JP2001253907A - Catalyst for polymerizing olefin, and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly active catalyst for polymerizing an olefin, and further to provide a method for efficiently producing an olefin polymer. SOLUTION: This catalyst for polymerizing the olefin is obtained by bringing (A) a group 4 transition metal compound having a group comprising a cyclopentadiene-type anionic skeleton into contact with (B) a specific organoaluminum compound, (C) a specified boron compound and (D) a modified aluminumoxy compound obtained by reacting (D1) an aluminumoxy compound with (D2) a boron compound represented by the general formula: BQ1Q2Q3. The method for producing the olefin polymer comprises homopolymerizing or copolymerizing the olefins by using the catalyst for polymerizing the olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst prepared using a modified aluminum oxy 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 processes for producing olefin polymers using metallocene complexes. 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.

[0003] In order to solve this problem, many reports have been made on high activation by modification of an aluminum oxy compound. For example, Japanese Unexamined Patent Publication No. Hei.
In JP-A No. 2000-135, a benzene-insoluble aluminum oxy compound obtained by reacting aluminoxane with water is reported. In addition, JP-A-7-70145 reports an aluminum oxy compound obtained by reacting an aluminoxane with a cyclic alkoxyboron compound such as catecholborane. However, even these methods have not sufficiently solved the above-mentioned problems.

In Japanese Patent Application Laid-Open No. 4-353502,
Although a catalyst system comprising a transition metal compound, a boron compound, and an organoaluminum compound has been reported, the catalyst components were separately charged into the polymerization system, and the activity was insufficient from an industrial viewpoint. . JP-A-6
No. 329714 reports an olefin polymerization method using an aluminum oxy compound having an electron-withdrawing group such as a pentafluorophenoxy group as a catalyst component for olefin polymerization. However, its catalytic activity was not always sufficient.

[0005] Journal of Molecular Catalsis A: Chemic
al 132 (1998) 231-239.Choong Hoon Lee et al. reported on olefin polymerization using zirconocene with a compound obtained by reacting methylalumoxane with trispentafluorophenylborane, but its catalytic activity is still unknown. It was not always enough.

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 is obtained with high activity, further improvement in activity has been desired.

[0007]

In view of the above situation, an object of the present invention is to provide a highly active catalyst for olefin polymerization and an efficient method for producing an olefin polymer. Is to do.

[0008]

That is, the present invention provides the following:
(A), (B), (C) and (D)
Or contact (A), (C) and (D)
For olefin polymerization obtained by the above, and the olefin
Using a polymerization catalyst, olefins are homopolymerized or copolymerized.
It relates to a method for producing an olefin polymer to be polymerized.
You. (A) a group having a cyclopentadiene-type anion skeleton
Group 4 transition metal compound having (B) at least one selected from the following (B1) to (B3)
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
_TwoLinear aluminoxane having a structure represented by the following formula (provided that 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
(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 and (LH)⁺Is Bren
Sted acid. (D) (D1) an aluminum oxy compound, and (D)
2) General formula BQ¹Q^TwoQ ^Three(However, B is trivalent valence
Is a boron atom in the form¹~ Q^ThreeIs a halogen atom, carbonized
Hydrogen group, halogenated hydrocarbon group, substituted silyl group, alcohol
Xy or disubstituted amino groups which are the same
Or different. ) Boron compound
The modified aluminum oxy compound obtained by the reaction of the present invention is described below in more detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Transition metal compound The transition metal compound used in the present invention is a Group 4 transition metal compound having a group having a cyclopentadiene-type anion skeleton.

The Group 4 transition metal compound referred to here is a periodic table of elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 198).
9) Group 4 transition metal compounds, for example, titanium compounds, zirconium compounds, hafnium compounds and the like. Preferably, it is a compound of titanium or a compound of zirconium. The group having a cyclopentadiene-type anion skeleton here is the same as the group shown as a substituent Cp described later.

The transition metal compound used in the present invention is preferably a transition metal compound represented by the following general formula [I] or [II]. ^{_{Cp m MX 1 4-m [}} I] (Cp p MX 1 q) 2 X 2 r [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. X ¹ is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It represents an aralkyloxy group, an aryloxy group, a disubstituted amino group, an alkylthio group, an aralkylthio group, an arylthio group, an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² is the sixteenth element of the periodic table
Indicates a group atom. m is an integer satisfying 1 ≦ m ≦ 4, p is a number satisfying 1 ≦ p ≦ 3, and q is 0 ≦ q ≦
Is a number that satisfies 2, r is 1 or 2, and is an integer that satisfies p + q + r = 4. When a plurality of Cp, X ¹ and X ² are present in one molecule, they may be the same or different. In addition, a plurality of Cp,
A plurality of X ^{1 s} , or Cp and X ¹ may be bonded directly or via a cross-linking group. )

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). 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.
Specifically, 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-Pentamethylcyclopentadienyl
Group, η^Five-Ethylcyclopentadienyl group, η^Five-N-pu
Ropylcyclopentadienyl group, η^Five-Isopropyl
Clopentadienyl group, η^Five-N-butylcyclopenta
Dienyl group, η^Five-Sec-butylcyclopentadienyl
Group, η^Five-Tert-butylcyclopentadienyl
Group, η^Five-Phenylcyclopentadienyl group, η^Five-Bird
Methylsilylcyclopentadienyl group, η^Five-Tert
-Butyldimethylsilylcyclopentadienyl group, η^Five
-Indenyl group, η^Five-Methylindenyl group, η^Five−Jimme
Tilindenyl group, η^Five-N-propylindenyl group,
η^Five-Isopropylindenyl group, η^Five-N-butylin
Denenyl group, η^Five-Tert-butylindenyl group, η^Five−
Phenylindenyl group, η^Five-Methylphenylindeni
Group, η^Five-Naphthylindenyl group, η^Five-Trimethylsi
Rilindenyl group, η^FiveA tetrahydroindenyl group,
η^FiveA fluorenyl group, η^Five-Methylfluorenyl group, η
^Five-Dimethylfluorenyl group, η^Five-Tert-butyl ether
Fluorenyl group, η^Five-Di-tert-butylfluorenyl
Group, η^FiveA phenylfluorenyl group, η^Five-Diphenyl
Fluorenyl group, η^Five-Trimethylsilylfluorenyl
Group, η^Five-Bistrimethylsilylfluorenyl group or the like
And preferably η^FiveA cyclopentadienyl group,
η^Five-Methylcyclopentadienyl group, η^Five-N-butyl
Cyclopentadienyl group, η^Five-Tert-butylsic
Lopentadienyl group, η^Five-Tetramethylcyclopenta
Dienyl group, η^Five-Pentamethylcyclopentadienyl
Group, η^Five-Indenyl group, η^Five-Tetrahydroindenyl
Group, or η^Five-A fluorenyl group.

Examples of the halogen atom in the substituent X ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

As the alkyl group for the substituent X ¹ ,
An alkyl group having 1 to 20 carbon atoms is preferable, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, sec-butyl group, tert-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., more preferably methyl group, ethyl group, isopropyl group, tert -A 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, Perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group,
Examples include a perchlorobutyl group and a perbromopropyl group. 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 in the substituent X ¹ is preferably an aralkyl group having 7 to 20 carbon atoms, for example, benzyl, (2-methylphenyl) methyl,
(3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (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, (2,3 , 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, anthracenylmethyl group and the like, more preferably benzyl group is there. All of these aralkyl groups are a fluorine atom, a chlorine atom,
A part thereof may be substituted with a halogen atom such as 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.

