JP2002293818A - Catalyst for olefin polymerization and production method of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high active catalyst for olefin polymerization which is prepared using a metallocene transition metal compound and to provide an efficient production method of an olefin polymer using the catalyst. SOLUTION: The catalyst is obtained by contacting the following (A), (B), (C) and (D). The production method uses the catalyst. (A): a transition metal compound represented by the formula CpYMX<1> 2 [I] or (CpYMX<1> n )2 X<2> 2-n [II] [wherein, M is a transition metal atom of the group 4; X<1> is a halogen atom or alkyl group or the like; X2 is an atom of the group 16; Y is a σ-bond group to M through an atom of the group 15 or 16; Cp and Y are bond directly or through a crosslinking group; n is 0 or 1], (B): a specific organoaluminum compound, (C): a specific boron compound, (D): an amine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a highly active olefin polymerization catalyst prepared by using a metallocene transition metal compound and a method for efficiently producing an olefin polymer using the olefin polymerization catalyst.

[0002]

2. Description of the Related Art Many reports have already been made on a method for producing an olefin polymer using a metallocene complex. For example, in JP-A-58-19306,
A method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported. This screw (η
^In a method for producing an olefin polymer using ⁵ -cyclopentadienyl) zirconium dichloride and methylaluminoxane, the activity is insufficient from an industrial viewpoint, and the molecular weight of the obtained olefin polymer is low. Was something.

JP-A-11-152306 discloses a method for polymerizing ethylene using a catalyst prepared from pentafluoroaniline, triisobutylaluminum, and ethylenebisindenylzirconium dichloride. From a viewpoint, its activity was insufficient.

Japanese Patent Application Laid-Open No. 7-501846 discloses a catalyst prepared from N, N-dimethylaniline, methylaluminoxane, and dimethylsilylene (tert-butylamino) (η ⁵ -tetramethylcyclopentadienyl) titanium dichloride. The method of copolymerizing ethylene and 1-butene by using is reported, but its activity was insufficient from an industrial viewpoint.

[0005] JP-A-7-157509 uses a catalyst prepared from ethylenebisindenyl zirconium dichloride, triisobutylaluminum, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and a Lewis base. Although ethylene polymerization has been reported, its activity was insufficient from an industrial viewpoint.

In Japanese Patent Application Laid-Open No. 9-87313, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, triisobutylaluminum and N A method for producing a copolymer of ethylene and hexene-1 using a catalyst prepared from N, N-dimethylanilinium tetrakispentafluorophenylborate has been reported. Although the union has been obtained with high activity, further improvement in activity has been desired from an industrial viewpoint.

[0007]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a highly active olefin polymerization catalyst prepared by using a metallocene transition metal compound, and an efficient olefin using the olefin polymerization catalyst. An object of the present invention is to provide a method for producing a polymer.

[0008]

Means for Solving the Problems The present invention provides the following (A):
The object is achieved by a catalyst for olefin polymerization obtained by bringing (B), (C) and (D) into contact with each other, and a method for producing an olefin polymer using the catalyst for olefin polymerization. (A) A transition metal compound represented by the following general formula [I] or [II]. _{^{CpYMX 1 2 [I] (CpYMX}} 1 n) , respectively, in ^{_{2 X 2 2-n [II}} ] ( 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 represents 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. Y represents a group which is σ-bonded to M via an atom of Group 15 or Group 16 of the periodic table of the element, and Cp and Y are bonded directly or via a bridging group. n is 0 or 1. When a plurality of Cp, Y, M, X ¹ and X ² are present in one molecule, they may be the same or different. ) (B) the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E may or may not be the same.
Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a is a number satisfying 0 <a ≦ 3. (C): a boron compound represented by any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a general formula G ⁺ (BQ ^{1 Q 2 Q 3 Q 4)} - boron compound represented by (C3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent atom Is a valence boron atom, and 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 or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. (D): amine compound

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (A) Transition metal compound The transition metal compound used in the present invention is represented by the following general formula [I]
Or a transition metal compound represented by [II]. _{^{CpYMX 1 2 [I] (CpYMX}} 1 n) , respectively, in ^{_{2 X 2 2-n [II}} ] ( 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 represents 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. Y represents a group which is σ-bonded to M via an atom of Group 15 or Group 16 of the periodic table of the element, and Cp and Y are bonded directly or via a bridging group. n is 0 or 1. When a plurality of Cp, Y, M, X ¹ and X ² are present in one molecule, they may be the same or different. )

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

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

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.

