group, a hexylene group and an octylene group.

The arylene group may be a monocyclic ring or a condensed ring.
A valent aromatic group can be mentioned as an example, and specific examples thereof include a 1,2-phenylene group, a 1,3-phenylene group,
1,4-phenylene group, 1,2-naphthylene group, 1,3
-Naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group,
2,5-naphthylene group, 2,6-naphthylene group, 2,7
-Naphthylene group, 1,2-anthranylene group, 1,3-
Examples thereof include anthranylene group, 1,4-anthranylene group, and an arylene group in which a hydrocarbon group having 1 to 5 carbon atoms is substituted. Preferred is a 1,2-phenylene group.

X ¹ and X ² in the above general formula [I] are hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, and number of carbon atoms. 1-20 alkoxy groups, 1-20 carbon atoms
Is an aryloxy group or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different. Preferred is a halogen atom.

When X ¹ and X ² are halogen atoms, specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the case where X ¹ and X ² are hydrocarbon groups include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group and tertiary group. Butyl group, normal pentyl group, neopentyl group, normal hexyl group, normal octyl group, phenyl group, 2-methylphenyl group, 3-
Examples thereof include a methylphenyl group, a 4-methylphenyl group, a naphthyl group and a benzyl group.

Specific examples of the case where X ¹ and X ² are halogenated hydrocarbon groups include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 1, 1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 1-chloroethyl group Group, 2-chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2-trichloroethyl group, 1,1,
2,2-tetrachloroethyl group, pentachloroethyl group, bromomethyl group, dibromomethyl group, tribromoethyl group, 1-bromoethyl group, 2-bromoethyl group,
1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2-tribromoethyl group, 1,1,2,2
-Tetrabromoethyl group, pentabromoethyl group, 2-
Fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group,
2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,3,4
-Trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group,
2,3,4,5-tetrafluorophenyl group, 2,3
4,6-tetrafluorophenyl group, pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,3,4-
Trichlorophenyl group, 2,3,5-trichlorophenyl group, 2,3,6-trichlorophenyl group, 2,3
4,5-tetrachlorophenyl group, 2,3,4,6-tetrachlorophenyl group, pentachlorophenyl group, 2-
Bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4-dibromophenyl group, 2,5-dibromophenyl group, 2,
6-dibromophenyl group, 2,3,4-tribromophenyl group, 2,3,5-tribromophenyl group, 2,3
Examples thereof include a 6-tribromophenyl group, a 2,3,4,5-tetrabromophenyl group, a 2,3,4,6-tetrabromophenyl group and a pentabromophenyl group.

When X ¹ and X ² are alkoxy groups, specific examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, primary butoxy group, secondary butoxy group and tertiary butoxy group. , Isobutoxy group, normal pentoxy group, neopentoxy group, normal hexoxy group, normal octoxy group and the like.

When X ¹ and X ² are aryloxy groups, specific examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group and a naphthyloxy group.

When X ¹ and X ² are disubstituted amino groups, specific examples thereof include dimethylamino group, diethylamino group, dinormalpropylamino group, diisopropylamino group, dinormalbutylamino group and di-secondary butyl group. Examples thereof include an amino group, ditertiary butylamino group, diisobutylamino group, dinormal hexylamino group, dinormal octylamino group, and diphenylamino group.

Specific examples of the compound represented by the general formula [I] include (μ-methanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ
-Methanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {methylene (biscyclopentadiene) (Enyl) zirconium chloride}, (μ-methanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ- Methanedioxo) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, ( -Methanedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {ethylene (bismethyl Cyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (Μ-Methanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-methanedioxo) bis {dimethylsilylene (bistetramethylcyclopenta Dienyl) zirconium chloride}, (μ
-Methanedioxo) bis {(bisindenyl) zirconium chloride}, (μ-methanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-methanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ-methanedioxo) bis { Dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,2-ethanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -1,2-ethanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 2-ethanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2 -Ethanedioxo)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,2-ethanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2
-Ethanedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,2- Ethanedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo )
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,2-ethanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2
-Ethanedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {(bisindenyl) zirconium chloride}, (μ-1,2-
Ethanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,2-ethanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,2-ethanedioxo)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,3-propanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride }, (Μ-1,3-propanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {ethylene (biscyclopentadienyl) zirconium Chloride}, (μ-1,3-propanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {methylene (bistetramethylcyclopentadiene (Enyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {dimethyl Styrene (biscyclopentadienyl) zirconium dichloride},