The aryl group in the substituent X ¹ includes:
An aryl group having 6 to 20 carbon atoms is preferable, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 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, 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,
Examples include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group, and the like, and more preferably a phenyl group. All of these aryl 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, or an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituted silyl group in the substituent X ¹ is a silyl group substituted by a hydrocarbon group, wherein the hydrocarbon group includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-propyl group. -Alkyl group having 1 to 10 carbon atoms such as -butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and aryl group such as phenyl group. Can be Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. Di-substituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert -Butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group,
Examples include trisubstituted silyl groups having 3 to 20 carbon atoms such as tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group, preferably trimethylsilyl group, tert-
A 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 in the substituent X ¹ is preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a sec-butoxy group. ,
tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-
Examples thereof include a dodeoxy group, an n-pentadeoxy group, and an n-icosoxy group, and more preferred are a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group. All of these alkoxy 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 aralkyloxy group for the substituent X ¹ is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group, a (2-methylphenyl) methoxy group, a (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-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (N-butylphenyl) methoxy group, (sec-
(Butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy And more preferably a 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 the substituent X ¹ is preferably an aryloxy group having 6 to 20 carbon atoms, such as a phenoxy group, a 2-methylphenoxy group,
-Methylphenoxy group, 4-methylphenoxy group, 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-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-ter
t-butyl-3,4-dimethylphenoxy group, 2-te
rt-butyl-3,5-dimethylphenoxy group, 2-t
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, sec-butylphenoxy group, tert-butylphenoxy group, n
-Hexylphenoxy group, n-octylphenoxy group,
Examples thereof include an n-decylphenoxy group, an n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group. 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 the substituent X ¹ is 2
An amino group substituted with one hydrocarbon group or a silyl group, wherein the hydrocarbon group includes, for example, a methyl group,
C 1-10 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group. Examples thereof include an aryl group having 6 to 10 carbon atoms such as an alkyl group and a phenyl group, and an aralkyl group having 7 to 10 carbon atoms such as a benzyl group. As the silyl group, a trimethylsilyl group, ter
and a t-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, di-tert-butylamino 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, preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, and a di-ter
a t-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 the substituent X ¹ is preferably an alkylthio group having 1 to 20 carbon atoms.
For example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, 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, they are a methylthio group, an ethylthio group, 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 the substituent X ¹ is preferably an aralkylthio group having 7 to 20 carbon atoms, for example, a benzylthio group, a (2-methylphenyl) methylthio group, a (3-methylphenyl) methylthio group,
(4-methylphenyl) methylthio group, (2,3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) A methylthio group, a (3,4-dimethylphenyl) methylthio group,
(3,5-dimethylphenyl) methylthio group, (2,
3,4-trimethylphenyl) methylthio group, (2,
3,5-trimethylphenyl) methylthio group, (2,
3,6-trimethylphenyl) methylthio group, (2
4,5-trimethylphenyl) methylthio group, (2,
4,6-trimethylphenyl) methylthio group, (3,
4,5-trimethylphenyl) methylthio group, (2,
3,4,5-tetramethylphenyl) methylthio group,
(2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (n- Propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec
-Butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group, (n-octylphenyl) methylthio group,
(N-decylphenyl) methylthio group, naphthylmethylthio group, anthracenylmethylthio group and the like,
More preferably, it is a benzylthio group. All of these aralkylthio 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 arylthio group in the substituent X ¹ is preferably an arylthio group having 6 to 20 carbon atoms.
For example, phenylthio group, 2-methylphenylthio group, 3
-Methylphenylthio group, 4-methylphenylthio group,
2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,
6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-te
rt-butyl-3-methylphenylthio group, 2-ter
t-butyl-4-methylphenylthio group, 2-tert
-Butyl-5-methylphenylthio group, 2-tert-
Butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group,
2,4,5-trimethylphenylthio group, 2,4,6-
Trimethylphenylthio group, 2-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-ter
t-butyl-3,4,5-trimethylphenylthio group,
2,3,4,6-tetramethylphenylthio group, 2-t
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, ter
Examples include a t-butylphenylthio group, an n-hexylphenylthio group, an n-octylphenylthio group, an n-decylphenylthio group, an n-tetradecylphenylthio group, a naphthylthio group, and an anthracenylthio group. All of these arylthio groups are a fluorine atom, a chlorine atom,
A part thereof may be substituted with a halogen atom such as 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.

The alkyl seleno group in the substituent X ¹ is preferably an alkyl seleno group having 1 to 20 carbon atoms, such as a methyl seleno group, an ethyl seleno group, an n-propyl seleno group, an isopropyl seleno group, an n-butyl seleno group, and a 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, etc., and more preferably methylseleno group, ethylseleno group, isopropylseleno group, or tert- group. It is a 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 the substituent X ¹ is preferably an aralkylseleno group having 7 to 20 carbon atoms, for example, a benzylseleno group, a (2-methylphenyl) methylseleno group, a (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group,
A (2,3-dimethylphenyl) methylseleno group, (2,3-
(4-dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-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) Chirusereno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n- propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (n- butylphenyl) methylseleno group, (sec-butylphenyl)
A methylseleno group, a (tert-butylphenyl) methylseleno group, a (n-hexylphenyl) methylseleno group,
Examples thereof include (n-octylphenyl) methylseleno group, (n-decylphenyl) methylseleno group, naphthylmethylseleno group, and anthracenylmethylseleno group, and more preferably benzylseleno group. All of these aralkylseleno 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 the substituent X ¹ is preferably an arylseleno group having 6 to 20 carbon atoms, for example, phenylseleno, 2-methylphenylseleno, 3-methylphenylseleno, 4-methylphenyl Seleno group, 2,3-dimethylphenylseleno group, 2,
4-dimethylphenylseleno group, 2,5-dimethylphenylseleno 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-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di-tert-butyl-3-methylphenylseleno group,
-Tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethylphenylseleno group, 2,3,4,5- Tetramethylphenylseleno group,
2-tert-butyl-3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenylseleno 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-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno group, n-
Examples thereof include an 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.

Preferably, X ¹ is independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, more preferably a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. is there.

X in the above general formula [I] or [II]
² represents an atom of Group 16 of the periodic table of the element, and specific examples include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. is there.

In the general formula [I] or [II], a plurality of Cp, a plurality of X ¹ ,
p and X ¹ may be bonded directly or via a crosslinking group. As the crosslinking group, periodic table of elements (IUPAC)
Inorganic chemical nomenclature, revised edition 1989), a divalent cross-linking group containing an atom belonging to Group 14 and the like are preferable, and a divalent cross-linking group containing a carbon atom or a silicon atom is preferable. More preferably, the atom bonded to Cp or X ¹ is a carbon atom and / or
Or a divalent bridging group which is a silicon atom, more preferably, the atom bonding to Cp or X ¹ is a carbon atom and / or a silicon atom, and the minimum number of atoms between the atoms bonding to Cp or X ¹ is A divalent bridging group of 3 or less (this includes Cp
And the case where the atom bonded to X ¹ is single. ).
Specifically, a methylene group, an ethylene group, a propylene group,
Dimethylmethylene group (isopropylidene group), diphenylmethylene group, tetramethylethylene group, silylene group,
A dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, a tetramethyldisilylene group, a dimethoxysilylene group, and the like, and particularly preferably a methylene group,
An ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene group. As the transition metal compound represented by the above general formula [I] or [II], C.I.
It is a transition metal compound in which p and X ¹ are bonded via a crosslinking group.

