JPH05301917A - Olefin-polymerization catalyst and production of olefin polymer using the catalyst - Google Patents

Abstract

PURPOSE:To provide a process for producing an olefin polymer using a catalyst having high polymerization activity per unit aluminum content in the catalyst. CONSTITUTION:An olefin is polymerized in the presence of a catalyst composed of a substance produced by bringing (A) a metallocene-type transition metal compound and (B) clay, a clay mineral or an ion-exchanging laminar compound (e.g. montmorillonite) into contact with (C) an organic aluminum compound or a catalyst composed of the above substance and (D) an organic aluminum compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a method for obtaining an olefin polymer in high yield using the catalyst.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin in the presence of a catalyst, a catalyst (1) is used.
A method using a metallocene and (2) aluminoxane has been proposed (JP-A-58-01930).
9 and JP-A-2-167307).

The polymerization method using these catalysts has a very high polymerization activity per transition metal as compared with the conventional method using the Ziegler-Natta catalyst composed of a titanium compound or a vanadium compound and an organoaluminum compound. A polymer having a narrow molecular weight distribution can be obtained.

[0004]

However, since a large amount of aluminoxane is required to obtain sufficient polymerization activity using these catalysts, the polymerization activity per aluminum is low, which is uneconomical. , It was necessary to remove the catalyst residue from the produced polymer. On the other hand, a method of polymerizing an olefin with a catalyst in which one or both of the above transition metal compound and aluminoxane is supported on an inorganic oxide such as silica or alumina has also been proposed (JP-A-61-108610). 60-135408
Japanese Patent Publication No. 61-296008, Japanese Patent Laid-Open No. 3-74
No. 412, No. 3-74415, etc.).

Further, there has been proposed a method of polymerizing an olefin with a catalyst in which one or both of a transition metal compound and an organoaluminum compound are supported on an inorganic oxide such as silica or alumina or an organic substance (Japanese Patent Laid-Open No. 1-10).
No. 1303, No. 1-207303, No. 3-2
No. 34709, No. 3-234710, and Japanese Patent Publication No. 3-501869). However, even in the methods proposed by these, the polymerization activity per aluminum is still insufficient, and the amount of the catalyst residue in the product is not negligible.

[0006]

As a result of studies to solve the above-mentioned problems, the present inventors have found a catalyst having a sufficiently high polymerization activity per transition metal and per aluminum, and arrived at the present invention. That is, the present invention is characterized by comprising a product obtained by contacting [A] metallocene-based transition metal compound, [B] clay, clay mineral or ion-exchange layered compound, and [C] organoaluminum compound. Olefin polymerization catalyst and [A]
A catalyst comprising a metallocene-based transition metal compound, [B] clay, a clay mineral or an ion-exchange layered compound, and a product obtained by contacting [C] an organoaluminum compound, and, if necessary, a [D] organoaluminum compound. In the presence of olefin, a method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin.

The present invention will be described in detail below. The metallocene-based transition metal compound, which is the component [A] used in the catalyst of the present invention, is a cyclopentadienyl-based ligand that may be substituted, that is, a substituent may be bonded to form a condensed ring. It is an organometallic compound composed of a pentadienyl ring-containing ligand and a transition metal of Groups 4, 5, and 6 of the long periodic table.

Preferred as such metallocene-based transition metal compound is a compound represented by the following general formula [1] or [2].

[0009]

Embedded image R ¹ _m (CpR ² _n ) (CpR ² _n ) MR ³ ₂ [1] [R ¹ _m (CpR ² _n ) (CpR ² _n ) MR ³ R ⁴ ] ⁺ R ^5- [2]

(However, in the formulas [1] and [2], (CpR ²
n) represents a cyclopentadienyl group or a substituted cyclopentadienyl group, which may be the same or different, and R ¹
Is the 14th element of the long periodic table of carbon, silicon, germanium, etc.
It is a covalent bond-linking group containing a group element, and each R ² may have the same or different hydrogen, halogen, a silicon-containing group, or a halogen-substituted group having 1 to 20 carbon atoms.
A hydrocarbon group, an alkoxy group, or an aryloxy group of R ² having two R ² adjacent to each other on the cyclopentadienyl ring.
When present at one carbon atom, they are bonded together to form C ₄
-C ₆ may form a ring. R ³ is hydrogen which may be the same or different, a halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group or an aryloxy group, and m Is 0 or 1, each n is an integer such that n + m = 5, and M
Is a metal of Groups 4, 5 and 6 of the long periodic table, R ⁴ is a neutral ligand coordinating to M, and R ^5- is a counter anion capable of stabilizing the above metal cation. Indicates. )

In the above general formula [1] or [2], R
¹ is the 14th of the long periodic table of carbon, silicon, germanium, etc.
It is a covalent bond-crosslinking group containing a group element and bonds two cyclopentadienyl ring-containing groups represented by the above CpR ² n. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group,
Isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group,
Silicon-containing cross-linking groups such as diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgermylene group, diethylgermylene group, dipropyl Germylene group,
Diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t
-Germanium-containing cross-linking groups such as -butylgermylene group, alkylphosphines, amines and the like. Of these, an alkylene group, an alkylidene group, and a silicon-containing bridging group are particularly preferably used.