(Μ-1,3-propanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {dimethylmethylene (bistetramethylcyclo) Pentadienyl) zirconium chloride},
(Μ-1,3-propanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride},
(Μ-1,3-propanedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {ethylene (bistetramethylcyclopentadienyl) zirconium Chloride}, (μ-1,3-propanedioxo)
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,3-propanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,
3-propanedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {(bisindenyl) zirconium chloride}, (μ
-1,3-propanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-
1,3-propanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,3-propanedioxo) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,4-butanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -1,4-butanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 4-butanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,4 -Butanedioxo)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,4-butanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4
-Butanedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,4- Butanedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo )
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,4-butanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4
-Butanedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {(bisindenyl) zirconium chloride}, (μ-1,4-
Butanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,4-butanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,4-butanedioxo)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,6-hexanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride }, (Μ-1,6-hexanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {ethylene (biscyclopentadienyl) zirconium Chloride}, (μ-1,6-hexanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {methylene (bistetramethylcyclopentadi) (Enyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {dimethyl Styrene (biscyclopentadienyl) zirconium dichloride}, (μ-1,6
-Hexanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-1,6-hexanedioxo) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,6-hexanedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {ethylene (bistetramethylcyclopenta) Dienyl) zirconium chloride}, (μ-
1,6-hexanedioxo) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,6-hexanedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
1,6-hexanedioxo) bis {(bisindenyl)
Zirconium chloride}, (μ-1,6-hexanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,6-hexanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ- 1,6-hexanedioxo) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,8-octanedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride }, (Μ-1,8-octanedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {ethylene (biscyclopentadienyl) zirconium Chloride}, (μ-1,8-octanedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {methylene (bistetramethylcyclopentadiene) Enyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {dimethyl Styrene (biscyclopentadienyl) zirconium dichloride}, (μ-1,8
-Octanedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-1,8-octanedioxo) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,8-octanedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {ethylene (bistetramethylcyclopenta Dienyl) zirconium chloride}, (μ-
1,8-octanedioxo) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,8-octanedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
1,8-octanedioxo) bis {(bisindenyl)
Zirconium chloride}, (μ-1,8-octanedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,8-octanedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ- 1,8-octanedioxo) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,2-benzenedioxo) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {(bismethylcyclopentadienyl) zirconium chloride }, (Μ-1,2-benzenedioxo) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {ethylene (biscyclopentadienyl) zirconium Chloride}, (μ-1,2-benzenedioxo) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {methylene (bistetramethylcyclopentadiene (Enyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {dimethyl Styrene (biscyclopentadienyl) zirconium dichloride}, (μ-1,2
-Benzenedioxo) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {dimethylmethylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-1,2-benzenedioxo) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,2-benzenedioxo) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {ethylene (bistetramethylcyclopenta Dienyl) zirconium chloride}, (μ-
1,2-benzenedioxo) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,2-benzenedioxo) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
1,2-benzenedioxo) bis {(bisindenyl)
Zirconium chloride}, (μ-1,2-benzenedioxo) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,2-benzenedioxo) bis {ethylene (bisindenyl) zirconium chloride}, (μ- 1,2-benzenedioxo) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-Methanedithio) bis {(biscyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-methanedithio)
Bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {methylene (biscyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {methylene (bismethylcyclopentadienyl) Zirconium chloride}, (μ-methanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-methanedithio) Bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-meta Dithio) bis {ethylene (bis cyclopentadienyl) zirconium dichloride}, (.mu. Metanjichio) bis {ethylene (bis-methyl cyclopentadienyl) zirconium dichloride},
(Μ-methanedithio) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-methanedithio) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ
-Methanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride},
(Μ-Methanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-methanedithio) bis {(bisindenyl) zirconium chloride}, (μ-methanedithio)
Bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-methanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-
Methanedithio) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,2-ethanedithio) bis {(biscyclopentadienyl) zirconium chloride},
(Μ-1,2-ethanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
1,2-ethanedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-
1,2-ethanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,
2-ethanedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-
1,2-ethanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-1 , 2-ethanedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ- 1,2-
Ethanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {Ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
1,2-ethanedithio) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride},
(Μ-1,2-ethanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-1,2-ethanedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,2-ethanedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride},
(Μ-1,2-ethanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,2-
Ethanedithio) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,3-propanedithio) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,3-propanedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, ( μ-1,3-propanedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (Μ-1,3-propanedithio)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,3-propanedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3
-Propanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 3-propanedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1 , 3-propanedithio)
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,3-propanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,3
-Propanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,3-propanedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,3-
Propanedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,3-propanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,3-propanedithio)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,4-butanedithio) bis {(biscyclopentadienyl) zirconium chloride},
(Μ-1,4-butanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
1,4-butanedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-
1,4-butanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,
4-butanedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-
1,4-butanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedithio) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-1 , 4-butanedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ- 1,4-
Butanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1,4-butanedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedithio) bis {Ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
1,4-butanedithio) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride},
(Μ-1,4-butanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,4-butanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-1,4-butanedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,4-butanedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride},
(Μ-1,4-butanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,4-
Butanedithio) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,6-hexanedithio) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,6-hexanedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, ( μ-1,6-hexanedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (Μ-1,6-hexanedithio)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,6-hexanedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6
-Hexanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 6-hexanedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1 , 6-hexanedithio)
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,6-hexanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,6
-Hexanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,6-
Hexanedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,6-hexanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,6-hexanedithio)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,8-octanedithio) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,8-octanedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, ( μ-1,8-octanedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (Μ-1,8-octanedithio)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,8-octanedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8
-Octanedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 8-octanedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1 , 8-octanedithio)
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,8-octanedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,8
-Octanedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,8-octanedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,8-
Octanedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,8-octanedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,8-octanedithio)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-1,2-benzenedithio) bis {(biscyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {(bismethylcyclopentadienyl) zirconium chloride}, (Μ-1,2-benzenedithio) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, ( μ-1,2-benzenedithio) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (Μ-1,2-benzenedithio)
Bis {dimethylmethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,2-benzenedithio) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2
-Benzenedithio) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-1, 2-benzenedithio) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1 , 2-benzenedithio)
Bis {dimethylsilylene (biscyclopentadienyl)
Zirconium chloride}, (μ-1,2-benzenedithio) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-1,2
-Benzenedithio) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {(bisindenyl) zirconium chloride}, (μ-1,2-
Benzenedithio) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-1,2-benzenedithio) bis {ethylene (bisindenyl) zirconium chloride}, (μ-1,2-benzenedithio)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-dimethyl-1,2-ethanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-
1,2-ethanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,2-ethanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,2-ethanediamino) bis {ethylene (biscyclo Pentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,2-ethanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl- 1,2-ethanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Dimethyl-1,2-ethanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,2-ethanediamino) bis {dimethylmethylene (bismethylcyclo) Pentadienyl) zirconium chloride}, (μ-
N, N'-dimethyl-1,2-ethanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Dimethyl-1,2-ethanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,2-ethanediamino) bis {ethylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N, N′-dimethyl-1,2-ethanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1, 2-ethanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Dimethyl-1,2-ethanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,2
-Ethanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,2-ethanediamino) bis {(bisindenyl) zirconium chloride}, (μ- N, N'-dimethyl-1,2-ethanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N'-dimethyl-
1,2-ethanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,2-ethanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-diethyl-1,2-ethanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-
1,2-ethanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-N,
N'-diethyl-1,2-ethanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,2-ethanediamino) bis {ethylene (biscyclo Pentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,2-ethanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl- 1,2-ethanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diethyl-1,2-ethanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,2-ethanediamino) bis {dimethylmethylene (bismethylcyclo) Pentadienyl) zirconium chloride}, (μ-
N, N'-diethyl-1,2-ethanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diethyl-1,2-ethanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,2-ethanediamino) bis {ethylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N, N′-diethyl-1,2-ethanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1, 2-ethanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diethyl-1,2-ethanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,2
-Ethanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,2-ethanediamino) bis {(bisindenyl) zirconium chloride}, (μ- N, N′-diethyl-1,2-ethanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-
1,2-ethanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,2-ethanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-diisopropyl-1,2
-Ethanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-1,2-ethanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -N, N'-diisopropyl-1,2-ethanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diisopropyl-1,2-ethanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,2-ethanediamino) bis {methylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N,
N'-diisopropyl-1,2-ethanediamino) bis {methylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diisopropyl-1,2-ethanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,2- Ethanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diisopropyl-1,2-ethanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
N, N'-diisopropyl-1,2-ethanediamino)
Bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-
1,2-ethanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diisopropyl-1,2-ethanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diisopropyl-1,2-ethanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-
1,2-ethanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,2-ethanediamino) bis {dimethylsilylene (bistetramethylcyclopenta Dienyl) zirconium chloride},
(Μ-N, N′-diisopropyl-1,2-ethanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,2-ethanediamino) bis {dimethylsilylene (bisindenyl) Zirconium chloride}, (μ-N, N′-diisopropyl-1,2-ethanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-
N, N'-diisopropyl-1,2-ethanediamino)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diphenyl-1,2-ethanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diphenyl-1,2-ethanediamino) Bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N′-diphenyl-1,2-ethanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,
2-ethanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,2-ethanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2
-Ethanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diphenyl-1,2-ethanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2-ethanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2-
Ethanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2-ethanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diphenyl-1,2-ethanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2- Ethanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,2-ethanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,
2-ethanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2-ethanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) ) Zirconium chloride}, (μ
-N, N'-diphenyl-1,2-ethanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-diphenyl-1,2-ethanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,2-ethanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-1,2-ethanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-dimethyl-1,3-propanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-
1,3-propanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N′-dimethyl-1,3-propanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3
-Propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,3-propanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3-
Propanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-dimethyl-1,3-propanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3-propanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3-propanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, ( μ-N, N′-dimethyl-1,3-propanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-dimethyl-1,3-propanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3- Propanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,3-propanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3
-Propanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,3-propanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) Zirconium chloride}, (μ
-N, N'-dimethyl-1,3-propanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-dimethyl-1,3-propanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,
3-propanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,3-propanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diethyl-1,3-propanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-
1,3-propanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N'-diethyl-1,3-propanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,3
-Propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N'-diethyl-1,3-propanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,3-
Propanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diethyl-1,3-propanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,3-propanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,3-propanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, ( μ-N, N′-diethyl-1,3-propanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diethyl-1,3-propanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,3- Propanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-diethyl-1,3-propanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,3
-Propanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,3-propanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) Zirconium chloride}, (μ
-N, N'-diethyl-1,3-propanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-diethyl-1,3-propanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,
3-propanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,3-propanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diisopropyl-1,3
-Propanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,3-propanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -N, N'-diisopropyl-1,3-propanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N '
-Diisopropyl-1,3-propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-1,
3-propanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diisopropyl-1,3-propanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diisopropyl-1,3-propanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-
1,3-propanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,3-
Propanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,3-propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride} , (Μ-N, N′-diisopropyl-1,3-propanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,
3-propanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,3-propanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium Chloride}, (μ-N,
N'-diisopropyl-1,3-propanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-1,3-propanediamino) bis {dimethylsilylene ( Bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diisopropyl-1,3-propanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-
Diisopropyl-1,3-propanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,3-propanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ- N, N'-diisopropyl-1,3-propanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diphenyl-1,3-propanediamino) bis {(biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diphenyl-1,3-propanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diphenyl-1,3-propanediamino)
Bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,3-propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-
N, N′-diphenyl-1,3-propanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,3-propanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,3-propanediamino) bis {dimethylmethylene (biscyclopentadienyl) ) Zirconium chloride}, (μ-N, N ′
-Diphenyl-1,3-propanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diphenyl-
1,3-propanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,3
-Propanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,3-propanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,3-propanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,3-propanediamino) bis {dimethylsilylene (biscyclopentadienyl) ) Zirconium chloride}, (μ-N, N ′
-Diphenyl-1,3-propanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diphenyl-
1,3-propanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,3
-Propanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,3-propanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-
N, N'-diphenyl-1,3-propanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N'-diphenyl-1,3-propanediamino) bis {dimethylmethylene (cyclopentadienyl) ) (Fluorenyl) zirconium chloride},

