JP2003300968A - Substituted cyclopentadiene compound and catalyst for polymerizing olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for polymerizing an olefin. <P>SOLUTION: This substituted cyclopentadiene compound represented by general formula (1) (R<SP>1</SP>is H, a 1 to 10C alkyl, a 7 to 20C aralkyl, or a 1 to 20C hydrocarbon-substituted silyl; R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>are each H, a 1 to 10C alkyl, a 1 to 10C alkoxy, a 6 to 20C aryl, a 6 to 20C aryloxy, a 7 to 20C aralkyl, a 7 to 20C aralkyloxy, or the like; R<SP>6</SP>, R<SP>7</SP>, R<SP>8</SP>and R<SP>9</SP>are each H, a halogen atom, a 1 to 10C alkyl, a 1 to 10C alkoxy, a 6 to 20C aryl, a 6 to 20C aryloxy, a 7 to 20C aralkyl, a 7 to 20C aralkyloxy, or the like), and the catalyst for polymerizing the olefin. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a substituted cyclopentadiene compound and a polymerization catalyst.

[0002]

2. Description of the Related Art A transition metal compound having a substituted cyclopentadiene compound as a ligand, that is, a so-called metallocene complex has been widely known as an olefin polymerization catalyst. However, a polymerization catalyst component containing a substituted cyclopentadiene having tetrazole via an aromatic ring has not been developed.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to provide a novel substituted cyclopentadiene compound and an olefin polymerization catalyst using the compound.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a substituted cyclopentadiene compound having a tetrazole and a cyclopentadiene ring as functional groups adjacent to each other on a benzene ring, and The present invention has been accomplished by finding a catalyst for olefin polymerization using the compound. That is, the present invention has the general formula (1) (In the formula, R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted carbon atom 7
To 20 aralkyl group and a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an optionally substituted C 1 to 10 carbon atom. Alkyl group, optionally substituted C1-10 alkoxy group, optionally substituted C6-20 aryl group, optionally substituted C6-20 aryloxy group, substituted An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms. A substituted amino group is shown, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon number. 1-10 alkoxy groups, units An optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted Also represents an aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ , and R ⁵ Adjacent groups in
R ⁶ and R ⁷ which are adjacent to each other and may form a ring,
Adjacent groups in R ⁸ and R ⁹ may be bonded to each other to form a ring, and the position of the double bond of cyclopentadiene may be arbitrary or a mixture. ) A substituted cyclopentadiene compound represented by the formula: (In the formula, M represents a transition metal atom of Group 4 of the periodic table,
X ¹ , X ² , X ³ , and X ⁴ are each independently halogen, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and 7 to 7 carbon atoms which may be substituted with a halogen atom. 20 aralkyl groups, aryl groups having 6 to 20 carbon atoms that may be substituted with halogen atoms, alkoxy groups having 1 to 20 carbon atoms that may be substituted with halogen atoms, and substituted with halogen atoms An aralkyloxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and 2 having 2 to 20 carbon atoms which may be substituted with a halogen atom. It represents a substituted amino group, and n represents 0 or 1. The present invention provides a catalyst for olefin weight, which comprises a complex obtained by reacting a transition metal compound represented by the formula (4) as a catalyst component.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
To do. Substituted cyclopentadiene represented by general formula (1)
In the compound, R⁶, R⁷, R ⁸, R⁹Halogen in
Atoms include fluorine, chlorine, bromine and iodine
An atom etc. are illustrated.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ and R ⁹ may have 1 to 10 carbon atoms which may be substituted.
Examples of the substituent of the alkyl group include a halogen atom and the like, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group Group, tetrafluoroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, trichloromethyl group and the like, Preferably, methyl group, ethyl group, isopropyl group, tert- Butyl group, amyl group.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, and the like, and examples of the substituent include an alkyl group, a fluorine atom, and the like. , For example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group,
2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group,
3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-
Trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3
4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-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 , N-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and their fluorine atom-substituted aryl groups are exemplified, and a phenyl group is preferable.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
7 to 20 carbon atoms which may be substituted in R ⁸ and R ⁹
Examples of the aralkyl group of include a benzyl group, a naphthylmethyl group, an anthracenylmethyl group, a diphenylmethyl group, and the like, examples of the substituent include an alkyl group, and specific examples include a benzyl group, ( 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, (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, (n-
Tetradecylphenyl) methyl group, naphthylmethyl group,
Examples thereof include anthracenylmethyl group, diphenylmethyl group and fluorine atom-substituted aralkyl groups thereof, and benzyl group is preferable.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
Examples of the substituent of the optionally substituted alkoxy group having 1 to 10 carbon atoms include a halogen atom and the like,
Specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-
Examples thereof include butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dexoxy group, and fluorine atom-substituted alkoxy groups thereof, preferably methoxy group and ethoxy group. And a tert-butoxy group.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a naphthoxy group, and an anthracenoxy group, and examples of the substituent include an alkyl group, a fluorine atom and the like, and specific examples include phenoxy group. Group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group Base,
3,4-dimethylphenoxy group, 3,5-dimethylphenoxy 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, 3,4,5
-Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethyl Phenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl group Examples thereof include a phenoxy group, a naphthoxy group, an anthracenoxy group, and fluorine-substituted aryloxy groups thereof.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
The hydrocarbon-substituted silyl group having 1 to 20 carbon atoms in R ⁸ and R ⁹ is a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group here is, for example,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group,
n-hexyl group, cyclohexyl group, n-octyl group,
an alkyl group having 1 to 10 carbon atoms such as an n-decyl group,
Examples thereof include aryl groups having 1 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthracenyl group. Examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups such as methylsilyl group, ethylsilyl group and phenylsilyl group, and disubstituted silyl groups such as dimethylsilyl group, diethylsilyl group and diphenylsilyl group. , Trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilyl group, tri-s
ec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n
Examples include 3-substituted silyl groups such as -hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group, and preferable examples include trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. The hydrocarbon group of each of these substituted silyl groups may be substituted with a fluorine atom.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
Is a hydrocarbon-substituted amino group having 1 to 20 carbon atoms in 2
An amino group substituted with one hydrocarbon group, wherein the hydrocarbon group is, for example, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, n-pentyl group,
An alkyl group having 1 to 10 carbon atoms such as neopentyl group, amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, phenyl group, tolyl group,
Examples thereof include aryl groups having 1 to 20 carbon atoms such as a xylyl group, a naphthyl group, and an anthracenyl group. Examples of the hydrocarbon-substituted amino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group. Group, te
rt-butylamino group, di-isobutylamino group, t
ert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group and the like, preferably dimethylamino group, diethylamino group and the like. . Examples of the halogen atom in the substituents R ⁶ , R ⁷ , R ⁸ and R ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom.