In the above general formula [I], m is 1 ≦ m ≦
An integer that satisfies 4. In the above general formula [II],
p is a number satisfying 1 ≦ p ≦ 3, q is a number satisfying 0 ≦ q ≦ 2, r is 1 or 2, and p +
It is an integer satisfying q + r = 4. m and p represent the number of Cp bonded to the transition metal atom M, and the transition metal compound used in the present invention is a transition metal compound in which a group having one cyclopentadiene-type anion skeleton is bonded to one transition metal atom. Metal compounds are preferred. That is, the transition metal compound used in the present invention is preferably a transition metal compound in which m in the general formula [I] is 1 or a general formula [I
I] is a transition metal compound in which p is 1.

The transition metal compound used in the present invention is more preferably a transition metal compound represented by the following general formula [III], [IV] or [V]. (In the general formulas [III], [IV] and [V], M represents a transition metal atom belonging to Group 4 of the periodic table of the element, and A represents an atom belonging to Group 16 of the periodic table of the element.) Show, J
Represents an atom belonging to Group 14 of the periodic table of the elements. Cp represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , 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, a substituted silyl group, an alkoxy group, an aralkyloxy group An aryloxy group, a disubstituted amino group,
Alkylthio group, aralkylthio group, arylthio group,
It represents an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² represents an atom of Group 16 of the periodic table of the element. 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 ¹ , X ² , R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different. )

The above general formula [III], [IV] or [V]
, M, Cp and X ² are the same as those in the general formula [I] or [II], respectively. X ¹ in the above general formula [III], [IV] or [V],
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently
It is the same as X ¹ in the general formula [I] or [II].

However, 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, among which R ¹ is particularly preferably an alkyl group, an aralkyl group, an aryl group or a substituted silyl group.

R ⁵ and R ⁶ in the above formulas [III], [IV] or [V] each independently represent 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 is preferred.

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

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

As such a transition metal compound, for example, as a specific example of a transition metal compound in which m in the general formula [I] is 1 and has no crosslinking group, (η ⁵ -cyclopentadienyl)
Titanium trichloride, (eta ⁵ - cyclopentadienyl) titanium trimethyl, (eta ⁵ - cyclopentadienyl) (dimethylamino) titanium dichloride,
(Eta ⁵ - cyclopentadienyl) (diethylamino) titanium dichloride, (eta ⁵ - cyclopentadienyl) (di -n- butylamino) titanium dichloride, (eta ⁵ - cyclopentadienyl) (di -n- octyl amino) titanium dichloride, (eta ⁵ - cyclopentadienyl) (diphenylamino) titanium dichloride, (eta ⁵ - cyclopentadienyl) (methoxy)
Titanium dichloride, (eta ⁵ - cyclopentadienyl) (ethoxy) titanium dichloride, (eta ⁵ - cyclopentadienyl) (tert-butoxy) titanium dichloride, (eta ⁵ - cyclopentadienyl) (phenoxy) titanium dichloride, (eta ⁵ - cyclopentadienyl) (2,6-di -tert- butyl phenoxy) titanium dichloride, - such as (eta ⁵ cyclopentadienyl) (2-tert-butyl-4-methylphenoxy) titanium dichloride and, eta of these compounds ⁵ - cyclopentadienyl eta ⁵ - methylcyclopentadienyl, eta ⁵ - dimethyl cyclopentadienyl, eta ⁵
-Trimethylcyclopentadienyl,? ⁵ -tetramethylcyclopentadienyl,? ⁵ -pentamethylcyclopentadienyl,? ⁵ -ethylcyclopentadienyl,? ⁵
-N-butylcyclopentadienyl, η ⁵ -tert-
Butylcyclopentadienyl, eta ⁵ - di-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 - compound was changed to fluorenyl compounds changing the titanium to zirconium or hafnium, dimethyl dichloride,
Transition metal compounds such as dibenzyl, dimethoxide, diphenoxide, compounds changed to bis (dimethylamide) or bis (diethylamide) and the like can be mentioned.

Specific examples of the transition metal compound having m of 2 in the general formula [I] and having no bridging group include bis (η ⁵ -cyclopentadienyl) titanium dichloride and bis (η
⁵ - cyclopentadienyl) titanium dichloride, bis (eta ⁵ - dimethyl cyclopentadienyl) titanium dichloride, bis (eta ⁵ - trimethyl cyclopentadienyl) titanium dichloride, bis (eta ⁵
- tetramethylcyclopentadienyl) titanium dichloride, bis (eta ⁵ - pentamethylcyclopentadienyl) titanium dichloride, bis (eta ⁵ - ethyl cyclopentadienyl) titanium dichloride, bis (eta ^5-n-butyl cyclopentadiene Dienyl) titanium dichloride, bis (η ⁵ -tert-butylcyclopentadienyl) titanium dichloride, bis (η ⁵ −
Trimethylsilylcyclopentadienyl) titanium dichloride, bis (η ⁵ -tert-butyldimethylsilylcyclopentadienyl) titanium dichloride,
Bis (η ⁵ -phenylcyclopentadienyl) titanium dichloride, bis (η ⁵ -indenyl) titanium dichloride, bis (η ⁵ -fluorenyl) titanium dichloride and the like, and compounds in which titanium of these compounds is changed to zirconium or hafnium, Examples thereof include transition metal compounds such as compounds in which dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamide) or bis (diethylamide).

Specific examples of the transition metal compound having m in the general formula [I] and having a crosslinking group include dimethylsilylene (methylamino) (η ⁵ -cyclopentadienyl) titanium dichloride and dimethylsilylene (tert-butyl). Amino) (η ⁵ -cyclopentadienyl) titanium dichloride, dimethylsilylene (phenylamino)
(Η ⁵ -cyclopentadienyl) titanium dichloride, dimethylsilylene (cyclohexylamino) (η ⁵
-Cyclopentadienyl) titanium dichloride and the like, and η ⁵ -cyclopentadienyl of these compounds are converted to η ⁵
- methylcyclopentadienyl, eta ⁵ - tetramethylcyclopentadienyl, eta ⁵ - ethylcyclopentadienyl, eta ^{5-n-butylcyclopentadienyl,} eta ⁵ -TE
rt-butylcyclopentadienyl, η ⁵ -di-ter
t- 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 - compound change fluorenyl, change dimethylsilylene diethyl silylene, diphenyl silylene, methylene, ethylene or dimethylmethylene (isopropylidene), diphenylmethylene, tetramethylethylene, the tetramethyl silylene Compound, titanium changed to zirconium or hafnium, dichloride changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamide) or bis (diethylamide) Such transition metal compound Tsu and the like.