(Μ-N, N'-dimethyl-1,4-butanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-
1,4-butanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,4-butanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,4-butanediamino) bis {ethylene (biscyclo Pentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,4-butanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl- 1,4-butanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Dimethyl-1,4-butanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,4-butanediamino) bis {dimethylmethylene (bismethylcyclo) Pentadienyl) zirconium chloride}, (μ-
N, N'-dimethyl-1,4-butanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Dimethyl-1,4-butanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,4-butanediamino) bis {ethylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N, N′-dimethyl-1,4-butanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1, 4-butanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Dimethyl-1,4-butanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,4
-Butanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,4-butanediamino) bis {(bisindenyl) zirconium chloride}, (μ- N, N′-dimethyl-1,4-butanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-
1,4-butanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,4-butanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-diethyl-1,4-butanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-
1,4-butanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-N,
N'-diethyl-1,4-butanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,4-butanediamino) bis {ethylene (biscyclo Pentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,4-butanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl- 1,4-butanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diethyl-1,4-butanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,4-butanediamino) bis {dimethylmethylene (bismethylcyclo) Pentadienyl) zirconium chloride}, (μ-
N, N'-diethyl-1,4-butanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diethyl-1,4-butanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,4-butanediamino) bis {ethylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N, N′-diethyl-1,4-butanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1, 4-butanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diethyl-1,4-butanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,4
-Butanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,4-butanediamino) bis {(bisindenyl) zirconium chloride}, (μ- N, N′-diethyl-1,4-butanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-
1,4-butanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,4-butanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-diisopropyl-1,4
-Butanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -N, N'-diisopropyl-1,4-butanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diisopropyl-1,4-butanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {methylene (bismethylcyclopentadienyl) ) Zirconium chloride}, (μ-N,
N'-diisopropyl-1,4-butanediamino) bis {methylene (bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,4- Butanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diisopropyl-1,4-butanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-
N, N'-diisopropyl-1,4-butanediamino)
Bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-
1,4-butanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diisopropyl-1,4-butanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N ′
-Diisopropyl-1,4-butanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-
1,4-butanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {dimethylsilylene (bistetramethylcyclopenta Dienyl) zirconium chloride},
(Μ-N, N′-diisopropyl-1,4-butanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {dimethylsilylene (bisindenyl) Zirconium chloride}, (μ-N, N′-diisopropyl-1,4-butanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-
N, N'-diisopropyl-1,4-butanediamino)
Bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N′-diphenyl-1,4-butanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) Bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N′-diphenyl-1,4-butanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,
4-butanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,4-butanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4
-Butanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diphenyl-1,4-butanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-
Butanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4- Butanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,4-butanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,
4-butanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) ) Zirconium chloride}, (μ
-N, N'-diphenyl-1,4-butanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-diphenyl-1,4-butanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,4-butanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-1,4-butanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride} ,