The alkyl group in the substituent X ¹ includes:
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, a benzyl group, a (2-methylphenyl) methyl group,
(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,
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 thereof include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable. All of these aryl 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 substituted silyl group in the substituent X ¹ is a silyl group substituted with a hydrocarbon group. Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n -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, and preferably trimethylsilyl group and 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, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy. ,
tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-
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 in the substituent X ¹ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, 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, for example, 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 aralkyl seleno groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The arylseleno group in the substituent X ¹ is preferably an arylseleno group having 6 to 20 carbon atoms, such as phenylseleno, 2-methylphenylseleno, 3-methylphenylseleno, and 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 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 ² in the general formula [II] represents an atom belonging to Group 16 of the periodic table of the elements, and specific examples thereof include an oxygen atom, a sulfur atom, and a selenium atom. It is a sulfur atom, more preferably an oxygen atom.

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

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

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

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

In the above general formulas [I] and [II], Cp and Y are bonded directly or via a crosslinking group. As the crosslinking group, the 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 divalent cross-linking group in which the atom bonding to Cp or Y is a carbon atom and / or a silicon atom, still more preferably, the atom bonding to Cp or Y is a carbon atom and / or a silicon atom. , Cp or Y is a divalent bridging group having a minimum number of atoms of 3 or less (including a single atom bonding to Cp or Y). More specifically, methylene, ethylene, propylene, dimethylmethylene (isopropylidene), diphenylmethylene, tetramethylethylene, silylene, dimethylsilylene, diethylsilylene, diphenylsilylene, tetramethyldiethylene Examples thereof include a silylene group and a dimethoxysilylene group, and particularly preferred are a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group, and a diphenylsilylene group.

The transition metal compound [I] or [II]
Specific examples of the transition metal compound represented by dimethylsilylene (methylamino) (cyclopentadienyl) titanium dichloride, dimethylsilylene (tert-
Butylamino) (cyclopentadienyl) titanium dichloride, dimethylsilylene (phenylamino) (cyclopentadienyl) titanium dichloride, dimethylsilylene (cyclohexylamino) (cyclopentadienyl) titanium dichloride, and cyclopentane of these compounds Dienyl is methylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, t
tert-butylcyclopentadienyl, di-tert-
Butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, methylindenyl, a compound in which phenylindenyl or fluorenyl is changed, dimethylsilylene is converted to diethylsilylene, diphenylsilylene, methylene, ethylene or isopropyl Compounds changed to redene, compounds changed from titanium to zirconium or hafnium, compounds changed from dichloride to dimethyl, dimethoxide, bis (dimethylamide) or bis (diethylamide),

Μ-oxobis {dimethylsilylene (methylamino) (cyclopentadienyl) titanium chloride}, μ-oxobis {dimethylsilylene (tert)
-Butylamino) (cyclopentadienyl) titanium chloride｝, μ-oxobis ｛dimethylsilylene (phenylamino) (cyclopentadienyl) titanium chloride｝, μ-oxobis ｛dimethylsilylene (cyclohexylamino) (cyclopentadienyl) Titanium chloride｝ and the like, and cyclopentadienyl of these compounds are replaced with methylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl,
n-butylcyclopentadienyl, tert-butylcyclopentadienyl, di-tert-butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, methylindenyl, phenylindenyl or Compounds changed to fluorenyl, compounds changed to dimethylsilylene for diethylsilylene, diphenylsilylene, methylene, ethylene or isopropylidene, compounds changed to titanium for zirconium or hafnium, compounds changed to chloride for methyl, methoxide, dimethylamide or diethylamide And

Di-μ-oxobis {dimethylsilylene (methylamino) (cyclopentadienyl) titanium}, di-μ-oxobis {dimethylsilylene (ter)
t-butylamino) (cyclopentadienyl) titanium, di-μ-oxobis {dimethylsilylene (phenylamino) (cyclopentadienyl) titanium}, di-μ-oxobis {dimethylsilylene (cyclohexylamino) (cyclopentane) Dienyl) titanium} or the like, and cyclopentadienyl of these compounds is converted to methylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl. Enyl, di-tert-butylcyclopentadienyl, te
rt-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, methylindenyl, a compound modified to phenylindenyl or fluorenyl,
Examples include compounds in which dimethylsilylene is changed to diethylsilylene, diphenylsilylene, methylene, ethylene or isopropylidene, and compounds in which titanium is changed to zirconium or hafnium.