As a specific example of the transition metal compound having m in general formula [I] and 2 having a crosslinking group, methylenebis (η
⁵ -cyclopentadienyl) titanium dichloride,
Isopropylidene-bis (eta ⁵ - cyclopentadienyl)
Titanium dichloride, dimethylsilylene bis (η ⁵
-Cyclopentadienyl) titanium dichloride, diphenylsilylenebis (η ⁵ -cyclopentadienyl)
Titanium dichloride, methylene bis (eta ⁵ - methylcyclopentadienyl) titanium dichloride, isopropylidene-bis (eta ⁵ - methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (eta ⁵ - methylcyclopentadienyl) titanium dichloride, diphenyl Shirirenbisu (eta ⁵ - methylcyclopentadienyl) titanium dichloride, methylene bis (eta ⁵ - dimethyl cyclopentadienyl) titanium dichloride, isopropylidene-bis (eta ⁵ - dimethyl cyclopentadienyl) titanium dichloride, dimethylsilylene bis (eta ⁵ - dimethyl cyclopentadienyl) titanium dichloride, diphenylsilylene bis (eta ⁵ - dimethyl cyclopentadienyl) titanium dichloride, methylene bis (Eta ⁵ - tetramethylcyclopentadienyl) titanium dichloride, isopropylidene-bis (eta ⁵ - tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (eta ⁵ - tetramethylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (eta ⁵ - tetramethylcyclopentadienyl) titanium dichloride, methylene bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride, isopropylidene-bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride, dimethyl Shirirenbisu (eta ^5-n-butyl cyclopentadienyl) titanium dichloride, diphenylsilylene bis (eta ^5-n-butyl cyclopentadienyl) titanium dichloride, methylene bis (eta
⁵ -tert-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (η ⁵ -ter
t- butyl cyclopentadienyl) titanium dichloride, dimethylsilylene bis (eta ^{5-tert-butylcyclopentadienyl)} titanium dichloride, diphenylsilylene bis (eta ^{5-tert-butylcyclopentadienyl)} titanium dichloride,

Methylenebis (η ⁵ -indenyl) titanium dichloride, isopropylidenebis (η ⁵ -indenyl) titanium dichloride, ethylenebis (η ⁵
- indenyl) titanium dichloride, dimethylsilylene bis (eta ⁵ - indenyl) titanium dichloride, diphenylsilylene bis (eta ⁵ - indenyl) titanium dichloride, methylene bis (eta ⁵ - methylindenyl) titanium dichloride, isopropylidene-bis (eta ⁵ - methyl indenyl) titanium dichloride, ethylenebis (eta ⁵ - methylindenyl) titanium dichloride, dimethylsilylene bis (eta ⁵ - methylindenyl) titanium dichloride, diphenylsilylene bis (eta ⁵ - methylindenyl) titanium dichloride, methylene bis (eta ⁵ - tetrahydroindenyl) titanium dichloride, isopropylidene-bis (eta ⁵ - tetrahydroindenyl) titanium dichloride, ethylenebis (eta ⁵ - Tet Tetrahydroindenyl)
Titanium dichloride, dimethylsilylene bis (η ⁵
-Tetrahydroindenyl) titanium dichloride,
Diphenylsilylene bis (eta ⁵ - tetrahydroindenyl) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - fluorenyl) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (eta ⁵ - fluorenyl) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl)
(Eta ⁵ - fluorenyl) titanium dichloride, diphenylsilylene (eta ⁵ - cyclopentadienyl) (eta ⁵ -
Transition metal compounds such as fluorenyl) titanium dichloride, compounds in which titanium of these compounds is changed to zirconium or hafnium, and compounds in which dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamide) or bis (diethylamide) And the like.

The transition metal compound represented by the general formula [II]
And μ-oxobis ｛bis (η^Five-Cyclopentadie
Nyl) titanium chloride｝, μ-oxobis ｛bis
(Η ^Five-Methylcyclopentadienyl) titanium chloride
Ride｝, μ-oxobis ｛bis (η^Five-Pentamethyl
Cyclopentadienyl) titanium chloride｝, μ-
Oxobis ｛(η^Five-Cyclopentadienyl) titanium
Muchloride｝, μ-oxobis ｛(η^Five-Cyclope
Nantadienyl) (methoxy) titanium chloride｝,
μ-oxobis ｛(η^Five-Cyclopentadienyl) (f
Enoxy) titanium chloride ニ ウ ム, μ-oxobis
｛(Η^Five-Cyclopentadienyl) (dimethylamino)
Titanium chloride｝, μ-oxobis ｛(η^Five−
Clopentadienyl) (diethylamino) titanium
Loride｝, μ-oxobis ｛isopropylidenebis
(Η^Five-Cyclopentadienyl) titanium chloride
｝, Μ-oxobis ｛dimethylsilylenebis (η^Five−
Cyclopentadienyl) titanium chloride｝, μ-
Oxobis ｛ethylenebis (η^Five-Cyclopentadieni
L) Titanium chloride｝, μ-oxobis ｛dimethi
Lucilylene bis (η^Five-Indenyl) titanium chlora
Id｝, μ-oxobis ｛ethylenebis (η^Five-Independence
Nyl) titanium chloride ニ ウ ム, μ-oxobis ｛iso
Propylidene (η^Five-Cyclopentadienyl) (η^Five−
Fluorenyl) titanium chloride｝, μ-oxobis
｛Dimethylsilylene (η^Five-Cyclopentadienyl)
(Tert-butylamino) titanium chloride｝,
μ-oxobis ｛dimethylsilylene (η^Five-Methylsic
Lopentadienyl) (tert-butylamino) titani
Um chloride｝, μ-oxobis ｛dimethylsilylene
(Η^Five-Tetramethylcyclopentadienyl) (ter
t-butylamino) titanium chloride
Titanium of these compounds is replaced with zirconium or hafni
Compound changed to chloride, chloride changed to methyl, benzyl
Methoxide, phenoxide, dimethylamide or
Transition metal compounds such as compounds converted to diethylamide
Things.

Further, as the transition metal compound represented by the general formula [II], for example, di-μ-oxobis オ bis (η ⁵
- cyclopentadienyl) titanium}, di -μ- Okisobisu {bis (eta ⁵ - methyl cyclopentadienyl) titanium}, di -μ- Okisobisu {bis (eta ⁵ - pentamethylcyclopentadienyl) titanium}, J-μ-
Okisobisu {(eta ⁵ - cyclopentadienyl) titanium dichloride}, di -μ- Okisobisu {(eta ⁵ - cyclopentadienyl) (methoxy) titanium}, di -μ-
Okisobisu {(eta ⁵ - cyclopentadienyl) (phenoxy) titanium}, di -μ- Okisobisu {(eta ⁵ - cyclopentadienyl) (dimethylamino) titanium}, di -μ- Okisobisu {(eta ⁵ - cyclo pentadienyl) (diethylamino) titanium}, di -μ- Okisobisu {isopropylidene bis (eta ⁵ - cyclopentadienyl) titanium}, di -μ- Okisobisu {dimethylsilylene bis (eta ⁵ - cyclopentadienyl) titanium }, di -μ- Okisobisu {ethylene bis (eta ⁵ - cyclopentadienyl) titanium}, di -μ- Okisobisu {dimethylsilylene bis (eta ⁵ - indenyl) titanium}, di -μ- Okisobisu {ethylene bis (eta ⁵ - indenyl) titanium}, di -μ- Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl Nil) (η ⁵ -fluorenyl) titanium｝, di-μ-oxobis ｛dimethylsilylene (η ⁵ -cyclopentadienyl) (tert-
Butylamino) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - methylcyclopentadienyl)
(Tert- butylamino) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (tert- butylamino) titanium} or the like, change titanium to zirconium or hafnium of these compounds And transition metal compounds such as the above compounds.