Adjacent groups of R ² , R ³ , R ⁴ and R ⁵ or adjacent groups of R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to form a ring.

As the substituted cyclopentadiene compound represented by the general formula (1), for example, 5- [2- (cyclopentadienyl) phenyl] -1H-tetrazole, 5-
[2- (2-methylcyclopentadienyl) phenyl]-
1H-tetrazole, 5- [2- (3-methylcyclopentadienyl) phenyl] -1H-tetrazole, 5- [2
-(2,3-Dimethylcyclopentadienyl) phenyl]
-1H-tetrazole, 5- [2- (2,4-dimethylcyclopentadienyl) phenyl] -1H-tetrazole, 5- [2- (2,3,4-trimethylcyclopentadienyl) phenyl] -1H -Tetrazole, 5- [2-
(2,3,5-Trimethylcyclopentadienyl) phenyl] -1H-tetrazole, 5- [2- (2,3,4,5)
-Tetramethylcyclopentadienyl) phenyl] -1
H-tetrazole, 5- [2- (2-dimethylaminomethylcyclopentadienyl) phenyl] -1H-tetrazole, 5- [2- (3-dimethylaminomethylcyclopentadienyl) phenyl] -1H-tetrazole, 5
-[2- (inden-1-yl) phenyl] -1H-tetrazole, 5- [2- (2-methylinden-1-yl) phenyl] -1H-tetrazole, 5- [2- (2-
Phenylinden-1-yl) phenyl] -1H-tetrazole, 5- [2- (fluoren-1-yl) phenyl] -1H-tetrazole

5- [2- (cyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2- (2-methylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2- ( 3-Methylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2-
(2,3-Dimethylcyclopentadienyl) phenyl]-
1-methyltetrazole, 5- [2- (2,4-dimethylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2- (2,3,4-trimethylcyclopentadienyl) phenyl]- 1-methyltetrazole, 5
-[2- (2,3,5-Trimethylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2-
(2,3,4,5-Tetramethylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2- (2
-Dimethylaminomethylcyclopentadienyl) phenyl] -1-methyltetrazole, 5- [2- (3-dimethylaminomethylcyclopentadienyl) phenyl] -1
-Methyltetrazole, 5- [2- (inden-1-yl) phenyl] -1-methyltetrazole, 5- [2-
(2-Methylinden-1-yl) phenyl] -1-methyltetrazole, 5- [2- (2-phenylinden-1-yl) phenyl] -1-methyltetrazole, 5
-[2- (Fluoren-1-yl) phenyl] -1-methyltetrazole

5- [2- (cyclopentadienyl) phenyl] -1-benzyl, 5- [2- (2-methylcyclopentadienyl) phenyl] -1-benzyl, 5- [2-
(3-Methylcyclopentadienyl) phenyl] -1-
Benzyl, 5- [2- (2,3-dimethylcyclopentadienyl) phenyl] -1-benzyl, 5- [2- (2,4
-Dimethylcyclopentadienyl) phenyl] -1-benzyl, 5- [2- (2,3,4-trimethylcyclopentadienyl) phenyl] -1-benzyl, 5- [2- (2,2
3,5-Trimethylcyclopentadienyl) phenyl]-
1-benzyl, 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1-benzyl, 5- [2- (2-dimethylaminomethylcyclopentadienyl) phenyl ] -1-benzyl, 5- [2-
(3-Dimethylaminomethylcyclopentadienyl) phenyl] -1-benzyl, 5- [2- (inden-1-yl) phenyl] -1-benzyl, 5- [2- (2-methylindene-1-) Il) phenyl] -1-benzyl, 5-
[2- (2-phenylinden-1-yl) phenyl]-
1-benzyl, 5- [2- (fluoren-1-yl) phenyl] -1-benzyl