Each CpR ² n is a cyclopentadienyl group or a substituted cyclopentadienyl group which may be the same or different. Here, R ² is hydrogen, which may be the same or different, fluorine such as fluorine, chlorine, bromine and iodine,
Silicon-containing groups such as trimethylsilyl, triethylsilyl and triphenylsilyl groups, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl,
A hydrocarbon group having 1 to 20 carbon atoms which may have a halogen group such as chloromethyl or chloroethyl group, an alkoxy group such as methoxy, ethoxy, propoxy or butoxy group, or a phenoxy, methylphenoxy or pentamethylphenoxy group. And other aryloxy groups.

Here, two R's²Is cyclopentadi
When present on two adjacent carbon atoms of an enyl ring,
Combined with each other C_Four~ C₆Form a ring, indenyl, te
Trahydroindenyl, fluorenyl, octahydrof
It may be a fluorenyl group or the like. Of these, R²When
And particularly preferably hydrogen, a methyl group, and two R
²Bound to each other by indenyl, tetrahydroindeni
A fluor, fluorenyl or octahydrofluorenyl group
It is a formed hydrocarbon group.

R ³ may be the same or different, hydrogen, halogen such as fluorine, chlorine, bromine and iodine, a silicon-containing group such as trimethylsilyl, triethylsilyl and triphenylsilyl group, methyl, ethyl, propyl, butyl and isobutyl. , Pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, chloromethyl, chloroethyl, and other hydrocarbon groups having 1 to 20 carbon atoms, which may have a halogen substituent, methoxy, ethoxy, propoxy, It is an alkoxy group such as butoxy group and an aryloxy group such as phenoxy, methylphenoxy and pentamethylphenoxy group, and hydrogen, chlorine and methyl group are particularly preferable.

M is two cyclopentadienyl rings R ¹
It is 0 when they are not combined with and is 1 when they are combined. Each n is 4 when m is 1 and 5 when m is 0. M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or a metal of Group 4, 5 or 6 of the long periodic table, and particularly preferably titanium, zirconium or hafnium.

R ⁴ is a neutral ligand that coordinates to M such as tetrahydrofuran, and R ^5- is the above-mentioned tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, dicarbaundecaborate and the like. General formula [2]
It shows a counter anion capable of stabilizing the metal cations therein. The catalyst of the present invention is an isotactic polymer,
Both syndiotactic and atactic polymers can be produced.