Specific examples of the transition metal compound represented by the general formula [III] include methylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (η ⁵ -cyclo Pentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( η ⁵ -cyclopentadienyl) (3-
Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, methylene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3-phenyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetra Methylcyclopentadienyl) (3
- trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-
Methoxy-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropylidene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (eta ⁵ - cyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert Butyl-5-methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3, 5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵
-Tetramethylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-phenyl-2 - phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl Enyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η
⁵ -tetramethylcyclopentadienyl) (3-ter
t- butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,

[0048] diphenylmethylene (eta ⁵ - cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-phenyl-2 phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3
- trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclo Pentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetra Methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride , diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5- Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride And compounds in which titanium is changed to zirconium or hafnium and dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamide) or bis (diethylamide). , (Η ⁵
- cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl)
(Η ⁵ -n-butylcyclopentadienyl), (η ⁵ -t
ert- butylcyclopentadienyl), (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -ter
t-butyldimethylsilylcyclopentadienyl),
(Η ⁵ -indenyl), (η ⁵ -methylindenyl),
(Eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to (3,5-dimethyl-2-phenoxy) the (2-phenoxy), (3-methyl-2-phenoxy), (3 , 5-Di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-)
Phenoxy) or a transition metal compound such as a compound changed to (3-trimethylsilyl-2-phenoxy),

Dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (eta ⁵ - cyclopentadienyl) (3
-Methyl-2-phenoxy) titanium dichloride,
Dimethyl cyclohexylene (eta ⁵ - cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3,5-di -te
rt- butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( eta ⁵ - cyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵
-Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (1-naphthoxy-2)
- yl) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl -2 −
Phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵
-Tetramethylcyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵
-Tetramethylcyclopentadienyl) (5-methyl-
3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethyl Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5
-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and η ⁵ -cyclopentadienyl of these compounds ⁵ -methylcyclopentadienyl, η ⁵
-Dimethylcyclopentadienyl,? ⁵ -trimethylcyclopentadienyl,? ⁵ -ethylcyclopentadienyl),? ^5- n-propylcyclopentadienyl,? ^5-
Isopropyl cyclopentadienyl, eta ^{5-n-butylcyclopentadienyl,} eta ^{5-sec-butylcyclopentadienyl,} eta ⁵ - isobutyl cyclopentadienyl, eta ^{5-tert-butylcyclopentadienyl,} eta ⁵
-Trimethylsilylcyclopentadienyl, η ⁵ -te
rt-butyldimethylsilylcyclopentadienyl, η
⁵ - phenyl-cyclopentadienyl, eta ⁵ - indenyl,
eta ⁵ - methylindenyl, eta ⁵ - phenyl indenyl or eta ⁵ - compound change fluorenyl, 2-phenoxy-3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert-butyl-dimethyl, Compounds in which silyl-2-phenoxy is changed, dimethylsilylene is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene, compounds in which titanium is changed to zirconium or hafnium, dichloride is dimethyl, dibenzyl, dimethoxide, diphenoxide, bis And transition metal compounds such as compounds changed to (dimethylamide) or bis (diethylamide).

The transition metal compound represented by the general formula [IV]
As a specific example, μ-oxobis ｛isopropylidene
(Η^Five-Cyclopentadienyl) (2-phenoxy) thio
Tantalum chloride, μ-oxobis isopropyl
Den (η^Five-Cyclopentadienyl) (2-phenoxy
C) Titanium methoxide, μ-oxobis isop
Lopiriden (η^Five-Cyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium
Muchloride｝, μ-oxobis ｛isopropylidene
(Η^Five-Cyclopentadienyl) (3-tert-butyl)
Ru-5-methyl-2-phenoxy) titanium methoxy
Do, μ-oxobis {isopropylidene (η ^Five−
Rucyclopentadienyl) (2-phenoxy) titanium
Muchloride｝, μ-oxobis ｛isopropylidene
(Η^Five-Methylcyclopentadienyl) (2-phenoxy
C) Titanium methoxide, μ-oxobis isop
Lopiriden (η^Five-Methylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) thio
Tantalum chloride, μ-oxobis isopropyl
Den (η^Five-Methylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium
Mumethoxide｝, μ-oxobis ｛isopropylidene
(Η^Five-Tetramethylcyclopentadienyl) (2-f
Enoxy) titanium chloride ニ ウ ム, μ-oxobis
｛Isopropylidene (η^Five-Tetramethylcyclopenta
Dienyl) (2-phenoxy) titanium methoxy
Do, μ-oxobis {isopropylidene (η^Five-Tet
Lamethylcyclopentadienyl) (3-tert-butyl)
Ru-5-methyl-2-phenoxy) titanium chloride
Do, μ-oxobis {isopropylidene (η^Five-Tet
Lamethylcyclopentadienyl) (3-tert-butyl)
Ru-5-methyl-2-phenoxy) titanium methoxy
Do,

Μ-oxobis ｛dimethylsilylene (η ⁵
-Cyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛dimethylsilylene (η ⁵ − Cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵ −
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium methoxide {, μ
- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis ｛dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵
-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium Chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium methoxide and the like, compounds in which titanium is changed to zirconium or hafnium, compounds in which chloride is changed to methyl, benzyl, phenoxide, dimethylamide or diethylamide, (η ⁵ -cyclopentadienyl) To (η ⁵
- dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadienyl), (eta ⁵ - trimethylsilyl cyclopentadienyl), (eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl), (eta ⁵ - indenyl)
(Eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to
(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).

Specific examples of the transition metal compound represented by the general formula [V] include di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy)
Titanium, di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-
μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium},
Di-μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium, di-μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η ⁵ -tetramethyl) Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium},

Di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert- Butyl-5-methyl-2-phenoxy) titanium}, di-
μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium},
Di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethyl) Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium}, a compound in which titanium of these compounds is changed to zirconium or hafnium, (η ⁵ -cyclopentadienyl) is replaced by (η ⁵ -dimethylcyclopentadienyl), (η ^Five
- trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadienyl), (eta ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert - butyldimethylsilyl cyclopentadienyl), (eta ⁵ - indenyl), (eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to (2-phenoxy ) Is (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy),
(3,5-di-tert-butyl-2-phenoxy),
Compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy) are exemplified.

(B) Aluminum Compound The aluminum compound (B) used in the present invention is at least one aluminum compound selected from the following (B1) to (B3). (B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3) having a structure represented by _b the formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (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 are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. In the formula, c represents an integer of 1 or more.) As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and 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.

[0056] 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 that this is a mixture of 2) and (B3).

In the present invention, the above-mentioned (B1) 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 a general formula BQ ¹ Q ² Q ³ , (C2) a boron compound represented by a 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 each preferably represent 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 ⁴ are each a halogenated hydrocarbon group, and particularly preferably, each of Q ^{1 to} Q ⁴ is a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom. And most preferably each of Q ^{1 to} Q ⁴ is a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom.