(Μ-N, N'-dimethyl-1,6-hexanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-
1,6-hexanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N′-dimethyl-1,6-hexanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6
-Hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,6-hexanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6-
Hexanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-dimethyl-1,6-hexanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6-hexanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,6-hexanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, ( μ-N, N′-dimethyl-1,6-hexanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-dimethyl-1,6-hexanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6- Hexanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-dimethyl-1,6-hexanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6
-Hexanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-dimethyl-1,6-hexanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) Zirconium chloride}, (μ
-N, N'-dimethyl-1,6-hexanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-dimethyl-1,6-hexanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,
6-hexanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-dimethyl-1,6-hexanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diethyl-1,6-hexanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-
1,6-hexanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ-
N, N'-diethyl-1,6-hexanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,6
-Hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-diethyl-1,6-hexanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,6-
Hexanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride},
(Μ-N, N′-diethyl-1,6-hexanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,6-hexanediamino) bis {Dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,6-hexanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, ( μ-N, N′-diethyl-1,6-hexanediamino) bis {ethylene (biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diethyl-1,6-hexanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,6- Hexanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N,
N′-diethyl-1,6-hexanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diethyl-1,6
-Hexanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diethyl-1,6-hexanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) Zirconium chloride}, (μ
-N, N'-diethyl-1,6-hexanediamino) bis {(bisindenyl) zirconium chloride},
(Μ-N, N′-diethyl-1,6-hexanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,
6-hexanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diethyl-1,6-hexanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diisopropyl-1,6
-Hexanediamino) bis {(biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ -N, N'-diisopropyl-1,6-hexanediamino) bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N '
-Diisopropyl-1,6-hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N'-diisopropyl-1,
6-hexanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diisopropyl-1,6-hexanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-
Diisopropyl-1,6-hexanediamino) bis {dimethylmethylene (biscyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-
1,6-hexanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-
Hexanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride} , (Μ-N, N′-diisopropyl-1,6-hexanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,
6-hexanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {dimethylsilylene (biscyclopentadienyl) zirconium Chloride}, (μ-N,
N′-diisopropyl-1,6-hexanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {dimethylsilylene ( Bistetramethylcyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-
Diisopropyl-1,6-hexanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-N, N′-diisopropyl-1,6-hexanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ- N, N'-diisopropyl-1,6-hexanediamino) bis {dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium chloride},

(Μ-N, N'-diphenyl-1,6-hexanediamino) bis {(biscyclopentadienyl)
Zirconium chloride}, (μ-N, N′-diphenyl-1,6-hexanediamino) bis {(bismethylcyclopentadienyl) zirconium chloride}, (μ
-N, N'-diphenyl-1,6-hexanediamino)
Bis {(bispentamethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,6-hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-
N, N′-diphenyl-1,6-hexanediamino) bis {methylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,6-hexanediamino) bis {methylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,6-hexanediamino) bis {dimethylmethylene (biscyclopentadienyl) ) Zirconium chloride}, (μ-N, N ′
-Diphenyl-1,6-hexanediamino) bis {dimethylmethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diphenyl-
1,6-hexanediamino) bis {dimethylmethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,6
-Hexanediamino) bis {ethylene (biscyclopentadienyl) zirconium chloride}, (μ-N,
N′-diphenyl-1,6-hexanediamino) bis {ethylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,6-hexanediamino) bis {ethylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,6-hexanediamino) bis {dimethylsilylene (biscyclopentadienyl) ) Zirconium chloride}, (μ-N, N ′
-Diphenyl-1,6-hexanediamino) bis {dimethylsilylene (bismethylcyclopentadienyl) zirconium chloride}, (μ-N, N'-diphenyl-
1,6-hexanediamino) bis {dimethylsilylene (bistetramethylcyclopentadienyl) zirconium chloride}, (μ-N, N′-diphenyl-1,6
-Hexanediamino) bis {(bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-
1,6-hexanediamino) bis {dimethylsilylene (bisindenyl) zirconium chloride}, (μ-
N, N′-diphenyl-1,6-hexanediamino) bis {ethylene (bisindenyl) zirconium chloride}, (μ-N, N′-diphenyl-1,6-hexanediamino) bis {dimethylmethylene (cyclopentadienyl) ) (Fluorenyl) zirconium chloride} and the like.

