JP2002293788A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal compound useful for preparation of a highly active catalyst for olefin polymerization, the highly active catalyst for the olefin polymerization and an efficient method for producing the olefin polymer. SOLUTION: This transition metal compound is represented by general formulas [I]: CpMYX<1> 2 , or [II]: (CpMYX<1> )2 X<2> (wherein, M is a group 4 transition metal atom; Cp is a group having a cyclopentadiene-type anionic skeleton; Y is a group bonded by a σ-bond to M through a group 15 or 16 atom; Cp and Y are bonded to each other directly or through a cross-linking group; X<1> is a sulfonyloxy group; and X<2> is a group 16 atom). The catalyst for the olefin polymerization is obtained by bringing (A) the transition metal compound into contact with (B) a specific aluminum compound and/or (C) a specified boron compound. The method for producing the olefin polymer uses the catalyst for the olefin polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound having a sulfonyloxy group, an olefin polymerization catalyst prepared using the compound, and a method for producing an olefin polymer using the catalyst.

[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-58-19306,
A method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported. This screw (η
^In the method for producing an olefin polymer using ⁵ -cyclopentadienyl) zirconium dichloride and methylaluminoxane, the activity was insufficient from an industrial viewpoint.

In Japanese Patent Application Laid-Open No. 9-87313, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, triisobutylaluminum and N A method for producing a copolymer of ethylene and hexene-1 using N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate has been reported, and a copolymer of high molecular weight ethylene and hexene-1 has been reported. Although it has been obtained with high activity, further improvement in activity has been desired.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, the problem to be solved by the present invention, that is, an object of the present invention, is to provide a transition metal compound and a highly active olefin useful for preparing a highly active olefin polymerization catalyst. An object of the present invention is to provide a polymerization catalyst and an efficient method for producing an olefin polymer.

[0005]

According to the present invention, there is provided a compound represented by the following general formula:
According to the transition metal compound represented by [I] or [II]
Things. The present invention also provides the transition metal compound (A)
And the following (B) and / or (C)
Olefin polymerization catalyst, and the olefin polymer
Homopolymerization or co-polymerization of olefins using a joint catalyst
Related to the production method of the olefin polymer to be combined.
You. CpMYX¹ _Two [I] (CpMYX¹)_TwoX^Two [II] (In the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table of the elements, and Cp
Represents a group having a cyclopentadiene-type anion skeleton
You. Y is a member of group 15 or 16 of the periodic table of elements.
Is a group that is σ-bonded to M via a child, and Cp and Y are directly
Alternatively, they are bonded via a cross-linking group. X¹Is sulfonyl
X represents an oxy group;^TwoIs the origin of group 16 of the periodic table of elements
Indicates a child. All Cp when there are a plurality of Cp in one molecule,
M, Y, X¹Can be the same or different
good. In addition, a plurality of Cp and a plurality of X¹Direct with each other
Alternatively, they may be bonded via a crosslinking group. (B) at least one selected from the following (B1) to (B4)
Aluminum compound (B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_Two(B4) The above-mentioned (B2) and / or the above-mentioned (B3) and water
Obtained by reacting with a compound having an acid group
Modified aluminoxane compound (provided that E¹, E^TwoAnd E^Three
Are each a hydrocarbon group and all E¹, All E ^TwoYou
And all E^ThreeMay be the same or different.
Z represents a hydrogen atom or a halogen atom, and all Z
It may be the same or different. a satisfies 0 <a ≦ 3
B is an integer of 2 or more, c is an integer of 1 or more
Represent. (C) one or more kinds selected from the following (C1) to (C3)
Boron compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino
Groups, which may be the same or different
No. G⁺Is an inorganic, organic or organometallic cation
L is a neutral Lewis base, (LH)⁺Is Bren
Sted acid. Hereinafter, the present invention will be described in more detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

In the above general formula [I] or [II],
The transition metal atom represented by M is the periodic table of the element (IU
PAC inorganic metal nomenclature, revised edition 1989), and includes transition metal atoms of Group 4, such as titanium atoms, zirconium atoms, and hafnium atoms. Preferably,
It is a titanium atom or a zirconium atom.

Cyclopentadi represented by the substituent Cp
Examples of the group having an ene-type anion skeleton include η^Five−
(Substituted) cyclopentadienyl group, η^Five-(Replace) in
Denenyl group, η^Five-(Substituted) fluorenyl group and the like.
To give a concrete example, for example, η^Five−cyclopentadiene
Group, η^Five-Methylcyclopentadienyl group, η^Five−Jimme
Tylcyclopentadienyl group, η^Five-Trimethylcyclo
Pentadienyl group, η^Five-Tetramethylcyclopentadi
Enyl group, η^Five-Ethylcyclopentadienyl group, η^Five−
n-propylcyclopentadienyl group, η^Five-Isopro
Pyrcyclopentadienyl group, η^Five-N-butylcyclo
Pentadienyl group, η^Five-Sec-butylcyclopenta
Dienyl group, η^Five-Tert-butylcyclopentadier
Nil group, η^Five-Phenylcyclopentadienyl group, η^Five−
Trimethylsilylcyclopentadienyl group, η^Five−te
rt-butyldimethylsilylcyclopentadienyl group,
η^Five-Indenyl group, η^Five-Methylindenyl group, η^Five−
Dimethylindenyl group, η^Five-N-propylindenyl
Group, η^Five-Isopropylindenyl group, η^Five-N-butyl
Indenyl group, η^Five-Tert-butylindenyl group,
η^Five-Phenylindenyl group, η ^Five-Methylphenylin
Denenyl group, η^Five-Naphthylindenyl group, η^Five-Trimethy
Lucylylindenyl group, η^Five-Tetrahydroindenyl
Group, η^FiveA fluorenyl group, η^Five-Methylfluorenyl
Group, η^Five-Dimethylfluorenyl group, η^Five-Tert-b
Tylfluorenyl group, η^Five-Di-tert-butyl full
Olenyl group, η^FiveA phenylfluorenyl group, η^Five-Ziff
Phenylfluorenyl group, η^Five-Trimethylsilylfluor
Renyl group, η^Five-Bistrimethylsilylfluorenyl group
And preferably η^Five-Cyclopentadieni
Group, η^Five-Methylcyclopentadienyl group, η^Five-N-
Butylcyclopentadienyl group, η^Five-Tert-buty
Rucyclopentadienyl group, η^Five-Tetramethylcyclo
Pentadienyl group, η^Five-Indenyl group, η^Five-Tetrahi
Droindenyl group, or η^Five-A fluorenyl group
You. In this specification, a transition metal compound name is used.
"Η^Five“-” May be omitted.

The substituent X ¹ represents a sulfonyloxy group,
Preferably, -OS (O) ₂ R (where, R is an alkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, having 1 to 10 carbon atoms,
Each may be substituted with a halogen atom. ).

The alkyl group having 1 to 10 carbon atoms for the substituent R includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-butyl and the like. Pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group,
alkyl groups such as n-decyl group; chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group,
Dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, perfluoropropyl group, Halogenated alkyl groups such as perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, Examples thereof include alkoxyalkyl groups such as a phenoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, and a phenoxyethyl group. Preferably, a methyl group, an ethyl group, an isopropyl group, rt- butyl group, a trifluoromethyl group or a methoxymethyl group.