Specific examples of compound (C1) include 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⁺(BQ¹Q^TwoQ^ThreeQ^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
¹Q^TwoQ ^ThreeQ^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).

[0066] 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.

As specific combinations of these, 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, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) 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.

(D) Modified Aluminum Oxy Compound The modified aluminum oxy compound used in the present invention includes (D1) an aluminum oxy compound and (D)
2) General formula BQ ¹ Q ² Q ³ (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, An alkoxy group or a di-substituted amino group, which may be the same or different.)

(D1) Aluminum oxy compound In producing the modified aluminum oxy compound of the present invention, an aluminum oxy compound is used. Examples of such aluminum oxy compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane, pentylaluminoxane, hexylaluminoxane and the like.

The aluminum oxy compound (D1) used in the present invention includes the following (D1a) and / or (D1a)
1b) is preferred. (D1a) Cyclic aluminoxane having a structure represented by the general formula ｛-Al (E ² ) -O-｝ _b (D1b) General formula E ³ ｛-Al (E ³ ) -O-｝ _c Al
E ³ linear aluminoxane having a structure represented by ₂ (but are each E ² and E ³ is a hydrocarbon group, all of E ² and all E ³ may or may not be the same. b represents an integer of 2 or more, and c represents an integer of 1 or more.
It is the same as 3). The most preferred aluminum oxy compound (D1) used in the present invention is isobutylaluminoxane. In the present invention, as the (D1) aluminum oxy compound, only one kind may be used, or two or more kinds may be used in combination.

(D2) Boron Compound The boron compound represented by the general formula BQ ¹ Q ² Q ³ used in producing the modified aluminum oxy compound of the present invention is the same as that described in the above (C1). is there.

As specific examples of the compound (D2), 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.

The modified aluminum oxy compound (D) of the present invention is obtained by reacting (D1) an aluminum oxy compound and (D2) a boron compound represented by the general formula BQ ¹ Q ² Q ³ . Such a reaction is preferably performed under an inert gas atmosphere. The reaction temperature is usually -80
To 200 ° C, preferably -50 to 150 ° C. The higher the reaction temperature, the better, and the reaction temperature is more preferably 50 to 150 ° C. Reaction time is usually 1
Minutes to 20 hours, preferably 2 minutes to 15 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 molar ratio (molar ratio) of each component in the present invention is not particularly limited, but the molar ratio of component (D1) to component (D2) is usually (D1) :( D2) =
A molar ratio in the range of 1: 3 to 1: 0.01 is employed,
Preferably, the molar ratio is in the range of 1: 1 to 1: 0.05.

The (D) of the present invention obtained by such a reaction
The modified aluminum oxy compound can be used as a catalyst component for olefin polymerization after isolation and purification such as recrystallization, but the reaction solution can be used as it is as a catalyst component for olefin polymerization.

[Polymerization of olefin] In the present invention,
An olefin polymerization catalyst obtained by bringing the above (A), (C) and (D) into contact with each other or (B) is used. The contact here means any method as long as the above (A), (C) and (D) or (B) comes into contact and a catalyst is formed, and may be diluted or diluted with a solvent in advance. A method of mixing the above (A), (C) and (D) or further (B) and contacting them, or a method of separately supplying them to a polymerization tank and contacting them in the polymerization tank to form a catalyst, etc. Can be adopted. 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 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 2,000.
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, and the ratio of (D) / [transition metal compound (A) Transition metal atom included] is usually 0.1 to 10,000.
Therefore, it is desirable to use each component so as to be preferably in the range of 5 to 2000.

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 0.001
~ 100 mmol / L, more preferably 0.05 ~
50 mmol / L, (B) and (D)
Usually 0.01 to 5000 mmol / L in terms of 1 atom
And more preferably, 0.1 to 2500 mmol / L,
More preferably, 0.1 to 2000 mmol / L,
(C) is usually from 0.001 to 500 mmol / L, preferably from 0.01 to 250 mmol / L, and more preferably from 0.05 to 100 mmol / L. desirable.

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 slurry state in which the components are suspended 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 and 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 having 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 of normal pressure to 350 MPa, preferably normal pressure to 300 MPa, particularly preferably 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 suitably performed 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. Generally, 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 tank type-tank type or 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 possible to produce olefin polymers having different properties by changing the temperature, pressure, and gas composition for each nuclear reaction zone.

The polymerization time is generally determined appropriately depending on the kind of the target polymer and the reaction apparatus, and there are no particular restrictions, 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.

[0087]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. 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: Determined using gel permeation chromatograph (150, C manufactured by Waters) under the following conditions. 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

Reference Example 1 (Transition metal compound: dimethyl
Rylene (η^Five-Tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy
B) Synthesis example of titanium dimethoxide <compound>) In a Schlenk tube, methanol was added to 10 ml of anhydrous ether.
0.131 g (4.1 mmol) is dissolved, and -78 ° C
Of methyl lithium with a concentration of 1.05 mol / L
The solution (3.9 ml, 4.1 mmol) was added dropwise. 20
Temperature to ℃ and confirm the end of gas generation,
After confirming the formation of lithium methoxide, cool to -78 ° C again.
Rejected. Prepared in another Schlenk tube in advance
Tylsilylene (η^Five-Tetramethylcyclopentadienyl
) (3-tert-butyl-5-methyl-2-pheno)
0.919 g of (xy) titanium dichloride (2.0 mm
ol) in 20 ml of anhydrous ether
After the transfer, the temperature was gradually raised to room temperature. Reaction solution
After concentration, 20 ml of toluene was added, and insolubles were removed by filtration.
The filtrate is concentrated, and dimethylsilylene (η^Five−
Tetramethylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium
Toxide (hereinafter referred to as “compound”) is converted into yellow crystals
And got. (0.86 g, 95%)   ¹H-NMR (270 MHz, C₆D₆) Δ7.26
(M, 2H), 4.13 (s, 6H), 2.33 (s,
3H), 1.97 (s, 6H), 1.89 (s, 6
H), 1.59 (s, 9H), 0.55 (s, 6H)

Example 1 (1) A dropping funnel was attached to a 50 ml three-necked flask, and after purging with nitrogen, a thermometer was attached. Polybutylaluminoxane (PBAO,
Tosoh Akzo, hexane solution: 0.68 mol /
l) 1.9 ml was charged into a flask and stirred. Trispentafluorophenylborane (Tosoh Akzo, I
5 ml of sopar-E solution (52.9 mmol / l) was charged into a dropping funnel and dropped at 25 to 30 ° C. After completion of the dropwise addition, the mixture was stirred at 25 to 30 ° C for 4 hours. A pale yellow transparent solution (hereinafter referred to as "compound A solution") was obtained (the Al concentration was 0.19 mol / l based on the charged amount).