5- [2- (cyclopentadienyl) phenyl] -1-trimethylsilyl, 5- [2- (2-methylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5- [2- (3- Methylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5- [2- (2,3-
Dimethylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5- [2- (2,4-dimethylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5-
[2- (2,3,4-trimethylcyclopentadienyl)
Phenyl] -1-trimethylsilyl, 5- [2- (2,3,
5-Trimethylcyclopentadienyl) phenyl] -1
-Trimethylsilyl, 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5- [2- (2-dimethylaminomethylcyclopentadienyl) phenyl]- 1-trimethylsilyl, 5- [2- (3-dimethylaminomethylcyclopentadienyl) phenyl] -1-trimethylsilyl, 5
-[2- (inden-1-yl) phenyl] -1-trimethylsilyl, 5- [2- (2-methylinden-1-yl) phenyl] -1-trimethylsilyl, 5- [2- (2
-Phenylinden-1-yl) phenyl] -1-trimethylsilyl, 5- [2- (fluoren-1-yl) phenyl] -1-trimethylsilyl

5- [2- (cyclopentadienyl) -1
-Naphthyl] -1H-tetrazole, 5- [2- (2-methylcyclopentadienyl) -1-naphthyl] -1H-
Tetrazole, 5- [2- (3-methylcyclopentadienyl) -1-naphthyl] -1H-tetrazole, 5-
[2- (2,3-dimethylcyclopentadienyl) -1-
Naphthyl] -1H-tetrazole, 5- [2- (2,4-
Dimethylcyclopentadienyl) -1-naphthyl] -1
H-tetrazole, 5- [2- (2,3,4-trimethylcyclopentadienyl) -1-naphthyl] -1H-tetrazole, 5- [2- (2,3,5-trimethylcyclopentadienyl) -1-Naphthyl] -1H-tetrazole, 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) -1-naphthyl] -1H-tetrazole, 5- [2- (2-dimethyl Aminomethylcyclopentadienyl) naphthyl] -1H-tetrazole, 5- [2
-(3-Dimethylaminomethylcyclopentadienyl)
-1-Naphthyl] -1H-tetrazole, 5- [2- (inden-1-yl) -1-naphthyl] -1H-tetrazole, 5- [2- (2-methylinden-1-yl)-
1-naphthyl] -1H-tetrazole, 5- [2- (2-
Phenylinden-1-yl) -1-naphthyl] -1H
-Tetrazole, 5- [2- (fluoren-1-yl)
-1-Naphthyl] -1H-tetrazole

5- [2- (cyclopentadienyl) naphthyl] -1-methyltetrazole, 5- [2- (2-methylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [ 2- (3-Methylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [2- (2,3-Dimethylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5 −
[2- (2,4-dimethylcyclopentadienyl) -1-
Naphthyl] -1-methyltetrazole, 5- [2- (2,
3,4-Trimethylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [2- (2,3,5
-Trimethylcyclopentadienyl) -1-naphthyl]
-1-methyltetrazole, 5- [2- (2,3,4,5
-Tetramethylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [2- (2-dimethylaminomethylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [ 2- (3-dimethylaminomethylcyclopentadienyl) -1-naphthyl] -1-methyltetrazole, 5- [2- (indene-
1-yl) -1-naphthyl] -1-methyltetrazole, 5- [2- (2-methylinden-1-yl) -1
-Naphthyl] -1-methyltetrazole, 5- [2- (2
-Phenylinden-1-yl) -1-naphthyl] -1
-Methyltetrazole, 5- [2- (fluorene-1-
1-naphthyl] -1-methyltetrazole

5- [2- (cyclopentadienyl) -1-
Naphthyl] -1-benzyl, 5- [2- (2-methylcyclopentadienyl) -1-naphthyl] -1-benzyl,
5- [2- (3-methylcyclopentadienyl) -1-
Naphthyl] -1-benzyl, 5- [2- (2,3-dimethylcyclopentadienyl) -1-naphthyl] -1-benzyl, 5- [2- (2,4-dimethylcyclopentadienyl)- 1-naphthyl] -1-benzyl, 5- [2- (2,
3,4-Trimethylcyclopentadienyl) -1-naphthyl] -1-benzyl, 5- [2- (2,3,5-trimethylcyclopentadienyl) -1-naphthyl] -1-benzyl, 5- [2- (2,3,4,5-Tetramethylcyclopentadienyl) -1-naphthyl] -1-benzyl, 5- [2- (2-dimethylaminomethylcyclopentadienyl) -1-naphthyl ] -1-benzyl, 5-
[2- (3-Dimethylaminomethylcyclopentadienyl) -1-naphthyl] -1-benzyl, 5- [2- (inden-1-yl) -1-naphthyl] -1-benzyl, 5
-[2- (2-Methylinden-1-yl) -1-naphthyl] -1-benzyl, 5- [2- (2-phenylinden-1-yl) -1-naphthyl] -1-benzyl, 5 −
[2- (Fluoren-1-yl) -1-naphthyl] -1-
Benzyl