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 above general formulas [III], [IV] or [V], M represents a transition metal atom of Group 4 of the periodic table of the element, and A represents an atom of 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. Multiple M, A, J, C
p, 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 aryl group. It is an oxy group, and among them, 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 general formulas [III], [IV] and [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], the atoms of Group 16 of the periodic table of the element represented by A include, for example, an oxygen atom, a sulfur atom and a selenium atom. Preferably, it is an oxygen atom.

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

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, 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,

Diphenylmethylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η 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 (dimethylamino) or bis (diethylamino). , (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^Five-Cyclopentadi
Enyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (η^Five-Cyclopentadienyl) (3
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilene (η^Five-Cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium
Dichloride, dimethylsilylene (η^Five-Cyclopentane
Dienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethyl silyl
(Η^Five-Cyclopentadienyl) (3,5-di-te
rt-butyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titani
Um dichloride, dimethylsilylene (η^Five-Cyclope
Antadienyl) (3-tert-butyldimethylsilyl)
-5-methyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Cyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichlorai
Dimethylsilylene (η^Five-Cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Cyclopentadienyl) (3,5-diamyl-2-f
Enoxy) titanium dichloride, dimethylsilylene
(Η^Five-Cyclopentadienyl) (1-naphthoxy-2
-Yl) titanium dichloride, dimethylsilylene
(Η^Five-Tetramethylcyclopentadienyl) (2-f
Enoxy) titanium dichloride, dimethylsilylene
(Η ^Five-Tetramethylcyclopentadienyl) (3-meth
Tyl-2-phenoxy) titanium dichloride, dime
Tylsilylene (η^Five-Tetramethylcyclopentadienyl
) (3,5-dimethyl-2-phenoxy) titanium
Dichloride, dimethylsilylene (η^Five-Tetramethyl
Cyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, dimethyl silyl
(Η^Five-Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) tita
Dichloride, dimethylsilylene (η^Five-Tetra
Methylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (η^Five-Tetramethylcyclopentadi
Enyl) (5-methyl-3-phenyl-2-phenoxy)
C) Titanium dichloride, dimethylsilylene (η^Five
-Tetramethylcyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Tetramethylcyclopentadienyl) (5-methyl-
3-trimethylsilyl-2-phenoxy) titaniumdi
Chloride, dimethylsilylene (η^Five-Tetramethylsi
Clopentadienyl) (3-tert-butyl-5-meth
Toxi-2-phenoxy) titanium dichloride, di
Methylsilylene (η^Five-Tetramethylcyclopentadie
Nyl) (3-tert-butyl-5-chloro-2-fe
Noxy) titanium dichloride, dimethylsilylene
(Η^Five-Tetramethylcyclopentadienyl) (3,5
-Diamyl-2-phenoxy) titanium dichlorai
Dimethylsilylene (η^Five-Tetramethylcyclopen
Tadienyl) (1-naphthoxy-2-yl) titanium
Dichloride, etc., and η of these compounds^Five-Cyclope
Ntadienyl to η^Five-Methylcyclopentadienyl, η^Five
-Dimethylcyclopentadienyl, η^Five-Trimethylsi
Clopentadienyl, η^Five-Ethylcyclopentadienyl
, Η^Five-N-propylcyclopentadienyl, η^Five-B
Sopropylcyclopentadienyl, η^Five-N-butyl
Clopentadienyl, η^Five-Sec-butylcyclopen
Tadienyl, η^Five-Isobutylcyclopentadienyl,
η^Five-Tert-butylcyclopentadienyl, η^Five−
Limethylsilylcyclopentadienyl, η^Five-Tert
-Butyldimethylsilylcyclopentadienyl, η^Five−
Phenylcyclopentadienyl, η^Five-Indenyl, η^Five
-Methylindenyl, η^Five-Phenylindenyl or
η^Five-Compound substituted with fluorenyl, 2-phenoxy
With 3-phenyl-2-phenoxy, 3-trimethylsilyl
2-phenoxy or 3-tert-butyldimension
Compounds changed to tylsilyl-2-phenoxy, dimethyl
Rusilylene is converted to diethylsilylene, diphenylsilylene,
Or a compound changed to dimethoxysilylene, titanium
Compound changed to zirconium or hafnium
Substance, dichloride to dimethyl, dibenzyl, dimethoxy
, Diphenoxide, bis (dimethylamino) or
Transition gold such as a compound changed to
Genus compounds and the like.