Example 1 (2) After replacing an autoclave type reactor equipped with a stirring blade having a capacity of 0.4 liter with argon, the reactor was charged with 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin. Was heated to 180 ° C. After raising the temperature, the ethylene pressure was increased to 2.5
Feed while adjusting to Mpa, and after the system is stabilized,
2.6 ml of the compound A solution (0.5 mm in terms of Al atom)
ol) and a heptane solution in which the compound and triisobutylaluminum are mixed (the concentration of the compound is 1 μm).
mol / ml, the concentration of triisobutylaluminum is 5
At 0 μmol / ml, the molar ratio of Al atoms to Ti atoms is 5
Adjusted to zero. ) In 0.5 ml (i.e., the compound
5 μmol, 25 μmo triisobutylaluminum
l) and N, N-dimethylanilinium (tetrakispentafluorophenyl) borate (hereinafter referred to as “compound”) in heptane slurry (concentration: 1 μmo
1 / ml). Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 0.82 dl / g, SCB was 32.6, melting points were 76.1 ° C. and 88.3 ° C., Mw
Was 48700 and Mw / Mn was 2.4 to obtain 6.04 g of an ethylene-hexene-1 copolymer. The polymerization activity per mole of Ti atom was 1.2 × 10 ⁷ g /
Timol.

Example 2 (1) A dropping funnel was attached to a 50 ml three-necked flask, and after purging with nitrogen, a thermometer was attached. Polybutylaluminoxane (PBAO,
Tosoh Akzo, hexane solution: 0.68 mol /
l) 1.28 ml was charged into a flask and stirred. 10 ml of trispentafluorophenylborane (Isopar-E solution: 52.9 mmol / l) was charged into a dropping funnel and dropped at 25 to 30 ° C. After dropping, 25-
The mixture was stirred at 30 ° C. for 4 hours. A light yellow transparent solution (hereinafter referred to as “compound B solution”) was obtained (from the charged amount,
Al concentration is 0.08 mol / l).

Example 2 (2) After replacing an autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged into the reactor. Was heated to 180 ° C. After raising the temperature, the ethylene pressure was increased to 2.5
Feed while adjusting to Mpa, and after the system is stabilized,
0.2 mmol of triisobutylaluminum and 0.31 ml of the compound B solution (0.025 mm in terms of Al atom)
ol) and a heptane solution in which the compound and triisobutylaluminum are mixed (the concentration of the compound is 1 μm).
mol / ml, the concentration of triisobutylaluminum is 5
At 0 μmol / ml, the molar ratio of Al atoms to Ti atoms is 5
Adjusted to zero. ) In 0.5 ml (i.e., the compound
5 μmol, 25 μmo triisobutylaluminum
l) and a heptane slurry of the compound (concentration is 1 μm)
(mol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 1.09 dl / g, SCB
32.0, melting points 78.6 ° C and 89.3 ° C, M
ethylene with w of 59100 and Mw / Mn of 2.4
2.90 g of hexene-1 copolymer was obtained. The polymerization activity per mole of Ti atom is 5.8 × 10 ⁶ g per 2 minutes.
/ Timol.

[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 as a solvent and 15 ml of hexene-1 as an α-olefin were charged.
The temperature was raised to 0 ° C. After raising the temperature, the ethylene pressure was increased to 2.5 MPa
After the system was stabilized and the system was stabilized, 0.2 mmol of triisobutylaluminum, a heptane solution in which the compound and triisobutylaluminum were mixed (the concentration of the compound was 1 μmol / ml, and the concentration of triisobutylaluminum was 50 μmol / 0.5 m
1 (ie, 0.5 μmol of the compound and 25 μmol of triisobutylaluminum), followed by a heptane slurry of the compound (slurry concentration, 1 μmol / m
l) 1.5 ml was charged. Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 1.04 dl / g and SCB was 31.
7, melting point of 78.3 ° C and 89.9 ° C, Mw of 565
00, ethylene-hexene having Mw / Mn of 1.9
2.33 g of 1 copolymer was obtained. The polymerization activity per mole of Ti atom was 4.7 × 10 ⁶ g / Timo per 2 minutes.
l.

[Comparative Example 2] 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 as a solvent and 15 ml of hexene-1 as an α-olefin were charged.
The temperature was raised to 0 ° C. After raising the temperature, the ethylene pressure was increased to 2.5 MPa
After the system was stabilized and the system was stabilized, 0.72 ml of polybutylaluminoxane (PBAO, manufactured by Tosoh Akzo Co., Ltd., hexane solution: 0.68 mol / l) (A
and a heptane solution in which the compound and polybutylaluminoxane were mixed (the concentration of the compound was 1 μmol / ml, the concentration of the polybutylaluminoxane was 50 μmol / ml, and the molar ratio of Al atom to Ti atom was Was adjusted to 50).
(That is, 0.5 μmol of the compound and 25 μmol of polybutylaluminoxane) and 1.5 ml of a heptane slurry of the compound (concentration: 1 μmol / ml) were added. Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was set to 0.
98, SCB 34.8, melting point 73.6 ° C and 8
2.20 g of an ethylene-hexene-1 copolymer having 4.9 ° C., Mw of 56300, and Mw / Mn of 2.4 was obtained.
3. The polymerization activity per mole of Ti atom is 4 minutes.
It was 4 × 10 ⁶ g / Timol.

Example 3 (1) A dropping funnel was attached to a 50 ml three-necked flask, and after purging with nitrogen, a thermometer was attached. Polybutylaluminoxane (PBAO,
Tosoh Akzo, hexane solution: 0.68 mol /
l) 10 ml was charged into a flask and stirred. Trispentafluorophenylborane (toluene solution: 0.19
mol / l) 3.6 ml was charged into a dropping funnel, and 25 to 25
It was added dropwise at 30 ° C. After completion of the dropping, at 30 ° C. for 20 minutes,
The mixture was stirred at 60 ° C for 3 hours and at 80 ° C for 1 hour. A pale yellow transparent solution (hereinafter referred to as "compound C solution") was obtained (the Al concentration was 0.5 mol / l based on the charged amount).

Example 3 (2) After replacing an autoclave-type reactor equipped with a stirring blade having a capacity of 0.4 liter with argon, the reactor was charged with 140 ml of cyclohexane as a solvent and 60 ml of hexene-1 as an α-olefin. Was heated to 180 ° C. After raising the temperature, the ethylene pressure was increased to 2.5
Feed while adjusting to Mpa, and after the system is stabilized,
2 ml of the compound C solution (corresponding to 1 mmol in terms of Al atom), 0.5 ml of a toluene solution of bis (η ⁵ -n-butylcyclopentadienyl) zirconium dichloride (concentration: 1 μmol / ml), and triisobutylaluminum Heptane solution (concentration is 1 mmol /
0.05 ml) and 1.5 ml of a compound heptane slurry (concentration: 1 μmol / ml). Polymerization was performed for 2 minutes. As a result of the polymerization, 3.75 g of an ethylene-hexene-1 copolymer was obtained. The polymerization activity per mole of Ti atom is 7.5 × 10 ⁶ g / T per 2 minutes.
imol.

Comparative Example 3 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon.
140 ml of cyclohexane as a solvent and 60 ml of hexene-1 as an α-olefin were charged.
The temperature was raised to 0 ° C. After raising the temperature, the ethylene pressure was increased to 2.5 MPa
After the system was stabilized and the system was stabilized, methyl isobutylaluminoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd., heptane solution: 1.77 mol / l) was added to 0.1%.
56 ml (corresponding to 1 mmol in terms of Al atom) and a toluene solution of bis (η ⁵ -n-butylcyclopentadienyl) zirconium dichloride (concentration 1 μmol / m
l) 1 ml was charged. Polymerization was performed for 2 minutes. As a result of the polymerization, 1.0 g of an ethylene-hexene-1 copolymer was obtained.
The polymerization activity per mole of Ti atom was 1.
It was 0 × 10 ⁶ g / Timol.