The above metallocene-based transition metal compounds are
Physically, if zirconium is taken as an example, it corresponds to the formula [1].
Bis (methylcyclopentadiene)
Le) zirconium dichloride, bis (ethylcyclope
N-dienyl) zirconium chloride, bis (methyl)
Cyclopentadienyl) zirconium dimethyl, bis
(Ethylcyclopentadienyl) zirconium dimethyl
Le, bis (methylcyclopentadienyl) zirconium
Dihydride, bis (ethylcyclopentadienyl) zil
Conium dihydride, bis (dimethylcyclopentadiene
Nyl) zirconium dichloride, bis (trimethylsilane)
Clopentadienyl) zirconium dichloride, bis
(Tetramethylcyclopentadienyl) zirconium di
Chloride, bis (ethyltetramethylcyclopentadi)
(Enyl) zirconium dichloride, bis (indeni
Le) zirconium dichloride, bis (dimethylcyclo)
Pentadienyl) zirconium dimethyl, bis (trime
Cylcyclopentadienyl) zirconium dimethyl, bi
Su (tetramethylcyclopentadienyl) zirconium
Dimethyl, bis (ethyltetramethylcyclopentadiene
Nyl) zirconium dimethyl, bis (indenyl) zil
Conium dimethyl, bis (dimethylcyclopentadiene
Le) zirconium dihydride, bis (trimethylcyclo)
Pentadienyl) zirconium dihydride, bis (ethyi)
Rutetramethylcyclopentadienyl) zirconium di
Hydride, bis (trimethylsilylcyclopentadiene
Le) zirconium dimethyl, bis (trimethylsilyl)
Clopentadienyl) zirconium dihydride, bis
(Trifluoromethylcyclopentadienyl) zirconi
Umdichloride, bis (trifluoromethylcyclope
N-dienyl) zirconium dimethyl, bis (triflu
Oromethylcyclopentadienyl) zirconium dihydrogen
Compound, isopropylidene-bis (indenyl) zirconi
Umdichloride, isopropylidene-bis (indeni
Z) Zirconium dimethyl, isopropylidene-pis
(Indenyl) zirconium dihydride, pentamethyl
Cyclopentadienyl (cyclopentadienyl) zirco
Aluminum dichloride, pentamethylcyclopentadiene
Ru (cyclopentadienyl) zirconium dimethyl, pe
N-methylcyclopentadienyl (cyclopentadienyl
Le) Zirconium dihydride, ethyl tetramethyl siku
Lopentadienyl (cyclopentadienyl) zirconium
Dihydrogen, isopropylidene (cyclopentadiene
Ru) (fluorenyl) zirconium dichloride, iso
Propylidene (cyclopentadienyl) (fluorenyl
) Zirconium dimethyl, dimethylsilyl (cyclope
(Dienyl) (fluorenyl) zirconium dimethy
L, isopropylidene (cyclopentadienyl) (full
Orenyl) zirconium dihydride, bis (cyclopen
Tadienyl) zirconium dichloride, bis (cyclo
Pentadienyl) zirconium dimethyl, bis (cyclo)
Pentadienyl) zirconium diethyl, bis (cyclo)
Pentadienyl) zirconium dipropyl, bis (shik)
Lopentadienyl) zirconium diphenyl, methyl
Clopentadienyl (cyclopentadienyl) zirconi
Umdichloride, ethylcyclopentadienyl (shik
Lopentadienyl) zirconium dichloride, methyl
Cyclopentadienyl (cyclopentadienyl) zirco
Dimethyl, ethylcyclopentadienyl (cyclo
Pentadienyl) zirconium dimethyl, methylcyclo
Pentadienyl (cyclopentadienyl) zirconium
Dihydride, ethylcyclopentadienyl (cyclopen
Tadienyl) zirconium dihydride, dimethylcyclo
Pentadienyl (cyclopentadienyl) zirconium
Dichloride, trimethylcyclopentadienyl
Lopentadienyl) zirconium dichloride, tetra
Methyl cyclopentadienyl (cyclopentadienyl)
Zirconium dichloride, bis (pentamethylcyclo)
Pentadienyl) zirconium dichloride, tetrame
Cylcyclopentadienyl (cyclopentadienyl) di
Ruconium dichloride, indenyl (cyclopentadi
(Enyl) zirconium dichloride, dimethyl cyclope
Zentadienyl (cyclopentadienyl) zirconium di
Methyl, trimethylcyclopentadienyl (cyclopen
Tadienyl) zirconium dimethyl, tetramethylsik
Lopentadienyl (cyclopentadienyl) zirconium
Dimethyl, bis (pentamethylcyclopentadiene
Z) Zirconium dimethyl, ethyl tetramethyl cyclo
Pentadienyl (cyclopentadienyl) zirconium
Dimethyl, indenyl (cyclopentadienyl) zirco
N-dimethyl, dimethylcyclopentadienyl
Lopentadienyl) zirconium dihydride, trimethyl
Cyclopentadienyl (cyclopentadienyl) dil
Conium dihydride, bis (pentamethylcyclopenta
Dienyl) zirconium dihydride, indenyl (sik
Lopentadienyl) zirconium dihydride, trimethyl
Rusilylcyclopentadienyl (cyclopentadienyl
Le) zirconium dimethyl, trimethylsilyl cyclope
Zentadienyl (cyclopentadienyl) zirconium
Hydride, trifluoromethylcyclopentadienyl
(Cyclopentadienyl) zirconium dichloride,
Trifluoromethyl cyclopentadienyl (cyclopen
Tadienyl) zirconium dimethyl, trifluoromethyl
Cyclopentadienyl (cyclopentadienyl) dil
Conium dihydride, bis (cyclopentadienyl)
(Trimethylsilyl) (methyl) zirconium, bis
(Cyclopentadienyl) (triphenylsilyl) (Me
Chill) zirconium, bis (cyclopentadienyl)
[Tris (dimethylsilyl) silyl] (methyl) zirco
Bis (cyclopentadienyl) [bis (methyl
(Silyl) silyl] (methyl) zirconium, bis (shiku)
Lopentadienyl) (trimethylsilyl) (trimethyl
Silylmethyl) zirconium, bis (cyclopentadiene)
Nyl) (trimethylsilyl) (benzyl) zirconium
Methylene, methylene-bis (cyclopentadienyl) zirconi
Umdichloride, ethylene-bis (cyclopentadiene
Nil) zirconium dichloride, isopropylidene-
Bis (cyclopentadienyl) zirconium dichlorate
Dimethylsilyl-bis (cyclopentadienyl) di
Ruconium dichloride, methylene-bis (cyclopen
Tadienyl) zirconium dimethyl, ethylene-bis
(Cyclopentadienyl) zirconium dimethyl, iso
Propylidene-bis (cyclopentadienyl) zirconi
Umdimethyl, dimethylsilyl-bis (cyclopentadiene
(Enyl) zirconium dimethyl, methylene-bis (cyclo)
Lopentadienyl) zirconium dihydride, ethylene
-Bis (cyclopentadienyl) zirconium dihydrogenation
, Isopropylidene-bis (cyclopentadienyl)
Zirconium dihydride, dimethylsilyl-bis (cycl
For example, lopentadienyl) zirconium dihydride.