5- [2- (cyclopentadienyl) -1
-Naphthyl] -1-trimethylsilyl, 5- [2- (2-
Methylcyclopentadienyl) -1-naphthyl] -1-
Trimethylsilyl, 5- [2- (3-methylcyclopentadienyl) -1-naphthyl] -1-trimethylsilyl, 5- [2- (2,3-dimethylcyclopentadienyl) -1-naphthyl] -1- Trimethylsilyl, 5- [2
-(2,4-Dimethylcyclopentadienyl) -1-naphthyl] -1-trimethylsilyl, 5- [2- (2,3,4
-Trimethylcyclopentadienyl) -1-naphthyl]
-1-Trimethylsilyl, 5- [2- (2,3,5-trimethylcyclopentadienyl) -1-naphthyl] -1-
Trimethylsilyl, 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) -1-naphthyl] -1
-Trimethylsilyl, 5- [2- (2-dimethylaminomethylcyclopentadienyl) -1-naphthyl] -1-
Trimethylsilyl, 5- [2- (3-dimethylaminomethylcyclopentadienyl) -1-naphthyl] -1-trimethylsilyl, 5- [2- (inden-1-yl)-
1-naphthyl] -1-trimethylsilyl, 5- [2- (2
-Methylinden-1-yl) -1-naphthyl] -1-
Trimethylsilyl, 5- [2- (2-phenylinden-1-yl) -1-naphthyl] -1-trimethylsilyl, 5- [2- (fluoren-1-yl) -1-naphthyl] -1-trimethylsilyl, etc. [2- (cyclopentadienyl) phenyl] of these compounds is exemplified.
[2- (cyclopentadienyl) -4-methylphenyl], [2- (cyclopentadienyl) -4,5-dimethylphenyl], [2- (cyclopentadienyl) -3-naphthyl], Modified compound, (inden-1-yl)
Compounds in which is changed to (inden-2-yl) and the like are also mentioned. The cyclopentadiene ring has isomers, but may be a single substance or a mixture.

Such a substituted cyclopentadienyl compound can be represented by the general formula (3) (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the same meanings as described above, and the double bond position of cyclopentadiene is arbitrary or a mixture. After the reaction with lithium azide, sodium azide, or potassium azide, preferably sodium azide, at a temperature of about 100 ° C. to 200 ° C. for usually 10 hours or more. , A protic acid, an alkyl bromide, a trialkylsilyl chloride, and the like are reacted to produce an electrophilic agent in one step.

Examples of the nitrile represented by the general formula (3) include 2-cyclopentadienylphenyl cyanide,
2- (2-methylcyclopentadienyl) phenyl cyanide, 2- (3-methylcyclopentadienyl) phenylcyanide, 2- (2,3-dimethylcyclopentadienyl) phenylcyanide, 2- ( 2,4-dimethylcyclopentadienyl) phenyl cyanide, 2- (2,3,4
-Trimethylcyclopentadienyl) phenyl cyanide, 2- (2,3,5-trimethylcyclopentadienyl) phenyl cyanide, 2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl cyan Nido, 2-
(2-Dimethylaminomethylcyclopentadienyl) phenyl cyanide, 2- (3-Dimethylaminomethylcyclopentadienyl) phenylcyanide, 2- (inden-1-yl) phenylcyanide, 2- (2- Methylinden-1-yl) phenyl cyanide, 2- (2-phenylinden-1-yl) phenylcyanide, 2- (fluoren-1-yl) phenylcyanide

2-cyclopentadienyl-1-naphthyl cyanide, 2- (2-methylcyclopentadienyl)-
1-naphthylcyanide, 2- (3-methylcyclopentadienyl) -1-naphthylcyanide, 2- (2,3-dimethylcyclopentadienyl) -1-naphthylcyanide, 2- (2,4-dimethylcyclopentadienyl) ) −
1-naphthyl cyanide, 2- (2,3,4-trimethylcyclopentadienyl) -1-naphthyl cyanide, 2-
(2,3,5-Trimethylcyclopentadienyl) -1-
Naphthyl cyanide, 2- (2,3,4,5-tetramethylcyclopentadienyl) -1-naphthyl cyanide,
2- (2-dimethylaminomethylcyclopentadienyl) -1-naphthylcyanide, 2- (3-dimethylaminomethylcyclopentadienyl) -1-naphthylcyanide, 2- (inden-1-yl) -1-naphthylcyanide, 2- (2-methylinden-1-yl) -1-naphthylcyanide, 2- (2-phenylinden-1-yl) -1-naphthylcyanide, 2- (fluorene-1-)
Il) -1-naphthyl cyanide, etc. are exemplified, and [2- (cyclopentadienyl) phenyl] of these compounds is
[2- (cyclopentadienyl) -4-methylphenyl], [2- (cyclopentadienyl) -4,5-dimethylphenyl], [2- (cyclopentadienyl) -3-naphthyl], Modified compound, (inden-1-yl)
Compounds in which is changed to (inden-2-yl) and the like are also mentioned. There are isomers of the cyclopentadiene ring, but they may be single or mixed.