The aryl group having 6 to 20 carbon atoms in the substituent R includes, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4- Xylyl group, 2,5-xylyl group, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Aryl groups such as octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group and anthracenyl group; 2-fluorophenyl group, 3-fluorophenyl group and 4-fluorophenyl group 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5- Fluorophenyl group, 2,6
-Difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-triphenyl group Fluorophenyl group, 2,4
6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group,
2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, perfluoroethylphenyl group, perfluoropropylphenyl group, perfluorobutylphenyl group, fluoronaphthyl group, fluoroanthracenyl A haloaryl group in which a fluorine atom is arbitrarily changed to a chlorine atom or a bromine atom; in the haloaryl group, a halogen atom is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, An alkoxyaryl group changed to an n-butoxy group, a sec-butoxy group, or a tert-butoxy group; a cyanoaryl group, a nitroaryl group and the like are preferable, and a phenyl group is preferable.

Examples of the aralkyl group having 7 to 20 carbon atoms in the substituent R include benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4
-Dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6 -Trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group,
(2,4,6-trimethylphenyl) methyl group, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
(N-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, and these are a fluorine atom, a chlorine atom,
A haloaralkyl group substituted with a halogen atom such as a bromine atom; in the haloaralkyl group, a halogen atom is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, or a tert- An alkoxyaralkyl group converted to a butoxy group; a cyanoaralkyl group, a nitroaralkyl group and the like, and a benzyl group is preferable.

The substituent R is preferably an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom, and more preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom. It is an alkyl group, particularly preferably a methyl group or a trifluoromethyl group.

X ² in the general formula [II] represents an atom belonging to Group 16 of the periodic table of the elements, and specific examples thereof include an oxygen atom, a sulfur atom, and a selenium atom. It is a sulfur atom, and more preferably an oxygen atom.

In the general formula [I] or [II], Y
Is a group σ-bonded to M via an atom of Group 15 or Group 16 of the periodic table of the elements, preferably Y is a group σ-bonded to M via a nitrogen atom or an oxygen atom; More preferably, Y is an amino group, an alkoxy group or an aryloxy group.

The amino group in Y is an amino group substituted with one or two hydrocarbon groups or a silyl group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, Carbon atoms such as alkyl groups having 1 to 10 carbon atoms such as isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and phenyl group Examples thereof include an aralkyl group having 7 to 10 carbon atoms such as an aryl group having 6 to 10 atoms and a benzyl group. Examples of the silyl group include a trimethylsilyl group and tert.
-Butyldimethylsilyl group and the like. Such amino groups include, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n
-Butylamino group, sec-butylamino group, tert
-Butylamino group, isobutylamino group, n-hexylamino group, n-octylamino group, phenylamino group,
Examples include a trimethylsilylamino group and a tert-butyldimethylsilylamino group, and preferably a methylamino group, an ethylamino group, an isopropylamino group,
t-butylamino group, trimethylsilylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butyl Amino group, diisobutylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bis (trimethylsilyl) amino group, bis (t
tert-butyldimethylsilyl) amino group and the like, preferably a methylamino group, an ethylamino group, an isopropylamino group, a tert-butylamino group, or a trimethylsilylamino group.

The alkoxy group in Y is preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and preferably methoxy group, ethoxy group, isopropoxy group or tert-butoxy group.

The aryloxy group for Y is preferably an aryloxy group having 6 to 20 carbon atoms, for example, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group,
2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl- 4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5
-A trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group,
2,4,6-trimethylphenoxy group, 2-tert-
Butyl-3,4-dimethylphenoxy group, 2-tert
-Butyl-3,5-dimethylphenoxy group, 2-ter
t-butyl-3,6-dimethylphenoxy group, 2,6-
Di-tert-butyl-3-methylphenoxy group, 2-
tert-butyl-4,5-dimethylphenoxy group,
2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3
4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3
4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-
Di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-
tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group Group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-
Examples include a tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group.

In the general formulas [I] and [II], Cp and Y are bonded directly or via a crosslinking group. As the crosslinking group, periodic table of elements (IUPA)
C inorganic chemical nomenclature, revised edition 1989), a divalent cross-linking group containing an atom belonging to Group 14 and the like, and preferably a divalent cross-linking group containing a carbon atom or a silicon atom. More preferably, the atom bonded to Cp or Y is a carbon atom and / or
Or a divalent bridging group which is a silicon atom, and more preferably, the atom bonded to Cp or Y is a carbon atom and / or
Or a divalent bridging group which is a silicon atom and has a minimum number of atoms of 3 or less between atoms bonding to Cp or Y (for example, Cp or Y
Includes the case where the atom bonding to is single. ). More specifically, methylene, ethylene, propylene, dimethylmethylene (isopropylidene), diphenylmethylene, tetramethylethylene, silylene, dimethylsilylene, diethylsilylene, diphenylsilylene, tetramethyldiethylene Examples thereof include a silylene group and a dimethoxysilylene group, and particularly preferred are a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group, and a diphenylsilylene group.

As such transition metal compounds, for example, specific examples of the transition metal compound represented by the general formula [I] include dimethylsilylene (methylamino) (η ⁵ -cyclopentadienyl) titanium bis (trifluoromethanesulfonate) dimethylsilylene (tert- butylamino) (eta ⁵ - cyclopentadienyl) titanium bis (trifluoromethanesulfonate), dimethylsilylene (phenylamino) (eta ⁵ - cyclopentadienyl) titanium bis (trifluoromethanesulfonate), dimethylsilylene (Cyclohexylamino) (η
Such as ⁵ -cyclopentadienyl) titanium bis (trifluoromethanesulfonate) and η of these compounds.
⁵ -cyclopentadienyl by η ⁵ -methylcyclopentadienyl, η ⁵ -tetramethylcyclopentadienyl, η ⁵
- ethylcyclopentadienyl, eta ^{5-n-butylcyclopentadienyl,} eta ^{5-tert-butylcyclopentadienyl,} eta ⁵ - di-tert-butylcyclopentadienyl, eta ⁵ - trimethylsilylcyclopentadienyl , eta ^{5-tert-butyldimethylsilyl-cyclopentadienyl,} eta ⁵ - phenyl-cyclopentadienyl, eta ⁵
- indenyl, eta ⁵ - methylindenyl, eta ⁵ - phenyl indenyl or eta ⁵ - compound change fluorenyl, dimethylsilylene diethyl silylene, diphenyl silylene, methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, tetra A compound in which methylethylene or tetramethyldisilylene is changed, a compound in which titanium is changed to zirconium or hafnium, bis (trifluoromethanesulfonate) is dimethanesulfonate, dibenzenesulfonate, bis (perfluoroethanesulfonate), diethanesulfonate, Dipropane sulfonate, bis (4-
Transition metal compounds such as compounds converted to toluenesulfonate) or bis (perfluorobenzenesulfonate) are included.

As the transition metal compound represented by the general formula [II], μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (tert-butylamino) titanium trifluoromethanesulfonate}, μ-oxobis {dimethylsilylene ( eta ⁵ - cyclopentadienyl) (tert-butylamino) titanium trifluoromethanesulfonate}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl)
(Tert-butylamino) titanium trifluoromethanesulfonate and the like, and compounds obtained by changing titanium of these compounds to zirconium or hafnium;
η ⁵ -cyclopentadienyl is converted to η ⁵ -ethylcyclopentadienyl, η ⁵ -n-butylcyclopentadienyl, η ⁵
-Tert-butylcyclopentadienyl, η ⁵ -di-
tert- butyl cyclopentadienyl, eta ⁵ - trimethylsilyl cyclopentadienyl, eta ^{5-tert-butyldimethylsilyl-cyclopentadienyl,} eta ⁵ - phenyl-cyclopentadienyl, eta ⁵ - indenyl, eta ⁵ - methylindenyl , Η ⁵ -phenylindenyl or η ^5-
Transition metal compounds, such as a compound in which fluorenyl is changed to, a compound in which trifluoromethanesulfonate is changed to methanesulfonate, benzenesulfonate, perfluoroethanesulfonate, ethanesulfonate, propanesulfonate, 4-toluenesulfonate, or perfluorobenzenesulfonate, are exemplified.