Further, the compounds in which zirconium is changed to titanium or hafnium in the above specific examples can be similarly exemplified. Further, compounds having chloride changed to bromide, methyl, ethyl, benzyl and the like can be similarly exemplified.

(2) Organoaluminum Compound The compound (A) used in the present invention includes (A1)
General formula, E¹ _aAlZ _3-aOrganoaluminum indicated by
Compound, (A2) general formula {-Al (E^Two) -O-｝_bso
A cyclic aluminoxane having the structure shown, and (A
3) General formula E ^Three｛-Al (E^Three) -O-}_cAlE^Three _Twoso
A linear aluminoxane having the structure shown (provided that E
¹, E^Two, E^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms,
All E ¹, All E^TwoAnd all E^ThreeIs the same
Or different. Z represents hydrogen or halogen
However, all Z may be the same or different. a
Is a number from 0 to 3, and b and c represent an integer of 1 or more. )
Or a mixture of two or three of them
It is.

Specific examples of the organoaluminum compound (A1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum. Dialkyl aluminum chloride such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum chloride, etc., alkyl aluminum such as methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride, etc. Dichloride, dimethyl Mini um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

[0059] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having a structure represented by _b (A2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 E in the linear aluminoxane (A3) having the structure shown
Specific examples of ² and E ³ include alkyl groups such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl. b and c are integers of 1 or more. Preferably, E ² and E ³ are methyl groups and isobutyl groups, and b and c are 1-40.

The above aluminoxanes can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

(3) Compound Reacting with Transition Metal Compound to Form Ionic Complex In the present invention, the compound used as the compound (B) to react with transition metal compound to form an ionic complex is As long as it is capable of forming an ionic complex by reacting with the transition metal compound formed in the reaction between the transition metal compound represented by the general formula [I] and the compound (A),
Either one can be used.

Preferably, (B1) a Lewis acid capable of converting a transition metal compound into a cation to form a corresponding non-coordinating anion, (B2) a general formula Z ⁺ A ⁻ (where Z ⁺ oxidizes a transition metal. The ligand can be extracted from a cationic oxidizing agent that can be converted into a cation, or a transition metal compound formed in the reaction of the transition metal compound represented by the general formula [I] with the compound (A). Is a cation and A ^- is the corresponding non-coordinating anion.)
Or a compound represented by the formula (B3) general formula (L-H)
⁺ A ⁻ (where L is a neutral Lewis base and (L−H)
⁺ Is a Bronsted acid, can make the transition metal a cation, and A ⁻ is the corresponding non-coordinating anion. ). More preferably, (B1), (B2) and (B3) are each a boron compound.

The Lewis acid (B1) is more preferably a boron compound represented by the general formula BQ ¹ Q ² Q ³ . However, B is boron in a trivalent valence state, and Q
^{1 to} Q ³ are halogen, a hydrocarbon group containing 1 to 20 carbons, a halogenated hydrocarbon group containing 1 to 20 carbons, 1
To a silyl group containing 20 carbons, an alkoxy group containing 1 to 20 carbons, and an amino group containing 1 to 20 carbons, which may be the same or different.

Specific examples of the Lewis acid (B1) include tris (pentafluorophenyl) borane and tris (2,2).
3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

The above general formula Z⁺A^-Compound represented by
(B2) is more preferably the general formula Z⁺(BQ¹Q
^TwoQ^ThreeQ^Four)^-Is a boron compound represented by. However, B
Is boron in a trivalent state, Q¹~ Q^FourIs above
Q in Lewis acid (B1) ¹~ Q^ThreeIs the same as

As specific examples of the compound represented by the general formula Z ⁺ (BQ ₁ Q ₂ Q ₃ Q ₄ ) ^- , a cationic oxidant Z ⁺ includes a ferrocenium cation and an alkyl-substituted ferrocenium. Cations, silver cations, etc. are represented by the general formula [I]
Examples of Z ⁺ , which is a cation capable of extracting a ligand from the transition metal compound formed in the reaction of the transition metal compound represented by and the compound (A), include a triphenylmethyl cation. Noncoordinating is anion _{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,
5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl)
Examples thereof include borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate and tetrakis (3,5-bistrifluoromethylphenyl) borate.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, but most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

[0068] Further, the above-mentioned general formula (L-H) ⁺ A ^- in the compound represented by (B3) is more preferably the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - Is a boron compound represented by. However, B is boron in a trivalent valence state, and Q ^{1 to} Q ⁴ are Q in the above Lewis acid (B1).
Is the same as that of the ¹ ~Q ^3.