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, dimethylamino or diethylamino, (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
A compound in which isopropylene is changed to methylene or ethylene, or dimethylsilylene is changed to diethylsilylene or diphenylsilylene, (2-phenoxy) is (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2)
-Phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy).

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-
Okisobisu {methylene (eta ⁵ - cyclopentadienyl)
(2-phenoxy) titanium}, di -μ- Okisobisu {methylene (eta ⁵ - cyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobismethylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobismethylene (η ⁵ -Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis {methylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium} , Di-μ-oxobis {methylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {ethylene (η ⁵ -cyclopenta Dienyl) (2-phenoxy)
Titanium｝, di-μ-oxobis ｛ethylene (η ⁵ −
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium｝, di-μ-oxobis {ethylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium｝, di-μ-oxobis ｛ethylene (η ⁵ -methylcyclopentadienyl) )
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {ethylene (η
⁵ - tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {ethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-t
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｝, di-μ-
Okisobisu {diethyl silylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {diethyl silylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2 -Phenoxy) titanium}, di-μ-oxobis {diethylsilylene (η ⁵ -methylcyclopentadienyl) (2-
Phenoxy) titanium}, di -μ- Okisobisu {diethyl silylene (eta ⁵ - methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {diethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2
-Phenoxy) titanium}, di-μ-oxobis {diethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {diphenyl Silylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium｝, di-μ-oxobis ｛diphenylsilylene (η ⁵ -cyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis} diphenylsilylene (η ⁵
-Methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {diphenylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {diphenylsilylene (η ⁵
-Tetramethylcyclopentadienyl) (2-phenoxy) titanium｝, di-μ-oxobis ｛diphenylsilylene (η ⁵ -tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium} and the like, and compounds in which titanium of these compounds is changed to zirconium or hafnium;
The - (eta ⁵ cyclopentadienyl) (η ⁵ - dimethyl cyclopentadienyl), (η ⁵ - trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert - butylcyclopentadienyl), (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) (3-methyl-2-phenoxy), (3,5
-Dimethyl-2-phenoxy), (3,5-di-ter
t-butyl-2-phenoxy), (3-phenyl-5-
Compounds changed to (methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy) are exemplified.

The transition metal compound represented by the general formula [III] is synthesized, for example, in the same manner as described in JP-A-9-87313. The transition metal compound represented by the general formula [IV] or [V] is obtained by, for example, reacting the transition metal compound represented by the general formula [III] with 0.5 times or 1 mole of water. It is manufactured by At this time, a method of directly reacting the transition metal compound with a required amount of water, a method of charging the transition metal compound into a solvent such as a hydrocarbon containing the required amount of water, and a method of adding the transition metal to a solvent such as a dried hydrocarbon. A method in which a compound is charged and an inert gas containing a required amount of water or the like is further allowed to flow can be adopted.

[0052] (B) an organoaluminum compound used in the organic aluminum compound present invention have the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E is be different even in the same Z is a hydrogen atom or a halogen atom, and all Zs may be the same or different; a represents a number satisfying 0 <a ≦ 3.) . E
Is preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group.

[0053] Specific examples of the organic aluminum compound represented by the general formula E _a AlZ _3-a, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; dimethylaluminum chloride, Dialkylaluminum chlorides such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; dimethylaluminum Idoraido, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride. More preferably, it is trialkylaluminum, and still more preferably, trimethylaluminum, triethylaluminum, or triisobutylaluminum.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one of boron compound represented by can be used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q ⁴ are each at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

Specific examples of the 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 or organic cation, and B is boron in a trivalent valence state. And Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as

[0058] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (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).

[0061] 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. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

(D) Amine compound As the amine compound used in the present invention, a primary amine compound is preferable. As such an amine compound, a compound represented by the general formula RNH ₂ (where R is 1 to 1 carbon atoms) is preferable.
Indicate 20 halogenated hydrocarbon groups. ).