The transition metal compound used in the present invention is more preferably a transition metal compound represented by the following general formula [III] or [IV]. (In the above general formula [III] or [IV],
M represents a transition metal atom of Group 4 of the periodic table of the element;
Represents an atom belonging to Group 16 of the periodic table of the element, and J represents an atom belonging to Group 14 of the periodic table of the element. Cp represents a group having a cyclopentadiene-type anion skeleton. R ¹ , R ² , R
³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group,
Substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, alkylseleno group,
It represents an aralkylseleno group or an arylseleno group.
X ¹ represents a sulfonyloxy group, and X ² represents an atom belonging to Group 16 of the periodic table of the elements. R ¹ , R ² , R ³ , R ⁴ , R ⁵
And R ⁶ may be arbitrarily combined to form a ring. All M, A, J, Cp, X when there are a plurality of in one molecule
¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different. )

M, Cp, X ¹ and X ² in the general formula [III] or [IV] are each represented by the general formula [I]
Or similar to those in [II]. R ¹ , R ² , R ³ , R ⁴ , R ^{5 in the} above general formula [III] or [IV]
Examples of the halogen atom for R ⁶ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Preferably it is a chlorine atom or a bromine atom, more preferably a chlorine atom.

The alkyl group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula [III] or [IV] is preferably an alkyl group having 1 to 20 carbon atoms. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, ter
t-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. And a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, or an amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, a perbromopropyl group, and the like. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an aralkyl group having 7 to 20 carbon atoms. Benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl Group,
(2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4 -Trimethylphenyl) methyl group,
(2,3,5-trimethylphenyl) methyl group, (2
3,6-trimethylphenyl) methyl group, (3,4,5
-Trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl Group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl)
Methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) Methyl group, (n-pentylphenyl) methyl group,
(Neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracene A benzyl group; and more preferably a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula [III] or [IV] is preferably an aryl group having 6 to 20 carbon atoms. Phenyl group, 2-tolyl group, 3-tolyl group,
4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4
-Xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-
Trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,
3,4,6-tetramethylphenyl group, 2,3,5,6
A tetramethylphenyl group, a pentamethylphenyl group,
Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like, and more preferably a phenyl group. All of these aryl groups are a fluorine atom, a chlorine atom, a bromine atom,
It may be partially substituted with a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituted silyl group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula [III] or [IV] is a silyl group substituted with a hydrocarbon group, Here, as the hydrocarbon group, for example, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, sec
-Butyl group, tert-butyl group, isobutyl group, n-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. 1 to 20 carbon atoms
Examples of the substituted silyl group include those having 1 to 2 carbon atoms such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group.
0-substituted silyl group having 2 to 20 carbon atoms such as mono-substituted silyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl Group, tri-n-butylsilyl group, tri-sec-
Carbon such as butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group and triphenylsilyl group; Examples include a trisubstituted silyl group having 3 to 20 atoms, preferably a trimethylsilyl group, te
It is an rt-butyldimethylsilyl group or a triphenylsilyl group. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an alkoxy group having 1 to 20 carbon atoms. Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n- Examples include a dodeoxy group, an n-pentadesoxy group, an n-icosoxy group, and more preferably a methoxy group, an ethoxy group, an isopropoxy group, or a tert- group.
Butoxy group. All of these alkoxy groups are
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The aralkyloxy group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula [III] or [IV] is preferably an aralkyloxy group having 7 to 20 carbon atoms. For example, benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,
3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy Group,
(3,5-dimethylphenyl) methoxy group, (2,3
4-trimethylphenyl) methoxy group, (2,3,5-
(Trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4 (5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetra (Methylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (se
(c-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-
(Decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like, and more preferably benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aryloxy group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an aryloxy group having 6 to 20 carbon atoms. For example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,
6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-
Butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-
5-methylphenoxy group, 2-tert-butyl-6-
Methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3
6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group,
2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert- Butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2, 3,4,5-tetramethylphenoxy group, 2-
tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-
tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl -3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5
-Dimethylphenoxy group, pentamethylphenoxy group,
Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, s
ec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. All of these aryloxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The disubstituted amino group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is substituted with two hydrocarbon groups or silyl groups. An amino group, wherein the hydrocarbon group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl An alkyl group having 1 to 10 carbon atoms such as a group, an n-hexyl group or a cyclohexyl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group. Examples of the silyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of such a disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, and a di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, and a bistrimethylsilylamino group. Each of these disubstituted amino groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyl group such as a benzyloxy group. Part may be substituted with an oxy group or the like.