General formula (L-H) ⁺ (BQ ₁ Q ₂ Q ₃ Q ₄ )
Specific examples of the compound represented by ⁻ include (L-H) ⁺ which is a Bronsted acid, such as trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium. Examples of (BQ ₁ Q ₂ Q ₃ Q ₄ ) ^- , which is a non-coordinating anion, include the same ones as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal) Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5
-Bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl)
Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (normal butyl) ammonium tetrakis (pentane) Fluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the present invention, the transition metal complex represented by the general formula [I] and the compound (A), or further the compound (B) can be added in any order during the polymerization and used. A reaction product obtained by previously contacting a combination of any of those compounds may be used.

The amount of each catalyst component used is such that the compound (A) / transition metal complex molar ratio is 0.1 to 10000, preferably 5 to 2000, and the compound (B) / transition metal complex molar ratio is 0. It is desirable to use each component so that it is in the range of 01 to 100, preferably 0.5 to 10. Regarding the concentration when each catalyst component is used in a solution state, the transition metal complex represented by the general formula [I] is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. Compound (A) is converted into Al atom,
0.01-500 mmol / l, preferably
0.1 to 100 mmol / liter, compound (B) is
0.0001 to 5 mmol / liter, preferably
It is desirable to use each component so that it is in the range of 0.001 to 1 mmol / liter.

In the present invention, as the monomer used for polymerization, any of olefins having 2 to 20 carbon atoms, diolefins and the like can be used, and two or more kinds of monomers can be used at the same time. Specific examples of these include ethylene, propylene, butene-1, pentene-
1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 4-methylpentene-1, vinylcyclohexane and the like are exemplified, but the present invention is not limited to the above compounds. Absent. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, propylene and butene-1, and the like. The present invention should not be limited to the above compounds.

The polymerization method is also not particularly limited, but for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, methylene dichloride and the like. Solvent polymerization using a halogenated hydrocarbon as a solvent, slurry polymerization, vapor phase polymerization in a gaseous monomer or the like is possible, and either continuous polymerization or batch polymerization is possible.

The polymerization temperature may be in the range of -50 ° C to 200 ° C, but is particularly preferably in the range of -20 ° C to 100 ° C, and the polymerization pressure is preferably atmospheric pressure to 60 kg / cm ² G. Generally, the polymerization time is appropriately determined depending on the kind of the desired polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0076]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The properties of the polymers in the examples were measured by the following methods.

(1) MFR: inner diameter 2.095 ± 0.00
Amount of resin per 10 minutes (g /
10 min).

(2) MFRR: Resin load and 2.160 when the load in the above MFR measurement was 21.60 kg.
It was expressed as the ratio of the resin outflow amount in kg. That is, MFR
R = (outflow amount at a load of 21.60 kg) / (load 2.
The flow rate at 160 kg).

(3) α-Olefin content: Determined from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (IR-810 manufactured by JASCO Corporation), and 1000
Expressed as the number of short chain branches (SCB) per carbon.

Example 1 (1) Preparation of (μ-1,6-hexanedioxo) {bis (biscyclopentadienyl) zirconium chloride} / toluene solution Under a nitrogen atmosphere, a 100 ml four-necked flask equipped with a stirrer. Among them, 1,6-hexanediol (196 mg, 1.66)
mmol) was added to the toluene 20ml, to there, ⁿ Bu
Hexane solution of Li (concentration 1.62 mol / l) 2.0
5 ml ( ⁿ BuLi 3.32 mmol) was added dropwise at 5 ° C., and the mixture was stirred for 1 hour. Furthermore, it stirred at 50 degreeC for 1 hour, and obtained the cloudy solution. Subsequently, 969 mg of biscyclopentadienyl zirconium dichloride (3.32 mmo
l) was dissolved in 100 ml of toluene, and the solution was added at 5 ° C for 3
It was slowly added over 0 minutes and stirred for 1 hour to obtain a dark reddish brown solution. Further, the mixture was stirred at room temperature for 1 hour to obtain an orange-brown solution, which had a Zr concentration of 0.0272 mmol / ml and had the following structural formula: (μ-1,6-hexanedioxo) {bis (biscyclopentadienyl) Zirconium chloride} in toluene solution.

Embedded image

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and then a toluene solution of (μ-1,6-hexanedioxo) {bis (biscyclopentadienyl) zirconium chloride} prepared in (1) above (Zr conversion) so,
0.75 μmol) was added. Polymerization was carried out for 30 minutes while controlling the temperature at 70 ° C. As a result of polymerization, SCB =
17.3, MFR = 0.44, MFRR = 36 ethylene-butene-1 copolymer, zirconium 1 mol
Per hour, 1.4 × 10 ⁷ g was produced per hour.

Example 2 (1) Preparation of (μ-1,2-benzenedioxo) {bis (biscyclopentadienyl) zirconium chloride} / toluene solution Under a nitrogen atmosphere, a 100 ml four-necked flask equipped with a stirrer. 1,2-benzenediol 110 mg (1.00
mmol) was added to the toluene 20ml, to there, ⁿ Bu
Li solution in hexane (concentration 1.62 mol / l) 1.2
4 ml ( ⁿ BuLi 2.00 mmol) was added dropwise at 5 ° C. over 5 minutes, and the mixture was stirred for 30 minutes. Furthermore, it stirred at room temperature for 30 minutes. Subsequently, a solution of 585 mg (2.00 mmol) of biscyclopentadienylzirconium dichloride in 58.5 ml of toluene was added at 5 ° C., and 2.5
Stir for hours and then overnight at room temperature. A light yellowish brown solution is obtained, which has a Zr concentration of 0.0251 mmol / ml and has the following structural formula (μ-1,2-benzenedioxo).
A toluene solution of {bis (biscyclopentadienyl) zirconium chloride} was prepared.