Examples of the transition metal compound represented by the general formula (2) include titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, tetrabenzyl titanium, tetrabenzyl zirconium, tetraisopropoxy titanium, tetraisopropoxy zirconium and tetra. Isopropoxyhafnium, triisopropoxytitanium trichloride, triisopropoxyzirconium chloride, diisopropoxytitanium dichloride, diisopropoxyzirconium dichloride,
Isopropoxytitanium trichloride, isopropoxyzirconium trichloride, tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, tetrakis (dimethylamino) zirconium,
Tetrakis (diethylamino) zirconium, Tetrakis (dimethylamino) hafnium, Tetrakis (diethylamino) hafnium, Tris (dimethylamino) titanium chloride, Tris (diethylamino) titanium chloride, Tris (dimethylamino) zirconium chloride, Tris (diethylamino) zirconium chloride, Tris (Dimethylamino) hafnium chloride, tris (diethylamino) hafnium chloride, bis (dimethylamino) titanium dichloride, bis (diethylamino) titanium dichloride, bis (dimethylamino) zirconium dichloride, bis (diethylamino)
Zirconium dichloride, bis (dimethylamino) hafnium dichloride, bis (diethylamino) hafnium dichloride, dimethylaminotitanium trichloride,
Diethylaminotitanium trichloride, dimethylaminozirconium trichloride, diethylaminozirconium trichloride, dimethylaminohafnium trichloride, diethylaminohafnium trichloride

Examples include titanium trichloride, zirconium trichloride, hafnium trichloride, tribromotitanium, tribromozirconium and tribromohafnium.

The reaction between the substituted cyclopentadienyl compound represented by the general formula (1) and the transition metal compound represented by the general formula (2) is usually carried out in a solvent inert to the reaction. Examples of such a solvent include benzene, an aromatic hydrocarbon solvent such as toluene, hexane, an aliphatic hydrocarbon solvent such as heptane, diethyl ether, tetrahydrofuran, an ether solvent such as 1,4-dioxane, and the like.
Hexamethylphosphoric amide, amide-based solvents such as dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and halogen-based solvents such as dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene. Examples thereof include protic solvents, preferably aromatic hydrocarbon solvents such as benzene and toluene, and aliphatic hydrocarbon solvents such as hexane and heptane. Such solvents may be used alone or in combination of two or more, and the amount used is not limited, but is usually 1 to 200 times by weight, preferably 3 to 10 times the weight of the substituted cyclopentadiene compound represented by the general formula (1). It is in the range of 50 times the weight.

The mixing ratio is usually 0.1 to 10 times mol, preferably 0.5 to 10 times, the molar amount of the transition metal complex represented by the general formula (2) with respect to the substituted cyclopentadiene compound represented by the general formula (1).
Mix at a ratio of about 1 time mol.

The reaction temperature is usually from -100 ° C to the boiling point of the solvent, preferably from -80 to 120 ° C.

After the reaction, low boiling components are distilled off under reduced pressure to obtain the target complex. The complex thus obtained can be used by adding the following compound (A) or further the following compound (B) in any order during the olefin polymerization reaction, and a combination of any of these compounds can be used in advance. The reaction product obtained by contact may be used for the polymerization reaction.

The compound (A) includes the following compounds (A1) to
One or more selected from (A3). (A1): Organoaluminum compound represented by the general formula E1aAlZ3-a (A2): Cyclic aluminoxane having a structure represented by the general formula {-Al (E2) -O-} b (A3): General formula E3 {-Al (E3) -O-} c A
a linear aluminoxane having a structure represented by 1E32 (wherein E1 to E3 are the same or different, a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different,
It represents a hydrogen atom or a halogen atom, a is 1, 2, or 3, b is an integer of 2 or more, and c is an integer of 1 or more. )

The compound (B) includes the following compounds (B1) to
One or more selected from (B3). (B1): a boron compound represented by the general formula BQ1 Q2 Q3, (B2): a boron compound represented by the general formula Z + (BQ1 Q2 Q3 Q4)-, (B3): a general formula (L-H) + (BQ1 Q2 Q3 Q4)
A boron compound represented by the formula (wherein B is a boron atom in a trivalent valence state, and Q is
1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 1-20 alkoxy group or a C2-C20 disubstituted amino group is shown. )

[Compound A] As the compound (A) used in the present invention, a known organoaluminum compound can be used. Preferably, (A1) the general formula E1 a AlZ3-
an organoaluminum compound represented by a, (A2) a cyclic aluminoxane having a structure represented by the general formula {-Al (E2) -O-} b, and (A3) a general formula E3 {-
A linear aluminoxane having a structure represented by Al (E3) -O-} c AlE3 2 (provided that E1, E2, E3
Is a hydrocarbon group having 1 to 8 carbon atoms, and all E1, all E2 and all E3 may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a is 0 <a ≦
B is an integer of 2 or more, and c is an integer of 1 or more. 2), or a mixture of 2 to 3 kinds thereof.