The alkylthio group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an alkylthio group having 1 to 20 carbon atoms. Methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group,
n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like, more preferably methylthio group, ethylthio group, It is an isopropylthio group or a tert-butylthio group. All of these alkylthio groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkylthio group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula [III] or [IV] is preferably an aralkylthio group having 7 to 20 carbon atoms. For example, benzylthio, (2-methylphenyl) methylthio, (3-methylphenyl) methylthio, (4-methylphenyl) methylthio, (2,
3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio Group, (3,5-dimethylphenyl) methylthio group,
(2,3,4-trimethylphenyl) methylthio group,
(2,3,5-trimethylphenyl) methylthio group,
A (2,3,6-trimethylphenyl) methylthio group,
(2,4,5-trimethylphenyl) methylthio group,
A (2,4,6-trimethylphenyl) methylthio group,
(3,4,5-trimethylphenyl) methylthio group,
(2,3,4,5-tetramethylphenyl) methylthio, (2,3,4,6-tetramethylphenyl) methylthio, (2,3,5,6-tetramethylphenyl) methylthio, (penta Methylphenyl) methylthio group,
(Ethylphenyl) methylthio group, (n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (se
c-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl)
Examples include a methylthio group, a (n-octylphenyl) methylthio group, a (n-decylphenyl) methylthio group, a naphthylmethylthio group, an anthracenylmethylthio group, and more preferably a benzylthio group. All of these aralkylthio groups are a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group,
It may be partially substituted with an alkoxy group such as an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The arylthio group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an arylthio group having 6 to 20 carbon atoms. Phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2,3-dimethylphenylthio, 2,4-
Dimethylphenylthio, 2,5-dimethylphenylthio, 2,6-dimethylphenylthio, 3,4-dimethylphenylthio, 3,5-dimethylphenylthio, 2-tert-butyl-3-methyl Phenylthio group, 2-tert-butyl-4-methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethyl Phenylthio group, 2,3
5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-t
tert-butyl-3,4-dimethylphenylthio group, 2
-Tert-butyl-3,5-dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert- Butyl-4,5-dimethylphenylthio group, 2,6-di-tert-butyl-4
-Methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl-3,4,5-trimethylphenylthio group, 2, 3,4,6-tetramethylphenylthio group, 2-tert-butyl-3,4,6-trimethylphenylthio group, 2,6-di-tert-butyl-
3,4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2-tert-butyl-
3,5,6-trimethylphenylthio group, 2,6-di-
tert-butyl-3,5-dimethylphenylthio group,
Pentamethylphenylthio group, ethylphenylthio group,
n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec-butylphenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group,
Examples include an n-decylphenylthio group, an n-tetradecylphenylthio group, a naphthylthio group, an anthracenylthio group, and the like. All of these arylthio groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The alkylseleno group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula [III] or [IV] is preferably an alkylseleno group having 1 to 20 carbon atoms. For example, methylseleno group, ethylseleno group, n-propylseleno group, isopropylseleno group, n
-Butylseleno group, sec-butylseleno group, tert
-Butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group, and the like. Preferred are a methylseleno group, an ethylseleno group, an isopropylseleno group, and a tert-butylseleno group. All of these alkylseleno groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aralkylseleno group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula [III] or [IV] is preferably an aralkylseleno group having 7 to 20 carbon atoms. For example, benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group, (2,3-dimethylphenyl) methylseleno group, (2,4-dimethyl A phenyl) methylseleno group,
A (2,5-dimethylphenyl) methylseleno group, (2,5-
(6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5- (Trimethylphenyl) methylseleno group, (2,3,6-trimethylphenyl) methylseleno group, (2,4,5-trimethylphenyl) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4 (5-trimethylphenyl) methylseleno group, (2,3,4,5-tetramethylphenyl) methylseleno group, (2,3,4,6-
Tetramethylphenyl) methylseleno group, (2,3,
5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group,
(N-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (n-hexylphenyl) methylseleno group, (n-octylphenyl) methylseleno group, (n-decylphenyl) A) a methylseleno group, a naphthylmethylseleno group, an anthracenylmethylseleno group and the like, and more preferably a benzylseleno group. All of these aralkyl seleno groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The arylseleno group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula [III] or [IV] is preferably an arylseleno group having 6 to 20 carbon atoms. For example, phenylseleno, 2-methylphenylseleno, 3-methylphenylseleno, 4-methylphenylseleno, 2,3-dimethylphenylseleno, 2,4-dimethylphenylseleno, 2,5-dimethyl Phenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-
Dimethylphenylseleno group, 2-tert-butyl-3
-Methylphenylseleno group, 2-tert-butyl-4
-Methylphenylseleno group, 2-tert-butyl-5
-Methylphenylseleno group, 2-tert-butyl-6
-Methylphenylseleno group, 2,3,4-trimethylphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,
4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2-tert-butyl-
3,4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-ter
t-butyl-3,6-dimethylphenylseleno group, 2,
6-di-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4 2,5-trimethylphenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenyl Seleno group, 2-tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group, 2,3,5
6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6-trimethylphenylseleno group, 2,
6-di-tert-butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butyl Phenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno group,
Examples thereof include an n-octylphenylseleno group, an n-decylphenylseleno group, an n-tetradecylphenylseleno group, a naphthylseleno group, and an anthracenylseleno group.
All of these arylseleno groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group,
An aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group, wherein R ¹ is an alkyl group, an aralkyl group,
An aryl group or a substituted silyl group is particularly preferred.

R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

In the general formula [III] or [IV], A
Examples of the atoms of Group 16 of the periodic table of the element represented by include an oxygen atom, a sulfur atom, and a selenium atom. Preferably, it is an oxygen atom.

In the general formula [III] or [IV], J
Examples of the atoms belonging to Group 14 of the periodic table of the element represented by include a carbon atom, a silicon atom, and a germanium atom. Preferably, it is a carbon atom or a silicon atom.

The transition metal compound represented by the general formula [III]
As a specific example of methylene (η^Five-Cyclopentadie
Nyl) (3,5-dimethyl-2-phenoxy) titanium
Mbis (trifluoromethanesulfonate), methylene
(Η^Five-Cyclopentadienyl) (3-tert-butyl)
Ru-2-phenoxy) titanium bis (trifluorome
Tansulfonate), methylene (η^Five-Cyclopentadi
Enyl) (3-tert-butyl-5-methyl-2-f
Enoxy) titanium bis (trifluoromethanesulfo
Nate), methylene (η^Five-Cyclopentadienyl)
(3-phenyl-2-phenoxy) titanium bis (g
Trifluoromethanesulfonate), methylene (η^Five−
Clopentadienyl) (3-tert-butyldimethyl
Silyl-5-methyl-2-phenoxy) titanium bis
(Trifluoromethanesulfonate), methylene (η^Five
-Cyclopentadienyl) (3-trimethylsilyl-5
-Methyl-2-phenoxy) titanium bis (trifur
Oromethane sulfonate), methylene (η^Five-Cyclope
Antadienyl) (3-tert-butyl-5-methoxy
-2-phenoxy) titanium bis (trifluorometa)
Sulfonate), methylene (η^Five-Cyclopentadie
Nyl) (3-tert-butyl-5-chloro-2-fe
Nonoxy) titanium bis (trifluoromethanesulfone)
), Methylene (η^Five-Tetramethylcyclopentadi
Enyl) (3,5-dimethyl-2-phenoxy) titani
Umbis (trifluoromethanesulfonate), methyle
(Η^Five-Tetramethylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium bis
(Trifluoromethanesulfonate), methylene (η^Five
-Tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titaniumbi
(Trifluoromethanesulfonate), methylene (η
^Five-Tetramethylcyclopentadienyl) (3-phenyl)
Ru-2-phenoxy) titanium bis (trifluorome
Tansulfonate), methylene (η^Five-Tetramethylsi
Clopentadienyl) (3-tert-butyldimethyl
Silyl-5-methyl-2-phenoxy) titanium bis
(Trifluoromethanesulfonate), methylene (η^Five
-Tetramethylcyclopentadienyl) (3-trimethyl
Lucylyl-5-methyl-2-phenoxy) titanium bi
(Trifluoromethanesulfonate), methylene (η
^Five-Tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium
Mbis (trifluoromethanesulfonate), methylene
(Η^Five-Tetramethylcyclopentadienyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titani
Umbis (trifluoromethanesulfonate),

Isopropylidene (η^Five-Cyclopentadi
Enyl) (3,5-dimethyl-2-phenoxy) titani
Umbis (trifluoromethanesulfonate), isop
Lopiriden (η^Five-Cyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium bis (tri
Fluoromethanesulfonate), isopropylidene (η
^Five-Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium bis (trif
Fluoromethanesulfonate), isopropylidene (η^Five
-Cyclopentadienyl) (3-phenyl-2-pheno
Xy) titanium bis (trifluoromethanesulfone)
G), isopropylidene (η^Five-Cyclopentadieni
) (3-tert-butyldimethylsilyl-5-methyl)
Ru-2-phenoxy) titanium bis (trifluorome
Tansulfonate), isopropylidene (η^Five-Cyclo
Pentadienyl) (3-trimethylsilyl-5-methyl
-2-phenoxy) titanium bis (trifluorometa)
Sulfonic acid), isopropylidene (η^Five-Cyclope
Antadienyl) (3-tert-butyl-5-methoxy
-2-phenoxy) titanium bis (trifluorometa)
Sulfonic acid), isopropylidene (η^Five-Cyclope
Antadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium bis (trifluoromethane
Sulfonate), isopropylidene (η^Five-Tetramethyi
Rucyclopentadienyl) (3,5-dimethyl-2-f
Enoxy) titanium bis (trifluoromethanesulfo
), Isopropylidene (η^Five-Tetramethylsic
Lopentadienyl) (3-tert-butyl-2-fe
Nonoxy) titanium bis (trifluoromethanesulfone)
Isopropylidene (η^Five-Tetramethylcyclo
Pentadienyl) (3-tert-butyl-5-methyl
-2-phenoxy) titanium bis (trifluorometa)
Sulfonic acid), isopropylidene (η^Five-Tetrame
Tylcyclopentadienyl) (3-phenyl-2-fe
Nonoxy) titanium bis (trifluoromethanesulfone)
Isopropylidene (η^Five-Tetramethylcyclo
Pentadienyl) (3-tert-butyldimethylsilyl
Ru-5-methyl-2-phenoxy) titanium bis (g
Trifluoromethanesulfonate), isopropylidene
(Η^Five-Tetramethylcyclopentadienyl) (3-t
Limethylsilyl-5-methyl-2-phenoxy) titani
Umbis (trifluoromethanesulfonate), isop
Lopiriden (η^Five-Tetramethylcyclopentadienyl
) (3-tert-butyl-5-methoxy-2-fe)
Nonoxy) titanium bis (trifluoromethanesulfone)
Isopropylidene (η^Five-Tetramethylcyclo
Pentadienyl) (3-tert-butyl-5-chloro
-2-phenoxy) titanium bis (trifluorometa)
Sulfonate),