Embedded image

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and subsequently, a toluene solution of (μ-1,2-benzenedioxo) {bis (biscyclopentadienyl) zirconium chloride} prepared in (1) above (Zr conversion) so,
0.75 μmol) was added. Polymerization was carried out for 30 minutes while controlling the temperature at 70 ° C. As a result of polymerization, SCB =
18.4 zirconium was added to an ethylene-butene-1 copolymer having 18.4, MFR = 0.47 and MFRR = 42.
Per hour, 1.4 × 10 ⁷ g was produced per hour.

Example 3 (1) Preparation of (μ-N, N′-dimethyl-1,6-hexanediamino) {bis (biscyclopentadienyl) zirconium chloride} / toluene solution Under a nitrogen atmosphere, a stirrer was used. during 100ml4-necked flask equipped with, n, N'-dimethyl-1,6-hexanediamine 170mg of (1.49 mmol) was added to toluene 20 ml, to which the ⁿ BuLi hexane solution (concentration 1.62
mol / l) 1.84 ml ( ⁿ BuLi 2.98 mm
ol) was added dropwise at 5 ° C. over 5 minutes, and the mixture was stirred for 30 minutes. Furthermore, it stirred at room temperature for 30 minutes. Subsequently, 871 mg (2.98 m) of biscyclopentadienyl zirconium dichloride
(5 mol) in a solution of 87.1 ml of toluene.
Was added, and the mixture was stirred for 2.5 hours and further stirred at room temperature overnight. A light dark brown solution was obtained, which had a Zr concentration of 0.0274 m.
A toluene solution of (μ-N, N′-dimethyl-1,6-hexanediamino) {bis (biscyclopentadienyl) zirconium chloride} having the following structural formula, which is mol / ml, was used.

Embedded image

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and then (μ-N, N′-dimethyl-1,2-hexanediamino) {bis (biscyclopentadienyl) zirconium chloride} prepared in (1) above. Of toluene solution (0.75 μmol in terms of Zr) was added.
Polymerization was carried out for 30 minutes while controlling the temperature at 70 ° C.
As a result of the polymerization, SCB = 20.0, MFR = 0.32, M
An ethylene-butene-1 copolymer having FRR = 38,
Per mol of zirconium per hour 1.9 ×
10 ⁷ g was produced.

Example 4 (1) Preparation of (μ-N, N′-diisopropyl-1,2-ethanediamino) {bis (biscyclopentadienyl) zirconium chloride} / toluene solution Under a nitrogen atmosphere, stirrer N, N′-diisopropylethylenediamine 13 in a 100 ml four-necked flask provided
3 mg (0.92 mmol) was added to 20 ml of toluene, and a solution of ⁿ BuLi in hexane (concentration: 1.62) was added thereto.
mol / l) 1.14 ml ( ⁿ BuLi 1.84 mm
ol) was added dropwise at 5 ° C., and the mixture was stirred for 30 minutes. Furthermore, it stirred at room temperature for 30 minutes. Then, 538 mg of biscyclopentadienyl zirconium dichloride (1.84 mmo)
A solution prepared by dissolving 1) in 53.8 ml of toluene was added at 5 ° C., and the mixture was stirred for 1.5 hours and further at room temperature for 1.5 hours. A reddish brown solution is obtained, which has a Zr concentration of 0.0245 m.
A toluene solution of (μ-N, N′-diisopropyl-1,2-ethanediamino) {bis (biscyclopentadienyl) zirconium chloride} having the following structural formula, which is mol / ml, was used.

[Chemical 6]

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and then (μ-N, N′-diisopropyl-1,2-ethanediamino) {bis (biscyclopentadienyl) zirconium chloride} prepared in (1) above. Of toluene solution (0.75 μmol in terms of Zr) was added. Polymerization was carried out for 30 minutes while controlling the temperature at 70 ° C. As a result of the polymerization, SCB = 17.1, MFR = 0.2
9, ethylene-butene-1 copolymer with MFRR = 40, per 1 mol of zirconium, per hour,
1.9 × 10 ⁷ g was produced.

Example 5 (1) (μ-1,2-ethanedithio) {bis (biscyclo)
Ropentadienyl) zirconium chloride} / Tolue
Preparation of a nitrogen solution 100 ml four-necked flask equipped with a stirrer under nitrogen atmosphere
In the product, 74 mg of 1,2-ethanedithiol (0.79 m
mol) to 10 ml of toluene, and ⁿBuL
hexane solution of i (concentration 1.62 mol / l) 0.98
ml (ⁿBuLi 1.58 mmol) was added dropwise at 5 ° C.
And stirred for 30 minutes. Furthermore, it stirred at room temperature for 1 hour.
Then, biscyclopentadienyl zirconium dichloride
Ride 462 mg (1.58 mmol) in toluene 4
Add the solution dissolved in 6.2 ml at 5 ° C and stir for 30 minutes
And further stirred at room temperature overnight. A light tan solution is obtained,
This has a Zr concentration of 0.0276 mmol / ml,
In the structural formula, (μ-1,2-ethanedithio) {bis (bis (bis
Cyclopentadienyl) zirconium chloride}
It was a ruene solution.

Embedded image

(2) Polymerization An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and then a toluene solution of (μ-1,2-ethanedithio) {bis (biscyclopentadienyl) zirconium chloride} prepared in (1) above (in terms of Zr, 0.
75 μmol). Polymerization was carried out for 10 minutes while controlling the temperature at 70 ° C. As a result of polymerization, SCB = 2
An ethylene-butene-1 copolymer having 2.9, MFR = 0.48 and MFRR = 51 was produced at 4.7 × 10 ⁷ g per mol of zirconium per hour.

Comparative Example 1 An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the system, methylalumoxane (MMAO manufactured by Toso Akzo Co., Ltd.
1.5 mmol of type3A toluene solution), and subsequently 0.75 μmol of biscyclopentadienylzirconium dichloride was added. Polymerization was carried out for 30 minutes while controlling the temperature at 70 ° C. As a result of polymerization, S
An ethylene-butene-1 copolymer having CB = 24.2, MFR = 0.65 and MFRR = 47 was added to zirconium 1
3.4 × 10 ⁷ g was produced per mol per hour.