Specific examples of the organoaluminum compound (A1) represented by the general formula E1 a AlZ3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum;
Dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum halide, dihexyl aluminum chloride; alkyl aluminum such as methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride Dichloride; Dialkyl aluminum hydride such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, and dihexyl aluminum hydride can be exemplified. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

A cyclic aluminoxane (A2) having a structure represented by the general formula {-Al (E2) -O-} b, and a structure represented by the general formula E3 {-Al (E3) -O-} c AlE3 2 Specific examples of E2 and E3 in the linear aluminoxane (A3) having are an alkyl group such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group and a neopentyl group. It can be illustrated. b is 2
The above is an integer, and c is an integer of 1 or more. Preferably, E2 and E3 are a methyl group, an isobutyl group, and b
Is 2 to 40 and c is 1 to 40.

The above aluminoxane can be produced by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in an appropriate organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water to prepare. In addition, a method in which a trialkylaluminum (eg, trimethylaluminum) is brought into contact with a metal salt containing crystal water (eg, copper sulfate hydrate) can be exemplified.

[Compound B] In the present invention, the compound (B)
Are (B1) a boron compound represented by the general formula BQ1 Q2 Q3, and (B2) a general formula Z + (BQ1 Q2 Q3 Q4
)-, A boron compound represented by the formula (B3), a general formula (L-
H) + (BQ1 Q2 Q3 Q4)-, which is a boron compound.

In the boron compound (B1) represented by the general formula BQ1 Q2 Q3, B is a boron atom in a trivalent valence state, Q1 to Q3 are halogen atoms and carbonization containing 1 to 20 carbon atoms. Hydrogen group, halogenated hydrocarbon group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms or 2 to 20 carbon atoms And a disubstituted amino group, which may be the same or different. Preferred Q1 to Q3 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.

Specific examples of the Lewis acid (B1) include tris (pentafluorophenyl) borane and tris (2,2).
3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Examples thereof include phenylbis (pentafluorophenyl) borane, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (B2) represented by the general formula Z + (BQ1 Q2 Q3 Q4)-, Z + is an inorganic or organic cation, B is a boron atom in a trivalent valence state, Q1 to Q4 are Q in (B1) above
The same as 1 to Q3.

Specific examples of the compound represented by the general formula Z + (BQ1 Q2 Q3 Q4)-include inorganic cations Z + such as ferrocenium cations, alkyl-substituted ferrocenium cations, and silver cations. Examples of Z + which is an organic cation include a triphenylmethyl cation. (BQ1 Q2 Q3 Q4)-includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) Examples include borate.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and more preferable examples include triphenylmethyltetrakis (pentafluorophenyl) borate.

Further, the general formula (L-H) + (BQ1 Q2 Q
In the boron compound (B3) represented by 3 Q4)-, L is a neutral Lewis base, (L-H) + is a Bronsted acid, and B is a boron atom in a trivalent valence state. Yes, Q1 to Q4 are Q1 to Q in (B1) above.
The same as in 3.

General formula (L-H) + (BQ1 Q2 Q3 Q4
Specific examples of the compound represented by)-include (L-H) + which is a Bronsted acid, such as trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium and triarylphosphonium. , (BQ1 Q2 Q3 Q4)-are the same as those mentioned above.

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

The amount of each catalyst component used is such that the molar ratio of compound (A) / complex is 0.1 to 10,000, preferably 5 to 20.
And the molar ratio of the compound (B) / complex is 0.00.
It is desirable to use each component so that it is in the range of 01 to 100, preferably 0.5 to 10. Regarding the concentration when each catalyst component is used in a solution state, the substituted cyclopentadiene compound represented by the general formula (1) is 0.0
001 to 5 mmol / liter, preferably 0.0
01 to 1 mmol / liter, compound (A) is 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, and compound (B) is 0.0001 to 5 in terms of Al atom. It is desirable to use each component in the range of mmol / l, preferably 0.001 to 1 mmol / l.