The compounds corresponding to the general formula [2] include bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) ( Tetraphenylborate)
Tetrahydrofuran complex, bis (methylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (methylcyclopentadienyl) ) Zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (chloride), (tetraphenylborate) ) Tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydr Furan complex, bis (tetramethylcyclopentadienyl) zirconium (chloride)
(Tetraphenylborate) tetrahydrofuran complex,
Bis (ethyltetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (methyl) (Tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (methyl)
(Tetraphenylborate) tetrahydrofuran complex,
Bis (ethyltetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (hydride) , (Tetraphenylborate) tetrahydrofuran complex, Bis (trimethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, Bis (ethyltetramethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex , Bis (trimethylsilylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex Bis (trimethylsilylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadiene) (Enyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (methyl)
(Tetraphenylborate) tetrahydrofuran complex,
Isopropylidene-bis (indenyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (Cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl ( Cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopenta Ethenyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadiene) (Phenyl) (fluorenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) ) Zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirco Um (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (ethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, Bis (cyclopentadienyl) (propyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (phenyl) zirconium (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (Chloride) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (chloro) (Telide) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) Tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, ethyl Cyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, dimethyl Cyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclopentadiene Ethenyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) dil Nitrogen (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl ) (Tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, cyclopentadienyl (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethyl Cyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, Limethyl cyclopentadienyl (cyclopentadienyl) zirconium (hydride)
(Tetraphenylborate) tetrahydrofuran complex,
Bis (pentamethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) ) Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trifluoromethylcyclopentadienyl (cyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (triphenylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex,
Bis (cyclopentadienyl) [tris (dimethylsilyl) silyl] zirconium (tetraphenylborate)
Tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (benzyl) zirconium (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) ) Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl) zirconium (chloride) (tetra (Phenyl borate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride) (the Laphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropyl Ridene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (hydride)
(Tetraphenylborate) tetrahydrofuran complex,
Examples include isopropylidene-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, and the like.

The same compounds as described above can be used for the other Group 4, 5 and 6 metal compounds such as titanium compounds and hafnium compounds. Further, a mixture of these compounds may be used. In the present invention, as the component (B), clay, clay minerals or ion-exchangeable layered compounds are used. Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally-occurring ones, but may be artificially synthesized ones.

As the component [B], clay, clay minerals, hexagonal closest packing type, antimony type, CdCl ₂
Examples thereof include ionic crystalline compounds having a layered crystal structure such as C type and CdI ₂ type. Specific examples of the component [B] include kaolin, bentonite, kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, talc, ummo group, montmorillonite group, vermiculite, ryokdee group, palygorskite, kaolinite, nacrite. , Dickite, halloysite and the like.

The component (B) preferably has a pore volume of 20 cc or more and a pore volume of 0.1 cc / g or more, particularly 0.3 to 5 cc / g, as measured by the mercury penetration method.

Here, the pore volume is measured by a mercury porosimetry method using a mercury porosimeter as a pore radius of 20 to 3
It is measured in the range of 0000Å. In this example, “Auto Pore 9200” manufactured by Shimadzu Corporation was used for measurement. When a compound having a pore volume of 20 Å or more and a pore volume of 0.1 cc / g or less is used as the component (B), it tends to be difficult to obtain high polymerization activity.

It is also preferable that the component [B] is chemically treated.

Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure of clay can be used. Specific examples include acid treatment, alkali treatment, salt treatment and organic substance treatment. The acid treatment not only removes impurities on the surface but also increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. Alkali treatment destroys the crystal structure of clay and causes a change in the structure of clay.
In the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative, etc. are formed to change the surface area and the interlayer distance.

By utilizing the ion exchange property and substituting the exchangeable ions between the layers with another large bulky ion, it is possible to obtain a layered substance in which the layers are expanded. That is, bulky ions play a pillar-like role for supporting the layered structure, and are called pillars. Introducing another substance between layers of layered substances is called intercalation.