The halogenated hydrocarbon group having 1 to 20 carbon atoms represented by the substituent R is preferably a fluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a fluoroethyl group, a perfluoroethyl group, a fluoropropyl group. , Perfluoropropyl group, fluorobutyl group,
Perfluorobutyl, perfluorohexyl, fluorophenyl, difluorophenyl, trifluorophenyl, perfluorophenyl, 3,5-bis (trifluoromethyl) phenyl, perfluoronaphthyl, fluorobenzyl , A perfluorobenzyl group, or a group obtained by changing the fluoro of these groups to chloro or bromo, more preferably a halogenated aryl group having 6 to 20 carbon atoms, and particularly preferably a perfluorobenzyl group. It is a phenyl group or a perfluoronaphthyl group.

Particularly preferred as such an amine compound is pentafluoroaniline.

[Polymerization of olefin] In the present invention,
An olefin polymerization catalyst obtained by contacting the above (A), (B), (C) and (D) is used. The contact here means any method as long as the above (A) to (D) come into contact with each other to form a catalyst. A method in which D) is mixed and brought into contact, or a method in which the components are separately supplied to a polymerization reactor and brought into contact in the polymerization reactor can be employed. In the present invention, when supplying the respective components to the polymerization reactor, the respective components can be charged and used in an arbitrary order, and can be obtained by bringing a combination of these optional components into contact with each other in advance. The reaction product obtained may be used.

The amount of each component used is usually such that the molar ratio of (B) / [transition metal atom contained in transition metal compound (A)] is from 0.1 to 10,000, preferably from 5 to 2,000.
The molar ratio of (C) / [the transition metal atom contained in the transition metal compound (A)] is 0.01 to 100, preferably 0.5.
Each component may be used such that the molar ratio of (D) / (the transition metal atom contained in the transition metal compound (A)) is from 0.1 to 10,000, and preferably from 5 to 2,000. desirable.

The concentration when each component is used in the form of a solution or suspended or slurried in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. Usually 0.001 to 200 mm in terms of transition metal atoms contained in the transition metal compound (A).
ol / L, more preferably 0.01 to 100 mmo
1 / L, more preferably 0.05 to 50 mmol /
L and (B) are usually 0.01 to 5000 mmol / L.
And more preferably 0.1 to 2500 mmol / L,
More preferably, 0.1 to 2000 mmol / L,
(C) is usually 0.001 to 500 mmol / L, more preferably 0.01 to 250 mmol / L, still more preferably 0.05 to 100 mmol / L, and (D)
Is preferably 0.01 to 5000 mmol / L, more preferably 0.1 to 2500 mmol / L, and still more preferably 0.1 to 2000 mmol / L.

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 can range from -50 ° C to 350 ° C, preferably from 0 ° C to 300 ° C, particularly preferably from 50 ° C to 300 ° C. Polymerization pressure is normal pressure ~
Although it can be in the range of 350 MPa, it is preferably normal pressure to 3 MPa.
00 MPa, particularly preferably normal pressure to 200 MPa.

The polymerization time is generally determined appropriately depending on the kind of the target polymer and the reaction apparatus, and there is no particular restriction. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0074]

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

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

(2) Content of the repeating unit derived from α-olefin in the copolymer of ethylene and α-olefin: infrared spectrophotometer (manufactured by PerkinElmer Co., Ltd.)
FTIR1600 series), ethylene and α-
It was determined from the characteristic absorption of the olefin and was 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.