In the present invention, the monomer used for polymerization may be any of olefins and diolefins having 2 to 20 carbon atoms, and two or more kinds of monomers may be used at the same time. Examples of such monomers are shown below, but the present invention is not limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,
Examples include decene-1,5-methyl-2-pentene-1, vinylcyclohexene and the like. Examples of the diolefin compound include a conjugated diene and a non-conjugated diene of a hydrocarbon compound, and specific examples of the compound include 1,5-hexadiene and 1,4 as specific examples of the non-conjugated diene compound.
-Hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,
4-methyl-1,4-hexadiene, 5-methyl-1,
4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2- Norbornene, 1,5-cyclooctadiene,
5,8-endomethylene hexahydronaphthalene and the like are exemplified, and specific examples of the conjugated diene compound include 1,3-
Butadiene, isoprene, 1,3-hexadiene, 1,
3-octadiene, 1,3-cyclooctadiene, 1,
3-cyclohexadiene etc. can be illustrated. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and the like, and further 5-ethylidene-2-norbornene. Combinations and the like are exemplified, but the present invention is not limited to the above compounds.

In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene,
Examples thereof include p-ethylstyrene, o-chlorostyrene, p-chlorostyrene, α-methylstyrene and divinylbenzene.

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

The polymerization temperature may be in the range of -50 ° C to 200 ° C, but particularly preferably in the range of -20 ° C to 100 ° C, and the polymerization pressure is atmospheric pressure to 6 MPa (60 kg / cm 2).
G) is preferred. The polymerization time is generally appropriately determined depending on the type of the target polymer and the reaction apparatus, but it can be usually in the range of 1 minute to 20 hours. Further, in the present invention, a chain transfer agent such as hydrogen may be added to control the molecular weight of the copolymer.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound in which a tetrazole moiety and a cyclopentadiene ring are bridged with an aromatic ring can be synthesized, and an olefin polymer can be obtained by a polymerization catalyst containing a complex obtained from the compound as a catalyst component.

[0052]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 Synthesis of 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1H-tetrazole 2- (2,3,4,5-tetramethylcyclo) under nitrogen atmosphere Pentadienyl) phenyl cyanide (5.0mmo
1), sodium azide (20.0 mmol) and magnesium chloride (10.0 mmol) in dimethylformamide (3.3 mL), and the mixture was stirred at 140 ° C. After confirming the disappearance of 2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl cyanide by gas chromatography, 10% aqueous sodium nitrite solution was added, and then diluted nitric acid and toluene were added to the organic layer. Was extracted. The oil obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography to obtain 5 as a pale yellow solid.
0.87 g (yield 65.3%) of-[2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1H-tetrazole was obtained. ¹ H-NMR (C ₆ D ₆ ) d 8.26-8.21 (m,
1H), 7.65-7.37 (m, 3H), 2.86-2.83 (m, 1H), 2.41-2.
26 (m, 1H), 2.15-2.02 (m, 3H), 1.65-1.54 (m, 6H), 1.
29-1.15 (m, 3H) .MS (EI) m / z 266, 223, 207, 195, 18
0, 165

Example 2 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1H-tetrazole and tetrakis
Preparation of a mixture of (dimethylamino) titanium 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1H-tetrazole (3.3 mm
solution of tetrakis (dimethylamino) titanium (3.3 mmol) in toluene (6.0 mL) at 0 ° C. 5 at 110 ° C
Reacted for hours. After cooling to room temperature, low-boiling substances were distilled off under reduced pressure to obtain a catalyst component containing 5- [2- (2,3,4,5-tetramethylcyclopentadienyl) phenyl] -1H-tetrazole. It was

<< Ethylene Homopolymerization >> Example 3 5.0 mL of toluene was charged into an autoclave under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.6 MPa and stabilized. Here, MMAO (250 μmo
1, 5.8 wt% Al, Tosoh Akzo) and 0.10 g of the catalyst component prepared in Example 2 in toluene solution (5
0.0 μL) was added and the mixture was polymerized for 30 minutes. The result of the polymerization,
1.3 g of polymer per 1 g of catalyst component per hour
5 × 10 ³ g was produced.

Example 4 Toluene (5.0 mL) was charged into an autoclave under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.6 MPa and stabilized. Here, a hexane solution of triisobutylaluminum (100 μL, 1.0 M, Kanto Kagaku), a toluene solution (50.0 μL) of 0.10 g of the catalyst component prepared in Example 2, and triphenylcarbenium tetrakispentafluorophenylborate. (0.
(75 μmol) was added and the mixture was polymerized for 30 minutes. As a result of the polymerization, the polymer was added per 1 g of the catalyst component per hour,
2.25 × 10 ³ g was produced.

Example 5 Except that dimethylanilinium tetrakispentafluorophenylborate was used instead of triphenylcarbenium tetrakispentafluorophenylborate.
Polymerization was carried out in the same manner as in Example 4. As a result of the polymerization, the amount of the polymer was 2.62 × 10 ³ g per 1 g of the catalyst component per 1 hour.
Manufactured.

Example 6 Polymerization was carried out in the same manner as in Example 4 except that trispentafluorophenylborane was used instead of triphenylcarbenium tetrakispentafluorophenylborate.
As a result of the polymerization, 9.76 × 10 ² g of a polymer was produced per 1 g of the catalyst component per hour.