With guest compound for intercalation
Then TiCl_Four, ZrCl_FourCationic inorganic compounds such as
Thing, Ti (OR)_Four, Zr (OR)_Four, PO (O
R)₃, B (OR)₃[R is alkyl, aryl, etc.]
Metal alcoholates such as [Al₁₃O _Four(OH)_{twenty four}]⁷⁺,
[Zr_Four(OH)₁₄]²⁺, [Fe₃O (OCOCH₃)
₆] ⁺And the like, such as metal hydroxide ions. these
These compounds can be used alone or in combination of two or more.
You may use. In addition, these compounds are intercalated.
Si (OR)_Four, Al (OR)₃, G
e (OR)_FourObtained by hydrolyzing metal alcoholate, etc.
Polymer, SiO₂Coexist with colloidal inorganic compounds such as
You can also let it. Also, as an example of the pillar, the water
Oxide ions are added after intercalation between the layers.
Examples thereof include oxides produced by thermal dehydration.

The component [B] may be used as it is, or may be used after newly adsorbing and adsorbing water or after heat-dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids. As the component [B], preferred is clay or clay mineral, and most preferred is
It is montmorillonite.

Examples of the organoaluminum compound used as the component [C] in the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum methoxide. And other halogen- or alkoxy-containing alkylaluminum, aluminoxane such as methylaluminoxane, and the like, among which trialkylaluminum is particularly preferable.

The contact method for obtaining the polymerization catalyst from the components [A], [B] and [C] is described in [B]
When the component is clay or clay mineral, the molar ratio of the transition metal in the component [A] to the hydroxyl group in the clay or clay mineral and the aluminum in the [C] organoaluminum compound is 1: 0.1 to 100000: 0. .1 to 100,000
00, especially from 1: 0.5 to 10000: 0.
The catalytic reaction is preferably carried out at 5 to 1,000,000.

When the component [B] is other than clay or clay mineral, the weight ratio of the transition metal in the component [A] to aluminum in the component [C] is 1 g of the component [B]. 0.00001-1 (g): 0.001-100
It is preferable to bring them into contact so as to give (g). Contact with pentane, hexane, heptane, in an inert gas such as nitrogen,
It may be carried out in an inert hydrocarbon solvent such as toluene or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, preferably room temperature to the boiling point of the solvent.

Furthermore, in the present invention, as the organoaluminum compound [D] used as necessary, [C]
Compounds similar to the components are included. The amount of the organoaluminum compound used at this time is such that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the component [D] is 1: 0.
Selected to be ~ 10,000. The order of contacting the catalyst components is not particularly limited, but they can be contacted in the following contacting order.

After the components [A] and [B] are contacted with each other, the component [C] is added. The component [B] is added after the component [A] and the component [C] are brought into contact with each other. After the component [B] and the component [C] are contacted with each other, the component [A] is added. In addition, the three components may be contacted at the same time. During or after the contact of each component of the catalyst, a solid such as a polymer such as polyethylene or polypropylene and an inorganic oxide such as silica or alumina may be present or contacted.

As the olefin used for the polymerization, ethylene, propylene, 1-butene, 1-hexene, 3-
Methyl-1-butene, 3-methyl-1-pentene, 4-
Examples include methyl-1-pentene, vinylcycloalkane, styrene, and derivatives thereof. Further, the polymerization can be suitably applied to not only homopolymerization but also generally known random copolymerization and block copolymerization.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but it is preferably atmospheric pressure to about 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight modifier in the polymerization system.

[0035]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples without departing from the gist thereof. Also, FIG.
Is a flowchart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not restricted by the flowchart unless it deviates from the gist thereof.

<Example 1> (1) Synthesis of catalyst component A commercially available montmorillonite (manufactured by Aldrich, Montmorillonit) was placed in a 300 ml round bottom flask.
e K10; 17 g of pore volume of 1.04 cc / g or more having a radius of 20 Å or more measured by mercury porosimetry method was collected, and after replacing the inside of the flask with nitrogen, 50 ml of toluene was added to form a slurry. Separately, 7.21 g of trimethylaluminum was dissolved in 50 ml of toluene. While vigorously stirring the montmorillonite slurry, a trimethylaluminum solution was slowly added dropwise thereto at room temperature. It generated heat with the generation of gas. The stirring was continued for 2 hours while appropriately cooling with ice water to obtain a grayish green slurry.