[0044] diphenylmethylene (eta ⁵ - cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-phenyl -
2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (Η ⁵ -cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3
-Tert-butyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium bis (trifluoromethanesulfonate) , diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η
⁵ -tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium bis (trifluoromethanesulfonate), diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium bis (Trifluoromethanesulfonate), a compound in which titanium of these compounds is changed to zirconium or hafnium, bis (trifluoromethanesulfonate) is dimethanesulfonate, dibenzenesulfonate, bis (perfluoroethanesulfonate), diethanesulfonate, propane sulfonate, bis (4-toluenesulfonate), or compound was changed to bis (perfluoro benzene sulfonate), - a (eta ⁵ cyclopentadienyl) (eta ⁵ - methyl cyclopentadienylide ), (Eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl), (eta ^5-n-butyl cyclopentadienyl)
(Η ⁵ -tert-butylcyclopentadienyl),
(Η ⁵ -trimethylsilylcyclopentadienyl),
(Eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl), (eta ⁵ - indenyl), (eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ -
(3,5-Dimethyl-2-phenoxy), a compound changed to (fluorenyl), (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy) , (3-phenyl-5-methyl-
Transition metal compounds such as 2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or compounds modified to (3-trimethylsilyl-2-phenoxy);

Dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η ^5-
Cyclopentadienyl) (3-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilene (η ⁵ -cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethyl silylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (3,5-di -Tert-butyl-2
- phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclo pentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-trimethylsilyl -2 - phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethyl Rushiriren (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-chloro -
2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - cyclopenta Dienyl) (1-
Naphthoxy-2-yl) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadiene Dienyl) (3-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3
5-dimethyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η
⁵ -tetramethylcyclopentadienyl) (3-ter
t-butyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η ⁵
-Tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl)
(3,5-di -tert- butyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy)
Titanium bis (trifluoromethanesulfonate),
Dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (5-methyl-3-
Trimethylsilyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-
tert-butyl-5-methoxy-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium bis (trifluoromethanesulfonate), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl ) (or a 1-naphthoxy-2-yl) titanium bis (trifluoromethanesulfonate), eta of these compounds ⁵ - cyclopentadienyl eta ⁵ - methylcyclopentadienyl, eta ⁵ - dimethyl cyclopentadienyl, η ⁵ - trimethyl Le cyclopentadienyl, eta ⁵
- ethylcyclopentadienyl, eta ^{5-n-propyl-cyclopentadienyl,} eta ⁵ - isopropyl-cyclopentadienyl, eta ^{5-n-butylcyclopentadienyl,} eta ⁵
-Sec- butylcyclopentadienyl, eta ⁵ - isobutyl cyclopentadienyl, eta ^{5-tert-butylcyclopentadienyl,} eta ⁵ - trimethylsilyl cyclopentadienyl, eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl , eta ⁵ - phenyl-cyclopentadienyl, eta ⁵ - indenyl, eta ⁵ - methylindenyl, eta
⁵ - phenyl indenyl or eta ⁵ - compounds that have changed fluorenyl, changing the 2-phenoxy 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert-butyldimethylsilyl-2-phenoxy, Compounds, compounds in which dimethylsilylene is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene, compounds in which titanium is changed to zirconium or hafnium, bis (trifluoromethanesulfonate) to dimethanesulfonate, dibenzenesulfonate, bis (perfluoroethane) Transition metal compounds such as sulfonates), diethanesulfonates, dipropanesulfonates, bis (4-toluenesulfonates), or compounds modified to bis (perfluorobenzenesulfonates) Things.

The transition metal compound represented by the general formula [IV]
As a specific example, μ-oxobis ｛isopropylidene
(Η^Five-Cyclopentadienyl) (2-phenoxy) thio
Tantalum trifluoromethanesulfonate｝, μ-oxo
Sobis diisopropylidene (η ^Five-Cyclopentadieni
) (3-tert-butyl-5-methyl-2-pheno)
Xix) titanium trifluoromethanesulfonate｝,
μ-oxobis ｛isopropylidene (η^Five-Methylsic
Lopentadienyl) (2-phenoxy) titanium tri
Fluoromethanesulfonate, μ-oxobisiso
Propylidene (η ^Five-Methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy
B) Titanium trifluoromethanesulfonate｝, μ
Oxobis ｛isopropylidene (η^Five-Tetramethyl
Cyclopentadienyl) (2-phenoxy) titanium
Trifluoromethanesulfonate｝, μ-oxobis
｛Isopropylidene (η^Five-Tetramethylcyclopenta
Dienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium trifluoromethanesulfone
To,

Μ-oxobis ｛dimethylsilylene (η ⁵
-Cyclopentadienyl) (2-phenoxy) titanium trifluoromethanesulfonate {, μ-oxobis} dimethylsilylene (η ⁵ -cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium trifluoromethanesulfonate {, μ
- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium trifluoromethanesulfonate}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - methylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium trifluoromethanesulfonate {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium trifluoromethanesulfonate}, μ-oxobis and the like - {dimethylsilylene (eta ^{5-tetramethylcyclopentadienyl)} (3-tert-butyl-5-methyl-2-phenoxy) titanium trifluoromethanesulfonate}, compound change titanium to zirconium or hafnium of these compounds , Trifluoromethanesulfonate, methanesulfonate, benzenesulfonate, perfluoroethanesulfonate, ethanesulfonate, propanesulfonate, 4-toluenesulfonate, or perfluo Compound was changed to benzenesulfonate, (eta ⁵ - cyclopentadienyl) a (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl), (eta ^5-n-butyl cyclopentadienyl ), (η ⁵ -tert- butyl cyclopentadienyl), (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert- butyldimethylsilyl cyclopentadienyl), (η ⁵ - indenyl), (eta ⁵ −
Methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to the isopropylene methylene or ethylene, or a compound of dimethylsilylene was changed to diethyl silylene or diphenylsilylene, (2- Phenoxy) is (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl- 2-phenoxy) or (3-trimethylsilyl-5-methyl-2)
-Phenoxy).

The above-mentioned transition metal compound of the present invention has a structure of X ¹
Is obtained by reacting a corresponding transition metal compound having a methyl group with a sulfonic acid, and reacting the transition metal compound thus obtained with 1 equivalent of water to obtain a μ-oxo type of the present invention. Is obtained.