Example 6 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
Feeding while adjusting to / cm ² and stabilizing the inside of the system, triisobutylaluminum 0.25 mmol, prepared in Example 1 (1) above (μ-1,6-hexanedioxo) {bis (bis Cyclopentadienyl) zirconium chloride} toluene solution (Zr conversion: 0.
7 μmol), followed by 2.1 μmol of trityl tetrakis (pentafluorophenyl) borate. 7
Polymerization was carried out for 30 minutes while controlling the temperature at 0 ° C. As a result of the polymerization, SCB = 17.4, MFR = 0.063, M
An ethylene-butene-1 copolymer having FRR = 56,
2.2 × per 1 mol of zirconium
10 ⁷ g was produced.

Comparative Example 2 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then 80 g of butane was used as a solvent.
20 g of butene-1 was charged as an α-olefin, and the temperature of the reactor was raised to 70 ° C. After heating, increase the ethylene pressure to 6 kg
/ Cm ^{2 It} was fed while adjusting the inside of the system to stabilize, and then triisobutylaluminum 0.25 mmol, biscyclopentadienyl zirconium dichloride 0.
7 μmol and subsequently 2.1 μmol of trityl tetrakis (pentafluorophenyl) borate were added. 70
Polymerization was carried out for 10 minutes while adjusting the temperature to ° C. As a result of polymerization, SCB = 21.4, MFR = 1.0, MFRR
= 30, the ethylene-butene-1 copolymer is 1.1 × 10 ⁸ per 1 mol of zirconium per hour.
g produced.

[0093]

As described in detail above, according to the present invention,
Containing a complex in which two transition metal atoms coordinated by a cyclopentadienyl group are linked by a covalent bond group having an atom of groups 15 and 16 and for highly active olefin polymerization at a temperature generally used in industry A catalyst is obtained. Further, it becomes possible to obtain a high molecular weight olefin polymer by using the catalyst.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (9)

[Claims] 1. A transition metal complex represented by the following general formula [I]:
And an olefin comprising the following compound (A):
In-polymerization catalyst. Embedded image(Where M¹, M^TwoIs transition gold of Group 4 of the Periodic Table of the Elements
Represents a genus atom, which may be the same or different, Cp
¹, Cp^Two, Cp^Three, Cp^FourIs cyclopentadienyl bone
Represents a group having a case and may be the same or different.
Yes. Cp¹And Cp^Two, Cp^ThreeAnd Cp^FourAre each non-water
It may be crosslinked with a crosslinking group having 1 to 20 elementary atoms.
L¹, L^TwoIs a group 15 or 16 atom, a transition metal atom and R
Is a covalent linking group that connects
May be. R is a covalent bond group having 1 to 20 carbon atoms
is there. X¹, X^TwoIs hydrogen atom, halogen atom, carbon atom
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
Hydrocarbon group, alkoxy group having 1 to 20 carbon atoms,
Aryloxy group having 1 to 20 carbon atoms or the number of carbon atoms
2 to 20 disubstituted amino groups, which may be the same or different.
May be. ) (A) Any of the following compounds (A1) to (A3)
Or a mixture of two or three of them. (A1) General formula E¹ _aAlZ_3-aOrganic Al
Minium compound (A2) General formula {-Al (E^Two) -O-｝_bIndicated by
Structured cyclic aluminoxane (A3) General formula E^Three｛-Al (E^Three) -O-｝_cAl
E^Three _TwoA linear aluminoxane having the structure¹~ E^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms
And all E¹, All E ^TwoAnd all E^ThreeAre the same
Or they may be different. Z is a hydrogen atom or halogen
Represents an atom, all Z being the same or different
good. a is a number from 0 to 3, and b and c are integers of 1 or more.
You. ) 2. A transition metal complex according to claim 1, which has the following formula:
Oref characterized by comprising compounds (A) and (B)
In-polymerization catalyst. (A) Any of the following compounds (A1) to (A3)
Or a mixture of two or three of them. (A1) General formula E¹ _aAlZ_3-aOrganic Al
Minium compound (A2) General formula {-Al (E^Two) -O-｝_bIndicated by
Structured cyclic aluminoxane (A3) General formula E^Three｛-Al (E^Three) -O-｝_cAl
E^Three _TwoA linear aluminoxane having the structure¹~ E^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms
And all E¹, All E ^TwoAnd all E^ThreeAre the same
Or they may be different. Z is a hydrogen atom or halogen
Represents an atom, all Z being the same or different
good. a is a number from 0 to 3, and b and c are integers of 1 or more.
You. ) (B) Reacts with a transition metal compound to form an ionic complex
Compound. 3. The olefin polymerization according to claim 1 or 2, wherein L ¹ and L ² are a covalent bond group connecting a transition metal atom and R with an oxygen atom, a sulfur atom or a nitrogen atom. catalyst. 4. The catalyst for olefin polymerization according to claim 1, wherein R is a linear alkylene group having 1 to 10 carbon atoms. 5. The catalyst for olefin polymerization according to claim 1, wherein R is an arylene group. 6. The compound (A) is triethylaluminum,
The catalyst for olefin polymerization according to any one of claims 1 to 5, which is triisobutylaluminum or methylaluminoxane. 7. The catalyst for olefin polymerization according to claim 2, wherein the compound (B) is a boron compound. 8. A method for producing an olefin polymer, which comprises using the olefin polymerization catalyst according to any one of claims 1 to 7. 9. The method for producing an olefin polymer according to claim 8, wherein the olefin polymer is an ethylene-α-olefin copolymer.