(2) Polymerization of ethylene 2.5 mg of biscyclopentadienyl zirconium dichloride was added to 4.8 ml of a 0.0179 M trimethylaluminum toluene solution at room temperature under a nitrogen atmosphere in 30 ml.
It was preliminarily contacted with the catalyst component slurry prepared in the above (1) for 4.7 minutes and preliminarily contacted for 20 minutes.

In a 2 liter induction-stirring autoclave substituted with purified nitrogen, toluene 50 at room temperature under a nitrogen stream.
0 ml and the above catalytic component contact mixture were added. After heating the mixed solution to 70 ° C., the ethylene partial pressure was 9 kgf / cm 2.
Ethylene was introduced so that the amount became ^2, and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Then, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 170 g of powdered polyethylene. The amount of polyethylene produced per 1 g of the transition metal catalyst component (biscyclopentadienyl zirconium dichloride, the same applies hereafter unless otherwise noted) was 6.80 × 10 ⁴ g, and the polymerization activity was 7600 g-PE.
/ G-cat · h · kgf · cm ⁻² . The amount of polyethylene produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and biscyclopentadienyl zirconium dichloride was 1600 g.

<Example 2> (1) Copolymerization of ethylene-propylene 0.27 mg of biscyclopentadienyl zirconium dichloride was mixed with 0.48 ml of a toluene solution of 0.0179 M trimethylaluminum in a nitrogen atmosphere at room temperature.
It was pre-contacted for 0 minutes and further pre-contacted for 20 minutes with 0.47 ml of the catalyst component slurry prepared in Example 1 (1) above.

Into a 2-liter induction-stirring autoclave replaced with purified nitrogen, toluene 3 was added at room temperature under a nitrogen stream.
00 ml and the above catalyst contact mixture were introduced. Furthermore, 600 ml of liquid propylene was introduced. After the temperature of the mixed solution was raised to 70 ° C., ethylene was introduced so that the ethylene partial pressure became 7.6 kgf / cm ^2, and polymerization was carried out for 1 hour. Then, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Thereafter, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 100 g of an ethylene-propylene copolymer. Transition metal catalyst component 1 g
The amount of the produced copolymer was 3.7 × 10 ⁵ g. The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and biscyclopentadienyl zirconium dichloride was 8600 g. The molecular weight distribution of the obtained copolymer was Mw / Mn = 2.1.

(2) Copolymerization of ethylene-propylene 0.25 mg of biscyclopentadienylzirconium dichloride was prepared at room temperature under a nitrogen atmosphere in Example 1 above.
0.47 m of catalyst component slurry produced by (1)
1 was pre-contacted for 20 minutes.

In a 2-liter induction-stirring autoclave substituted with purified nitrogen, toluene 3 was added at room temperature under a nitrogen stream.
00 ml and the catalyst component contact mixture described above were added. Furthermore, 600 ml of liquid propylene was introduced. Mixture 70
After the temperature was raised to ° C, ethylene was introduced so that the ethylene partial pressure became 7.6 kgf / cm ^2, and the polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave are heated to 30 ° C.
After the temperature was lowered to, the internal gas was purged to obtain 38.7 g of an ethylene-propylene copolymer. The amount of the copolymer produced per 1 g of the transition metal catalyst component was 1.54 × 10 ⁵ g. In addition, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite was 3300 g.

<Example 3> (1) Synthesis of catalyst component A commercially available kaolin (Fish) was placed in a 500 ml round bottom flask.
er Scientific Co. Manufactured: Acid-treated product: Pore volume of more than 20 Å radius measured by mercury porosimetry is 0.6
(91 cc / g) 6.46 g was sampled, and the inside of the flask was replaced with nitrogen, and then 200 ml of toluene was added to form a slurry. Separately, 7.21 g of trimethylaluminum is added to 50
Dissolved in ml toluene. The trimethylaluminum solution was slowly added dropwise at room temperature while vigorously stirring the kaolin slurry, and then refluxed for 2 hours to obtain a brown slurry.

(2) Copolymerization of ethylene-propylene 2.7 mg of biscyclopentadienyl zirconium dichloride was added to 0.44 ml of a 0.196 M solution of trimethylaluminum in toluene at room temperature under a nitrogen atmosphere.
It was pre-contacted for 14 minutes, and further pre-contacted with 14 ml of the catalyst component slurry prepared in Example 3 (1) above for 20 minutes.

Into a 2-liter induction-stirring autoclave substituted with purified nitrogen, toluene 3 was added at room temperature under a nitrogen stream.
00 ml and the catalyst component contact mixture described above were added. Furthermore, 600 ml of liquid propylene was introduced. Mixture 70
After the temperature was raised to ℃, the ethylene partial pressure was 7.6 kgf / cm ^2.
And ethylene was introduced so that the polymerization was carried out for 1 hour.
After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the autoclave contents were cooled to 30 ° C., and then the internal gas was purged to obtain 105 g of an ethylene-propylene copolymer. The amount of the copolymer produced per 1 g of the transition metal catalyst component is 3.9 × 10 ⁴ g
Met. The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with kaolin and biscyclopentadienyl zirconium dichloride was 844 g.