(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: dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl)
(Synthesis example of (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide <compound>)] In a Schlenk tube, 0.131 g (4.1 mmol) of methanol is dissolved in 10 ml of anhydrous ether, and -78.
A 1.05 mol / L methyllithium ether solution (3.9 ml, 4.1 mmol) was added dropwise at a temperature of ° C.
The temperature was raised to 20 ° C., and by confirming the end of gas generation, the formation of lithium methoxide was confirmed.
And cooled. Dimethylsilylene prepared in advance in another Schlenk tube (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.919 g (2.0
(mmol) in 20 ml of anhydrous ether was transferred to the previous reaction, and then gradually warmed to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were removed by filtration. The filtrate was concentrated, the following structural formula dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl)
(3-tert-Butyl-5-methyl-2-phenoxy) titanium dimethoxide was obtained as yellow crystals. (0.86 g, 95%) ¹ H-NMR (270 MHz, C ₆ D ₆ ) 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 After replacing an autoclave type reactor equipped with stirring blades having a capacity of 0.4 l with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 180 ° C. Temperature. After raising the temperature, the ethylene pressure was increased to 2.5
Feeding while adjusting to MPa, after the system is stabilized,
0.3 mmol of triisobutylaluminum and 50 μmol of pentafluoroaniline (concentration: 10 μmol /
The ml of toluene solution 5ml use), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound) and triisobutylaluminum in a heptane solution (compound concentration is 1
μmol / ml, the concentration of triisobutylaluminum is 50 μmol / ml), 0.5 ml (that is, 0.5 μmol of the compound and 25 μmol of triisobutylaluminum).
mol), followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 3 μm
mol in heptane (slurry concentration,
1 μmol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.93 dl / g, SCB was 33.3, and melting points were 74.9 ° C., 79.2 ° C., and 89.6 ° C.
As a result, 4.79 g of a copolymer of ethylene and hexene-1 having an Mw of 52100 and a molecular weight distribution (Mw / Mn) of 2.3 was obtained. The polymerization activity was determined per mole of Ti atom,
It was 9.6 × 10 ⁶ g / Timol per 2 minutes.

[Comparative Example 1] An autoclave type reactor equipped with a stirring blade having a capacity of 0.4 liter was replaced with argon, 185 ml of cyclohexane was added as a solvent, and 15 ml of hexene-1 was added as an α-olefin. Temperature. After raising the temperature, the ethylene pressure was increased to 2.5
Feeding while adjusting to MPa, after the system is stabilized,
Triisobutylaluminum 0.3 mmol, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound) and triisobutylaluminum were mixed 0.5 ml of a heptane solution (concentration of the compound is 1 μmol / ml, concentration of triisobutylaluminum is 50 μmol / ml) (that is, 0.5 μmol of the compound and 25 μmol of triisobutylaluminum) are added, and then N, N-dimethyl Anilinium tetrakis (pentafluorophenyl)
3 μmol of borate was added as a liquid (slurry concentration, 1 μmol / ml) slurried in heptane.
Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 1.09 d.
1 / g, SCB 31.7, melting point 76.1 ° C, 88.
At 0 ° C., Mw is 65,400, molecular weight distribution (Mw / Mn)
Was 1.8 and 2.21 g of a copolymer of ethylene and hexene-1 was obtained. The polymerization activity was determined per mole of Ti atom,
It was 4.4 × 10 ⁶ g / Timol per 2 minutes.

[Comparative Example 2] After replacing an autoclave-type reactor equipped with a stirring blade having a capacity 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, and the reactor was heated to 180 ° C. Temperature. After raising the temperature, the ethylene pressure was increased to 2.5
Feeding while adjusting to MPa, after the system is stabilized,
0.5 mmol of triisobutylaluminum and 0.5 mmol of pentafluoroaniline (concentration: 0.1 mmol
The l / ml of a heptane solution 5ml use), dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound) and triisobutylaluminum in a heptane solution (compound concentration 1 μmol / ml, triisobutylaluminum concentration 50 μmol / ml) 0.5 ml (ie, 0.5 μmol of compound, 2
5 μmol). Polymerization was performed for 2 minutes. As a result of the polymerization, almost no polymer was obtained.

Reference Example 2 A dropping funnel was attached to a 100 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. 20 ml of polybutylaluminoxane (PBAO, manufactured by Tosoh Akzo Co., Ltd., hexane solution: 1.08 mol / l) and 17.8 ml of toluene were charged into a flask and stirred. 5.4 ml of pentafluoroaniline (toluene solution: 2 mol / l) was charged into the dropping funnel,
It was added dropwise at 25-30 ° C. After dropping, 25-30 ° C
For 0.5 hour and at 50 ° C. for 1 hour. A clear, colorless solution was obtained. (The Al concentration is 0.5 mol based on the charged amount.)
/ L) (compound).

[Comparative Example 3] After replacing an autoclave-type reactor equipped with a stirring blade with a capacity 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, and the reactor was heated to 180 ° C. Temperature. After raising the temperature, the ethylene pressure was increased to 2.5
Feeding while adjusting to MPa, after the system is stabilized,
0.5 mmol of the compound and dimethylsilylene (η ⁵ −
Tetramethylcyclopentadienyl) (3-tert-
Heptane solution in which butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound) and triisobutylaluminum are mixed (compound concentration is 1 μmol
/ Ml, the concentration of triisobutylaluminum is 50 μm
ol / ml) in 0.5 ml (i.e., 0.5 μl of compound).
mol, 25μmol of triisobutylaluminum)
I put it in. Polymerization was performed for 2 minutes. As a result of the polymerization, almost no polymer was obtained.