<< Ethylene-Hexene Copolymerization >> Example 7 Toluene (5.0 mL) and hexene (5.0 μL) were charged into an autoclave under nitrogen, and after stabilizing at 40 ° C., ethylene was pressurized to 0.6 MPa to stabilize. . Here, hexane solution of triisobutylaluminum (100μ
L, 1.0 M, Kanto Kagaku), 0.10 g of the catalyst component prepared in Example 2 in toluene (50.0 μL), and triphenylcarbenium tetrakispentafluorophenylborate (0.75 μmol) were added, and the mixture was added for 30 minutes. Polymerized. As a result of the polymerization, 1.87 × 10 ³ g of a polymer was produced per 1 g of the catalyst component per hour.

Example 8 Except that dimethylanilinium tetrakispentafluorophenylborate was used instead of triphenylcarbenium tetrakispentafluorophenylborate.
Polymerization was carried out in the same manner as in Example 7. As a result of the polymerization, the amount of the polymer was 1.73 × 10 ³ g per 1 g of the catalyst component per 1 hour.
Manufactured.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takayuki Azumai             Sumitomo, 2-10-1 Tsukahara, Takatsuki City, Osaka Prefecture             Gaku Kogyo Co., Ltd. F-term (reference) 4J128 AA01 AB00 AB01 AC01 AC04                       AC05 AC06 AC07 AC08 AC09                       AC14 AC15 AC17 AC18 AC19                       AC24 AC25 AC26 AC27 AC29                       AC30 AE05 AE06 AE07 BA00A                       BA01B BA02B BA03B BA04B                       BA05B BB00A BB01B BB02B                       BB03B BC12B BC13B BC15B                       BC16B BC17B BC25B BC27B                       CB72A CB91A EA01 EB02                       EB04 EB05 EB07 EB08 EB09                       EB12 EB13 EB14 EB16 EB17                       EB18 EB21 EC01 EC02 ED01                       ED02 ED03 FA02 FA04 FA06                       FA09 GB01

Claims (6)

[Claims] 1. A general formula (1) (In the formula, R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted carbon atom 7
To 20 aralkyl group and a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an optionally substituted C 1 to 10 carbon atom. Alkyl group, optionally substituted C1-10 alkoxy group, optionally substituted C6-20 aryl group, optionally substituted C6-20 aryloxy group, substituted An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms. A substituted amino group is shown, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon number. 1-10 alkoxy groups, units An optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted Also represents an aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, and R ² , R ³ , R ⁴ , and R ⁵ Adjacent groups in
R ⁶ and R ⁷ which are adjacent to each other and may form a ring,
Adjacent groups in R ⁸ and R ⁹ may be bonded to each other to form a ring, and the position of the double bond of cyclopentadiene may be arbitrary or a mixture. ) A substituted cyclopentadiene compound represented by 2. The substituted cyclopentadiene compound according to claim 1, wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 3. The substituted cyclopentadiene compound according to claim ¹ , wherein R ¹ is a hydrogen atom. 4. A substituted cyclopentadiene compound according to any one of claims 1 to 3 and a general formula (2): (In the formula, M represents a transition metal atom of Group 4 of the periodic table,
X ¹ , X ² , X ³ , and X ⁴ are each independently halogen, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and 7 to 7 carbon atoms which may be substituted with a halogen atom. 20 aralkyl groups, aryl groups having 6 to 20 carbon atoms that may be substituted with halogen atoms, alkoxy groups having 1 to 20 carbon atoms that may be substituted with halogen atoms, and substituted with halogen atoms An aralkyloxy group having 7 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and 2 having 2 to 20 carbon atoms which may be substituted with a halogen atom. It represents a substituted amino group, and n represents 0 or 1. ) A catalyst for olefin polymerization, characterized by comprising a complex obtained by reacting a transition metal compound represented by the formula (1) with a compound (A) shown below. Compound (A)
Is one or more selected from the following compounds (A1) to (A3). (A1): Organoaluminum compound represented by the general formula E1aAlZ3-a (A2): Cyclic aluminoxane having a structure represented by the general formula {-Al (E2) -O-} b (A3): General formula E3 {-Al (E3) -O-} c A
a linear aluminoxane having a structure represented by 1E32 (wherein E1 to E3 are the same or different, a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different,
It represents a hydrogen atom or a halogen atom, a is 1, 2, or 3, b is an integer of 2 or more, and c is an integer of 1 or more. ) 5. A complex obtained by reacting the substituted cyclopentadiene compound according to any one of claims 1 to 3 with a transition metal compound represented by the general formula (2), the above compound (A) and the following compound: An olefin polymerization catalyst comprising a combination of (B). Compound (B) is
One or more selected from the following compounds (B1) to (B3). (B1): a boron compound represented by the general formula BQ1 Q2 Q3, (B2): a boron compound represented by the general formula Z + (BQ1 Q2 Q3 Q4)-, (B3): a general formula (L-H) + (BQ1 Q2 Q3 Q4)
A boron compound represented by the formula (wherein B is a boron atom in a trivalent valence state, and Q is
1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 1-20 alkoxy group or a C2-C20 disubstituted amino group is shown. ) 6. An olefin polymerization method using the olefin polymerization catalyst according to claim 4.