(B) Aluminum compound Aluminum compound (B) used in the present invention
Is one or more aluminum compounds selected from the following (B1) to (B4). (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula （-Al (E ² ) -O-｝ _b (B3) General formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
A linear aluminoxane having a structure represented by ₂ (B4) wherein (B2) and / or the (B3) and the modified aluminoxane compounds obtained by reacting a compound having a hydroxyl group (provided that, E ^1, E ^2, And E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ may be the same or different, and Z represents a hydrogen atom or a halogen atom; May be the same or different. A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.) E ¹ , E ² , or as the hydrocarbon group in E ^3, preferably a hydrocarbon group having 1 to 8 carbon atoms, an alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0051] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b
Is 2 to 40 and c is 1 to 40.

The above aluminoxane 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. The aluminoxane thus obtained and commercially available aluminoxane are usually (B
It is considered to be a mixture of 2) and (B3).

Further, a modified aluminoxane compound (B4) obtained by reacting such an aluminoxane (aluminoxane represented by the above (B2) and / or (B3)) with a compound having a hydroxyl group is formed and used. Are also preferred. Such a compound having a hydroxyl group is alcohol, phenol, or silanol.

Examples of the alcohol compound in the compound having a hydroxyl group include compounds represented by the following general formula. R ⁷ R ⁸ R ⁹ COH (wherein R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom
And 20 to 20 halogenated hydrocarbon groups, which may be the same or different. ) As the hydrocarbon group in the above general formula, an alkyl group,
An aralkyl group, an aryl group, an arylalkyl group and the like can be mentioned.

Examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, Examples include triphenylmethyl alcohol, tricyclohexylmethyl alcohol, trifluoromethyl alcohol, perfluoroethyl alcohol, hexafluoroisopropyl alcohol, perfluoropropyl alcohol, perfluorobutyl alcohol, and the like, and compounds in which fluoro is changed to chloro, bromo, or iodo. Is preferably a tertiary alcohol or an alcohol substituted with a halogen atom, and particularly preferably t.
tert-butyl alcohol, triphenylmethyl alcohol, tricyclohexylmethyl alcohol, perfluoro-tert-butyl alcohol or 1,1,1,
3,3,3-hexafluoroisopropyl alcohol.

As the phenol compound in the compound having a hydroxyl group, unsubstituted or substituted phenols can be used. Here, examples of the substituent include a halogen atom or an alkyl group, an aralkyl group, an aryl group, a silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a silyloxy group which may be substituted with a halogen atom.

Examples of such a phenol compound include 2-methylphenol, 2-ethylphenol, 2-n-butylphenol, 2-isobutylphenol, 2-tert-phenol.
t-butylphenol, 2-n-propylphenol,
2-isopropylphenol, 2-phenylphenol, 2-fluorophenol, 2-chlorophenol,
2-substituted phenols such as 2-bromophenol; 3-
Methylphenol, 3-ethylphenol, 3-n-butylphenol, 3-isobutylphenol, 3-te
3-substituted phenols such as rt-butylphenol, 3-n-propylphenol, 3-isopropylphenol, 3-phenylphenol, 3-fluorophenol, 3-chlorophenol, 3-bromophenol;
4-methylphenol, 4-ethylphenol, 4-n
-Butylphenol, 4-isobutylphenol, 4-
4-substituted phenols such as tert-butylphenol, 4-n-propylphenol, 4-isopropylphenol, 4-phenylphenol, 4-fluorophenol, 4-chlorophenol, 4-bromophenol;
2,6-dimethylphenol, 2,6-diethylphenol, 2,6-di-n-butylphenol, 2,6-diisobutylphenol, 2,6-di-tert-butylphenol, 2,6-di-n-propyl Phenol,
2,6-di-isopropylphenol, 2,6-diphenylphenol, 2,6-difluorophenol, 2,
2,6-disubstituted phenols such as 6-dichlorophenol and 2,6-dibromophenol; 2,4,6-trimethylphenol, 2,6-di-tert-butyl-4-
2,6, X such as methylphenol, 2,3,5,6-tetrafluorophenol and pentafluorophenol
-Substituted phenol (X is 1 selected from 3, 4 and 5)
Is more than one number. 2,3-substituted phenols such as 2,3-difluorophenol; 2,4-substituted phenols such as 2,4-difluorophenol; 3,5-dimethylphenol, 3,5-diethylphenol, 3,
5-di-n-butylphenol, 3,5-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-n-propylphenol, 3,5-diisopropylphenol, 3,5-diphenylphenol, 3,5-substituted phenols such as 3,5-difluorophenol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-bistrifluoromethylphenol, pentafluorophenol, pentachlorophenol, pentamethylphenol, etc. Catechol, resorcinol, hydroquinone, bisphenol-A, 2,2-thiobis-6-tert-
Phenol compounds having two or more hydroxyl groups such as butyl-4-methylphenol are exemplified. The phenol compound is preferably a phenol having a bulky substituent at the 2,6-position or a halogenated phenol, and particularly preferably pentafluorophenol. As the silanol compound, a tertiary silanol is preferable, and examples thereof include triphenylsilanol and tricyclohexylsilanol.

Particularly preferred as the compound having a hydroxyl group are pentafluorophenol, triphenylmethyl alcohol, tricyclohexylmethyl alcohol, perfluoro-tert-butyl alcohol and 1,1,1.
1,3,3,3-hexafluoroisopropyl alcohol. One of these compounds having a hydroxyl group may be used alone, or two or more of them may be used in combination.

The aluminoxane represented by (B2) and / or (B3) is preferably reacted with a compound having a hydroxyl group in an inert gas atmosphere. The reaction temperature is not particularly limited, but is -80C to 200C, preferably -50C to 120C. The reaction time is 1 minute to 12 hours, preferably 2 minutes to 5 hours. In such a reaction, a solvent may be used, or these compounds may be directly reacted without using a solvent. The solvent used is not particularly limited, and examples thereof include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Specific examples include hexane, heptane, benzene, toluene and the like.

The ratio (molar ratio) of each component is not particularly limited, but the molar ratio of aluminoxane to the compound having a hydroxyl group is usually 1: 0.001 to 1 for the compound having a hydroxyl group. : 1.1, preferably in the range of 1: 0.01 to 1: 1.

The modified aluminum oxy compound obtained by such a treatment can be used as a catalyst component for olefin polymerization after isolation and purification such as recrystallization.
This reaction solution can be used as it is as a catalyst component for olefin polymerization.

In the present invention, the above-mentioned (B1) or (B4) is particularly preferred as the aluminum compound (B).

(C) Boron Compound In the present invention, the boron compound (C) includes the following (C)
1) One or more boron compounds selected from (C3) are used. (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (C3) a general formula (L ^{-H) + (BQ 1 Q 2} Q 3 Q 4) - in the boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺ is an inorganic, organic or organometallic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. )

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are each preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms,
A halogenated hydrocarbon group containing from 20 to 20 carbon atoms,
A substituted silyl group containing 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms, more preferably Q ^{1 to} Q ³ are each a halogen atom, It is a hydrocarbon group containing 1 to 20 carbon atoms or a halogenated hydrocarbon group containing 1 to 20 carbon atoms. More preferably, Q ^{1 to} Q ³ are each a halogenated hydrocarbon group, and particularly preferably, each of Q ^{1 to} Q ³ is a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom. And most preferably, Q ^{1 to} Q ³ are each a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom.

As specific examples of the compound (C1), tris (pentafluorophenyl) borane, tris (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.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic, organic or organometallic cation, and B is a trivalent valence. Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in the above (C1).