[Comparative Example 4] An agitator with an inner volume of 0.4 liter
The autoclave type reactor equipped with stirring blades was replaced with argon.
Then, 140 ml of cyclohexane as a solvent was
60 ml of hexene-1 was charged as a refining 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,
0.3 mmol of triisobutylaluminum, penta
50 μmol of fluoroaniline (concentration 10 μmol /
5 ml toluene solution), biscyclopentane
Dienyl zirconium dichloride (compound) and tri
Heptane solution mixed with isobutylaluminum
The concentration of the compound was 1 μmol / ml,
0.5 ml of minium concentration of 50 μmol / ml)
(That is, 0.5 μmol of the compound was
Luminium (25 μmol), followed by N, N-di
Methylanilinium tetrakis (pentafluorophenyl
B) A solution prepared by slurrying 3 μmol of borate in heptane
(Slurry concentration, 1 μmol / ml).
Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 0.19 d.
1 / g, SCB 17.0, melting point 109.8 ° C, 11
At 4.0 ° C., Mw was 6600, and molecular weight distribution (Mw / M
Copolymerization of ethylene and hexene-1 wherein n) is 2.0
1.43 g of a body were obtained. The polymerization activity was equivalent to 1 mole of Ti atom.
2.9 × 10 per 2 minutes ⁶g / Timol
Was.

[0086]

As described in detail above, according to the present invention,
A highly active olefin polymerization catalyst prepared using a metallocene transition metal compound, particularly a highly active olefin polymerization catalyst at an efficient reaction temperature in an olefin polymerization industrial process is provided. According to the present invention, an efficient method for producing an olefin polymer using the olefin polymerization catalyst is provided, and its utility value is extremely large.

[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 F-term (reference) 4J028 AA01A AB01A AC01A AC09A AC10A AC27A AC28A BA00B BA01A BB00A BB01B BC12B BC13B BC15B BC16B BC17B CA17C CB62C CB63C CB64C CB65C EB02 AC02 EB03 AC01 EB03 AC01 EB03 AC01 EB03 AC01 EB04 AC02A BA00B BA01A BB00A BB01B BC12B BC13B BC15B BC16B BC17B CA17C CB62C CB63C CB64C CB65C EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 GB01 GB02

Claims (9)

[Claims] 1. The following (A), (B), (C) and (D)
A catalyst for olefin polymerization, which is obtained by bringing into contact with an olefin. (A) A transition metal compound represented by the following general formula [I] or [II]. _{^{CpYMX 1 2 [I] (CpYMX}} 1 n) , respectively, in ^{_{2 X 2 2-n [II}} ] ( 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 represents 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. Y represents a group which is σ-bonded to M via an atom of Group 15 or Group 16 of the periodic table of the element, and Cp and Y are bonded directly or via a bridging group. n is 0 or 1. When a plurality of Cp, Y, M, X ¹ and X ² are present in one molecule, they may be the same or different. ) (B) the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E may or may not be the same.
Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a is a number satisfying 0 <a ≦ 3. (C): a boron compound represented by any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a general formula G ⁺ (BQ ^{1 Q 2 Q 3 Q 4)} - boron compound represented by (C3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent atom Is a valence boron atom, and 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 or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. (D): amine compound 2. The olefin polymerization catalyst according to claim 1, wherein (D) is a primary amine compound. 3. The catalyst for olefin polymerization according to claim 1, wherein (D) is an amine compound represented by the general formula: RNH ₂ (where R is a halogenated hydrocarbon group having 1 to 20 carbon atoms). 4. The olefin polymerization catalyst according to claim 3, wherein R is a halogenated aryl group having 6 to 20 carbon atoms. 5. 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 following general formulas [III], [IV] and [V], M represents a transition metal atom of Group 4 of the periodic table of the element, and A represents an atom of 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. ) 6. The catalyst for olefin polymerization according to claim 1, wherein (B) is trimethylaluminum, triethylaluminum, or triisobutylaluminum. 7. The olefin according to claim 1, wherein (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. Catalyst for polymerization. 8. A process for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 1. 9. The method for producing an olefin polymer according to claim 8, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.