Comparative Example 4 (1) A dropping funnel was attached to a 50 ml three-necked flask, and after purging with nitrogen, a thermometer was attached. Polybutylaluminoxane (PBAO,
Tosoh Akzo, hexane solution: 0.96 mol /
l) was charged into a flask and stirred. Trispentafluorophenylborane (toluene solution: 0.2
0 mol / l) 9.4 ml was charged into a dropping funnel, and 25
It was added dropwise at ３０30 ° C. After completion of the dropwise addition, the temperature was raised to 95 ° C., and the mixture was stirred for 8 hours. A pale yellow transparent solution (hereinafter referred to as “compound D solution”) was obtained (from the amount charged, Al
The concentration is 0.49 mol / l).

[Comparative Example 4 (2)] After replacing an autoclave type reactor equipped with a stirring blade having a capacity of 0.4 l with argon, 140 ml of cyclohexane as a solvent and 60 ml of hexene-1 as an α-olefin were charged into the reactor. Was heated to 180 ° C. After raising the temperature, the ethylene pressure was increased to 2.5
Feed while adjusting to Mpa, and after the system is stabilized,
1.04 ml of the compound D solution (0.5 m in terms of Al atom)
mol), and a heptane solution in which bis-n-butylcyclopentadienyl zirconium dichloride (hereinafter referred to as “compound”) and triisobutylaluminum are mixed (the concentration of the compound is 1 μmol / ml, and the concentration of triisobutylaluminum is 50 μmol / ml
The molar ratio between Al atoms and Zr atoms was adjusted to 50. )
(I.e., 0.5 μmol of the compound and 25 μmol of triisobutylaluminum). 2
Polymerization was performed for minutes. As a result of polymerization, [η] was 0.49 dl.
/ G, SCB 9.3, melting point 111.2 ° C and 11
5.5 ° C., Mw: 20,700, Mw / Mn: 2.01,
1.37 g of ethylene-hexene-1 copolymer was obtained. The polymerization activity per mole of Zr atom is 2 minutes,
It was 2.7 × 10 ⁶ g / Zrmol.

[0104]

As described in detail above, according to the present invention, a highly active catalyst for olefin polymerization and a method for efficiently producing an olefin polymer are 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.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C07F 19/00 C07F 19/00 F term (reference) 4H048 AA03 AB40 VA10 VA20 VA75 VA80 4H049 VN01 VN05 VP01 VP02 VU14 VW10 4H050 AA03 AB40 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA03B BA04B BB01B BB02B BC12B BC13B BC15B BC16B BC17B BC25B BC27B EA01 EB02 EB04 EB05 EB07 EB09 EB10 EC02 FA01 FA02 FA04 FA07 FA10 GB01

Claims (12)

[Claims] 1. The following (A), (B), (C) and (D)
Or (A), (C) and
An olefin polymerization catalyst obtained by contacting (D). (A) a group having a cyclopentadiene-type anion skeleton
Group 4 transition metal compound having (B) at least one selected from the following (B1) to (B3)
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
_TwoLinear aluminoxane having a structure represented by the following formula (provided that 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
(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 and (LH)⁺Is Bren
Sted acid. (D) (D1) an aluminum oxy compound, and (D)
2) General formula BQ¹Q^TwoQ ^Three(However, B is trivalent valence
Is a boron atom in the form¹~ Q^ThreeIs a halogen atom, carbonized
Hydrogen group, halogenated hydrocarbon group, substituted silyl group, alcohol
Xy or disubstituted amino groups which are the same
Or different. ) Boron compound
Aluminum oxy compound obtained by reacting 2. The olefin polymerization catalyst according to claim 1, wherein (D1) is the following (D1a) and / or (D1b). (D1a) Cyclic aluminoxane having a structure represented by the general formula ｛-Al (E ² ) -O-｝ _b (D1b) General formula E ³ ｛-Al (E ³ ) -O-｝ _c Al
E ³ linear aluminoxane having a structure represented by ₂ (but are each E ² and E ³ is a hydrocarbon group, all of E ² and all E ³ may or may not be the same. b represents an integer of 2 or more, and c represents an integer of 1 or more.) 3. The olefin polymerization catalyst according to claim 1, wherein Q ^{1 to} Q ³ are each a halogenated hydrocarbon group. 4. The method according to claim 1, wherein (D) is (D1) and (D2) is 50
The catalyst for olefin polymerization according to any one of claims 1 to 3, which is a modified aluminum oxy compound obtained by reacting at from 150 to 150 ° C. 5. A compound represented by the following general formula [I] or [II]:
The olefin polymerization catalyst according to any one of claims 1 to 4, which is a transition metal compound represented by the following formula: _{^{Cp m MX 1 4-m [}} I] (Cp p MX 1 q) 2 X 2 r [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. X ¹ is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It represents an aralkyloxy group, an aryloxy group, a disubstituted amino group, an alkylthio group, an aralkylthio group, an arylthio group, an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² is the sixteenth element of the periodic table
Indicates a group atom. m is an integer satisfying 1 ≦ m ≦ 4, p is a number satisfying 1 ≦ p ≦ 3, and q is 0 ≦ q ≦
Is a number that satisfies 2, r is 1 or 2, and is an integer that satisfies p + q + r = 4. When a plurality of Cp, X ¹ and X ² are present in one molecule, they may be the same or different. In addition, a plurality of Cp,
A plurality of X ^{1 s} , or Cp and X ¹ may be bonded directly or via a cross-linking group. ) 6. The olefin polymer according to claim 5, wherein (A) is a transition metal compound represented by the general formula [I] or [II] wherein Cp and X ¹ are bonded via a crosslinking group. catalyst. (A) is a transition metal compound in which m in the general formula [I] is 1, or p in the general formula [II].
7. The catalyst for olefin polymerization according to claim 5, wherein the catalyst is a transition metal compound wherein is 1. 8. The method according to claim 1, wherein (A) is a transition metal compound represented by the following general formula [III], [IV] or [V].
4. The catalyst for olefin polymerization according to any one of 4. (In the general formulas [III], [IV] and [V], M represents a transition metal atom belonging to Group 4 of the periodic table of the element, and A represents an atom belonging to Group 16 of the periodic table of the element.) Show, J
Represents an atom belonging to Group 14 of the periodic table of the elements. Cp represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , 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, a substituted silyl group, an alkoxy group, an aralkyloxy group An aryloxy group, a disubstituted amino group,
Alkylthio group, aralkylthio group, arylthio group,
It represents an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² represents an atom of Group 16 of the periodic table of the element. 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 ¹ , X ² , R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different. ) 9. The catalyst for olefin polymerization according to claim 1, wherein (B) is triethylaluminum, triisobutylaluminum, methylaluminoxane, or butylaluminoxane. 10. The polymerization catalyst system according to claim 1, wherein (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 11. 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 1 to 10. 12. The method according to claim 1, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.
1. The method for producing the olefin polymer according to 1.