Example 4 (1) Component [A], bis (cyclopentadienyl)
Synthesis of (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex 7.5 g of commercially available biscyclopentadienyl zirconium dichloride was collected in a 300 ml round-bottomed flask, and the inside of the flask was replaced with nitrogen, and 120 ml of diethyl ether was added at -20 ° C. It was added to make a slurry. 32 ml of a hexane solution of methyllithium (1.6M) was slowly added to this slurry at -20 ° C, and the mixture was stirred at 0 ° C for 30 minutes.
It was stirred for a minute. Then the solvent was evaporated and the remaining solids were
Purified by sublimation under reduced pressure of 2 × 10 ⁻⁴ mmHg at 0 to 80 ° C.,
Biscyclopentadienylzirconium dimethyl was obtained. Separately, an aqueous solution of 3.40 g of silver nitrate and 6.84 g of sodium tetraphenylborate were mixed to obtain silver tetraphenylborate.

Biscyclopentadienylzirconium dimethyl synthesized as described above was dissolved in 10 ml of acetonitrile, and 1.0 g of silver tetraphenylborate was added to this solution.
Of acetonitrile (10 ml) was added at 0 ° C. and stirred for 1 hour. The resulting solution was separated from the solid, evaporated to dryness and then washed with cold acetonitrile. Then, it was recrystallized from acetonitrile and dried under reduced pressure for 48 hours. The obtained solid was recrystallized three times with tetrahydrofuran to obtain a bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex.

(2) Copolymerization of Ethylene-Propylene Copolymerization of ethylene-propylene was carried out by copolymerizing 0.55 mg of bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran obtained in the above Example 4 (1). The complex at room temperature under a nitrogen atmosphere at 0.196
Toluene solution of M trimethylaluminum 0.49 ml
Was pre-contacted for 30 minutes with 0.48 ml of the catalyst component slurry prepared in Example 1 (1).

In a 2 liter induction-stirring autoclave substituted with purified nitrogen, toluene 3 was added at room temperature under a nitrogen stream.
00 ml and the above catalytic component contact mixture were added.
Furthermore, 600 ml of liquid propylene was introduced. Mixture 70
After the temperature was raised to ° C, ethylene was introduced so that the ethylene partial pressure became 7.6 kgf / cm ^2, and the polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, 3 contents of autoclave
After the temperature was lowered to 0 ° C., the internal gas was purged to obtain 24.2 g of an ethylene-propylene copolymer. The amount of the copolymer produced per 1 g of the transition metal catalyst component (bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex) was 4.4 × 10 ^4.
It was g. The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and the component [A] was 2200 g.

<Comparative Example 1> 0.97 mg of biscyclopentadienyl zirconium dichloride was stirred at room temperature in a nitrogen atmosphere with a methylaluminoxane (molecular weight 1232; manufactured by Tosoh Akzo) 5.00 mmol toluene solution in terms of Al atoms for 30 minutes. It was pre-contacted.

In a 2-liter induction-stirring autoclave substituted with purified nitrogen, toluene 5 was added at room temperature under a nitrogen stream.
00 ml, a mixed solution of biscyclopentadienyl zirconium dichloride and methylaluminoxane was added. After heating the mixture to 70 ° C, the ethylene partial pressure was 9 kg.
Ethylene was introduced so as to be f / cm ² and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 11.6 g of powdered polyethylene. The amount of polyethylene produced per 1 g of the transition metal catalyst component is 1.20 ×
10 ⁴ g, polymerization activity is 1300 g-PE / g-cat.
It was h · kgf · cm ⁻² . The amount of polyethylene produced per 1 g of aluminum derived from methylaluminoxane was 86 g.

Example 5 (1) Synthesis of catalyst In a 100 ml round bottom flask, 8.9 mg of commercially available biscyclopentadienylzirconium dichloride was collected,
After replacing the inside of the flask with nitrogen, 25 ml of n-heptane was added to form a slurry. Separately, 1.18 g of trimethylaluminum and 3.72 g of commercially available montmorillonite were respectively collected, and 5 ml of n-heptane and 15 m, respectively.
1 was added. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, the montmorillonite slurry was added dropwise thereto at room temperature, and then the trimethylaluminum solution was added dropwise. It generated heat with the generation of gas. After the completion of dropping, stirring was continued for 2 hours to obtain a gray slurry. The zirconium concentration in the catalyst slurry is
It was 0.72 μmol / ml.