General formula G⁺ (BQ¹ Q^Two Q^Three Q^Four )^- so
G in the compound represented⁺ Specific examples of the inorganic
Lithium cation, sodium cation,
Potassium cation, silver cation, etc.
On: ferrocenium cation, alkyl-substituted ferro
Cerium cations and the like
Rukyphosphonium cation, tetraarylphosphoni
Cation, tetraalkylammonium, trial
Killsulfonium cation, diaryliodonium cation
Thion, trialkylcarbenium cation, triary
Alkenyl cation. G⁺ age
And preferably a carbenium cation, particularly preferred
Is a triphenylcarbenium cation. (BQ
¹ Q^Two Q ^Three Q^Four )^- As the tetrakis (pentaflu
Orophenyl) borate, tetrakis (2,3,5,6)
-Tetrafluorophenyl) borate, tetrakis
(2,3,4,5-tetrafluorophenyl) volley
G, tetrakis (3,4,5-trifluorophenyl)
Borate, tetrakis (2,3,4-trifluorophen)
Nyl) borate, phenyl tris (pentafluorophene)
Nyl) borate, tetrakis (3,5-bistrifluoro)
Romethylphenyl) borate and the like.

Specific examples of these combinations include lithium tetrakis (3,5-bistrifluoromethylphenyl) borate, sodium tetrakis (3,5-bistrifluoromethylphenyl) borate and potassium tetrakis (3,5-bistrifluoromethylphenyl). Phenyl)
Borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrabutylphosphonium tetrakis (pentafluorophenyl) borate, Tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylsulfonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluoro) Phenyl) borate, triphenylcarbeniumtetrakis (3,5-bistrif) (Fluoromethylphenyl) borate and the like, and most preferably, triphenylcarbeniumtetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

[0070] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{−, the same} as those described above can be mentioned.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, 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) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

The boron compound used in the present invention is preferably (C2) or (C3), particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) ) Borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization of olefin] In the present invention,
An olefin polymerization catalyst obtained by bringing the above (A) into contact with (B) and / or (C) is used. The contact here means any method as long as the above (A) and (B) and / or (C) are in contact with each other and a catalyst is formed. A method in which the above (A) and (B) and / or (C) are mixed and brought into contact with each other, or a method in which the catalyst is formed by separately supplying the mixture to a polymerization tank and bringing it into contact in the polymerization tank. it can. As a method for supplying each of the catalyst components to the polymerization tank, it is preferable to supply each of the catalyst components in an inert gas such as nitrogen or argon without moisture. In this case, arbitrary two or three components are mixed and contacted in advance. After the reaction, they may be separately supplied to the polymerization tank.

The olefin polymerization catalyst of the present invention is preferably an olefin polymerization catalyst obtained by contacting the above (A), (B1) and (C), or the above (A), (B1) and (B4) ) Is a catalyst for olefin polymerization obtained by contacting the above.

The amount of each component used is such that the molar ratio of (B) / [transition metal atom contained in the transition metal compound (A)] is usually 0.1 to 10000, preferably 5 to 2000,
Each component may be used such that the molar ratio of (C) / [transition metal atom contained in transition metal compound (A)] is usually 0.01 to 100, preferably 0.5 to 10. desirable.

When each component is used in the form of a solution or a suspension or slurry in a solvent, the concentration is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component. A) is usually 0.001
~ 200 mmol / L, more preferably 0.01 ~
100 mmol / L, more preferably 0.05 to 5
0 mmol / L and (B) are each converted into Al atoms,
It is usually 0.01 to 5000 mmol / L, more preferably 0.1 to 2500 mmol / L, still more preferably 0.1 to 2000 mmol / L, and (C) is usually 0.001 to 500 mmol / L. Preferably,
0.01 to 250 mmol / L, more preferably,
It is desirable to use each component so as to be in the range of 0.05 to 100 mmol / L.

The method for supplying each catalyst component, a mixture thereof, or a catalyst to the reactor is not particularly limited. A method in which each component is supplied in a solid state, a method in which a solution is dissolved in a hydrocarbon solvent, or a method in which each component is supplied in a suspended slurry state, are exemplified.

The olefins applicable to the polymerization in the present invention include olefins having 2 to 20 carbon atoms, particularly ethylene, α-olefins having 3 to 20 carbon atoms, and diolefins having 4 to 20 carbon atoms. And the like, and two or more types of monomers can be used at the same time. Specific examples of the olefin include linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, and 3-methylbutene-. Examples thereof include branched olefins such as 1,3-methylpentene-1, 4-methylpentene-1, and 5-methylhexene-1, and vinylcyclohexane, but the present invention is not limited to the above compounds. . Specific examples of the combination of monomers at the time of copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, propylene and butene-1, and the like. The invention should not be limited to these combinations.

The present invention is particularly useful for the production of copolymers of ethylene with α-olefins, especially propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1 and other α-olefins. Applicable.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and methylene dichloride and the like can be used. Solvent polymerization using a halogenated hydrocarbon as a solvent, or slurry polymerization, or a method called high-pressure ionic polymerization, in which the olefin polymer formed into an olefin in a supercritical fluid state under high temperature and pressure without solvent is melted. The polymerization can be carried out in a state in which the polymerization has been carried out, and furthermore, a gas phase polymerization in a gaseous monomer or the like is possible, and both continuous polymerization and batch polymerization are possible.

The polymerization temperature is usually in the range of -50 ° C to 350 ° C, preferably 0 ° C to 300 ° C, more preferably 50 ° C to 300 ° C. The present invention is suitably applied to high-temperature polymerization of high industrial value. The polymerization temperature is particularly preferably in the range of 150 to 300 ° C. The polymerization pressure is usually in the range from normal pressure to 350 MPa, preferably from normal pressure to 300 MPa, particularly preferably from normal pressure to 200 MPa.

The process for producing the olefin polymer of the present invention comprises:
Particularly, it is preferably carried out by a high-pressure ion polymerization method. Specifically, it is preferably carried out at a pressure of 30 MPa or more and a temperature of 100 ° C. or more. More preferably, the pressure is between 35 and
The operation is performed at 300 MPa and a temperature of 135 to 300 ° C.
In this case, the polymerization system may be either a batch system or a continuous system, but it is preferable to carry out the system in a continuous system. In general, a stirred tank reactor or a tubular reactor can be used as the reactor. The polymerization may be carried out in a single reaction zone, but may be carried out by dividing one reactor into a plurality of reaction zones, or by connecting a plurality of reactors in series or in parallel. When a plurality of reactors are used, any combination of a tank type-tank type or a tank type-tube type may be used. In the method of polymerizing in a plurality of reaction zones or a plurality of reactors, it is also possible to produce olefin polymers having different properties by changing the temperature, pressure, and gas composition for each reaction zone.

The polymerization time is generally determined appropriately depending on the kind of the target polymer and the reaction apparatus, and there is no particular condition to be restricted, but it 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.

[0084]

The present invention will be described below 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) Melting point of copolymer: Determined by using an SSC5000 thermal analysis system manufactured by Seiko Denshi Kogyo KK under the following conditions. Temperature rise: Raise the temperature to 150 ° C, hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

(2) Content of repeating unit derived from α-olefin in copolymer: infrared spectrophotometer (FTIR1600 series manufactured by PerkinElmer)
And obtained from the characteristic absorption of ethylene and α-olefin, and expressed as the number of short-chain branches per 1000 carbons (SCB).

(3) Intrinsic viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and an Ubbelohde viscometer set in a water bath maintained at 135 ° C. And the falling speed of the tetralin solution in which the sample was dissolved. (Unit: dl / g)

(4) Molecular weight and molecular weight distribution: It was determined under the following conditions using a gel permeation chromatograph (150, C, manufactured by Waters). The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-ortho-dichlorobenzene

Example 1 (1) Dimethylsilylene (η
⁵ -tetramethylcyclopentadienyl) (3-ter
Synthesis of t- butyl-5-methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate): toluene 20ml of dimethyl silylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dimethyl
36 g (5.6 mmol) were dissolved, and trifluoromethanesulfonic acid 1.76 g (11.8 mm
ol) in 10 ml of a toluene solution. After holding for 10 minutes, the temperature was gradually raised to 20 ° C., and stirring was continued for 2 hours. After concentrating the reaction solution, the residue was washed with hexane (5 ml).
In 3 times), dried dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl -
5-Methyl-2-phenoxy) titanium bis (trifluoromethanesulfonate) (compound) was obtained as red crystals (2.90 g, 75%). mp61.0-
62.5 ° C ¹ H NMR (270 MHz, C6D6) δ 7.10 (d, 1 H, J = 2 Hz), 7.0
6 (d, 1 H, J = 2 Hz), 2.17 (s, 3 H), 1.98 (s, 6 H),
1.88 (s, 6 H), 1.30 (s, 9 H), 0.42 (s, 6 H)

[Example 1 (2)] Polymerization After purging the autoclave type reactor equipped with a stirring blade with a capacity of 0.4 l with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
Was charged, and the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 Mpa and the mixture was fed. After the inside of the system was stabilized, 0.25 mmol of triisobutylaluminum and 1 ml of a heptane solution of the compound (the concentration of the compound was 1 μmol / ml) (that is, 1 ml) Compound (1 μmol) was charged, and then N, N-dimethylanilinium tetrakispentafluorophenyl borate (compound) in heptane slurry (slurry concentration, 1 μm)
(mol / ml). Polymerization was performed for 2 minutes. As a result of the polymerization, ethylene-hexene-1 having [η] of 0.85 dl / g, SCB of 33.0, melting points of 77.0 ° C. and 90.2 ° C., Mw of 47000, and Mw / Mn of 2.5. 5.09 g of a copolymer was obtained. The polymerization activity per mole of Ti atom is 5.1 × 10 ⁶ g / T per 2 minutes.
imol.

COMPARATIVE EXAMPLE 1 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, 185 ml of cyclohexane was added as a solvent, and 15 ml of hexene-1 was added as an α-olefin. Temperature. After raising the temperature, the ethylene pressure was increased to 2.5
Feed while adjusting to Mpa, and after the system is stabilized,
Triisobutylaluminum 0.2 mmol, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride in heptane (compound) and triisobutylaluminum were mixed 1 ml of the solution (the concentration of the compound is 1 μmol / ml and the concentration of triisobutylaluminum is 50 μmol / ml) (that is, 1 μmol of the compound and 5 μmol of triisobutylaluminum)
0 μmol) and then 3 ml of a compound heptane slurry (slurry concentration, 1 μmol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] is 0.8
9dl / g, SCB 33.8, melting points 77.7 ° C and 89.9 ° C, Mw 48700, Mw / Mn 2.6.
3.43 g of ethylene-hexene-1 copolymer was obtained. The polymerization activity per mole of Ti atom is per 2 minutes,
It was 3.4 × 10 ⁶ g / Timol.

[0092]

As described above in detail, according to the present invention, a transition metal compound containing a sulfonyloxy group, a highly active catalyst for olefin polymerization using the compound, and a method for efficiently producing an olefin polymer Is provided.

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hidenori Hanaoka 2-1-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industries Co., Ltd. (72) Yoshiaki Oda 2-27-1, Shinkawa, Chuo-ku, Tokyo F-term (reference) in Sumitomo Kagaku Kogyo Co., Ltd. BC25B EA01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EC01 EC02 FA01 FA02 FA04 FA06 FA07 4J128 AA01 AB00 AB01 AC01 AC02 AC09 AC10 AC19 AC20 AC22 AD00 BA00A BA01B BA02B BB00A BB01B BC12B EB02 EB02 EB02 EB02 EB02 FA02 FA04 FA06 FA07

Claims (9)

[Claims] 1. A transition metal compound represented by the following general formula [I] or [II]. _{^{CpMYX 1 2 [I] (CpMYX}} 1) 2 X 2 [II] ( respectively, in the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table of the elements, and Cp
Represents a group having a cyclopentadiene-type anion skeleton. Y is a group that is σ-bonded to M via an atom of Group 15 or Group 16 of the periodic table of the elements, and Cp and Y are bonded directly or via a cross-linking group. X ¹ represents a sulfonyloxy group, and X ² represents an atom belonging to Group 16 of the periodic table of the elements. All Cp when there are a plurality of Cp in one molecule,
M, Y, and X ¹ may be the same or different. In addition, a plurality of Cp and a plurality of X ¹ may be bonded directly or via a cross-linking group. ) 2. The method according to claim 1, wherein Y is M or M through a nitrogen atom or an oxygen atom.
2. The transition metal compound according to claim 1, which is a group which is σ-bonded to the transition metal compound. 3. The transition metal compound according to claim 1, wherein the transition metal compound is a transition metal compound represented by the following general formula [III] or [IV]. (In the above general formula [III] or [IV],
M represents a transition metal atom of Group 4 of the periodic table of the element;
Represents an atom belonging to Group 16 of the periodic table of the element, and J represents an atom belonging to Group 14 of the periodic table of the element. Cp represents a group having a cyclopentadiene-type anion skeleton. R ¹ , R ² , R
³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group,
Substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, alkylseleno group,
It represents an aralkylseleno group or an arylseleno group.
X ¹ represents a sulfonyloxy group, and X ² represents an atom belonging to Group 16 of the periodic table of the elements. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. All M, A, J, Cp, when there are a plurality of them in one molecule,
X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different. ) 4. X ¹ is —OS (O) ₂ R (where R is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl having 7 to 20 carbon atoms). A transition metal compound, which may be substituted with a halogen atom.). (5) The following (A), (B) and / or
An olefin polymerization catalyst obtained by contacting (C) with (A). (A) the transition metal compound according to any one of claims 1 to 4 (B) one or more kinds selected from the following (B1) to (B4)
Aluminum compound (B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_Two(B4) The above-mentioned (B2) and / or the above-mentioned (B3) and water
Obtained by reacting with a compound having an acid group
Modified aluminoxane compound (however, E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeAre the same
Or different. Z is a hydrogen atom or halogen
All Z are the same but different
Is also good. a is a number satisfying 0 <a ≦ 3, b is 2 or more
An integer and c represents an integer of 1 or more. (C) one or more kinds selected from the following (C1) to (C3)
Boron compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
Boron compound (where B is trivalent valence state)
Q is a urine atom¹~ Q^FourIs a halogen atom, hydrocarbon
Group, halogenated hydrocarbon group, substituted silyl group, alkoxy
Or disubstituted amino groups, which are the same and
May also be different. G⁺Is inorganic, organic or organic gold
L is a neutral Lewis base and (L
-H)⁺Is a Bronsted acid. ) 6. The olefin polymerization catalyst according to claim 5, wherein (B) is triethylaluminum, triisobutylaluminum, methylaluminoxane or butylaluminoxane. 7. The catalyst for olefin polymerization according to claim 5, wherein (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 8. A method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized using the olefin polymerization catalyst according to any one of claims 5 to 7. 9. The method for producing an olefin polymer according to claim 8, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.