(2) Polymerization of ethylene In a 2-liter induction stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and 3.9 ml of the catalyst slurry obtained in Example 5 (1) above were successively introduced. After the temperature of the mixed solution was raised to 70 ° C., ethylene was introduced so that the ethylene partial pressure was 9 kgf / cm ^2, and polymerization was carried out for 30 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave were cooled to 30 ° C., the internal gas was purged, and the powdered polyethylene 230
g was obtained. The amount of polymer produced per 1 g of the transition metal catalyst component was 2.8 × 10 ⁵ . The amount of polymer produced per g of aluminum derived from trimethylaluminum was 8500 g.

(3) Copolymerization of ethylene-propylene In a 2-liter induction-stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and 2.6 ml of the above catalyst slurry were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After raising the temperature of the mixed liquid to 70 ° C., the ethylene partial pressure was 7.6.
Ethylene was introduced so that the concentration would be kgf / cm ^2, and polymerization was carried out for 25 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Then, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 243 g of an ethylene-propylene copolymer. The amount of copolymer produced per 1 g of the transition metal catalyst component is 4.4 ×
It was 10 ⁵ g. Further, the amount of the copolymer produced from 1 g of aluminum derived from trimethylaluminum is 92
It was 00 g.

Example 6 (1) Synthesis of catalyst component Commercially available montmorillonite 1 was placed in a 300 ml round bottom flask.
After collecting 7.7 g and thoroughly replacing the inside of the flask with nitrogen,
80 ml of toluene was added to make a slurry. Separately, 5.86 g of trimethylaluminum was dissolved in 20 ml of toluene. While stirring the trimethylaluminum solution vigorously, the montmorillonite slurry was added dropwise thereto at room temperature. It generated heat with the generation of gas. After completion of dropping, the mixture was stirred for 2 hours to obtain a greenish gray slurry.

(2) Polymerization of ethylene-propylene 0.57 mg of biscyclopentadienylzirconium dichloride was added at room temperature under a nitrogen atmosphere at 10.10 mM.
1.9 ml of toluene solution of trimethylaluminum and 3
It was pre-contacted for 0 minutes and further pre-contacted with 1.3 ml of the catalyst component slurry prepared in Example 6 (1) above.

Into a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene and the above catalytic component contact mixture were introduced at room temperature under a nitrogen stream. Furthermore, 600 ml of liquid propylene was introduced. After heating the autoclave to 70 ° C, the ethylene partial pressure was 7.6 kgf.
Ethylene was introduced so that the ratio would be / cm ^2, and polymerization was carried out for 30 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. 310 g of an ethylene-propylene copolymer was obtained. The amount of the copolymer produced per 1 g of the transition metal catalyst component was 5.5 × 10 ⁵ g. Also,
The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and biscyclopentadienyl zirconium dichloride was 12000 g.

(3) Copolymerization of ethylene-propylene 0.50 mg of biscyclopentadienyl zirconium dichloride was added to 1.8 ml of toluene solution of 9.50 mM triethylaluminum in a nitrogen atmosphere at room temperature under a nitrogen atmosphere.
It was pre-contacted with the catalyst component slurry prepared in Example 6 (1) above for 1.1 minutes.

To a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene and the above catalytic component contact mixture were introduced at room temperature under a nitrogen stream. Furthermore, 600 ml of liquid propylene was introduced. After heating the autoclave to 70 ° C, the ethylene partial pressure was 7.6 kgf.
Ethylene was introduced so that the ratio would be / cm ^2, and polymerization was carried out for 30 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. 299 g of an ethylene-propylene copolymer was obtained. The amount of the copolymer produced per 1 g of the transition metal catalyst component was 6.0 × 10 ⁵ g. Also,
The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum contacted with montmorillonite and triethylaluminum contacted with biscyclopentadienylzirconium dichloride was 13000 g.

Example 7 (1) Synthesis of ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride The above complex was synthesized in the Journal of Organo.
metallic Chemistry, 232 (19
82) 233 as described for ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride.

(2) Polymerization of Propylene 0.82 mg of racemic ethylene bis (4,5,6,6)
7-Tetrahydroindenyl) zirconium dichloride was pre-contacted with 1.9 ml of a toluene solution of 10.10 mM trimethylaluminum for 30 minutes at room temperature under a nitrogen atmosphere, and the catalyst component slurry prepared according to Example 6 (1) above was further added. Pre-contact with 1.3 ml.

Into a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene and the above catalytic component contact mixture were introduced at room temperature under a nitrogen stream. Furthermore, 600 ml of liquid propylene was introduced. The temperature of the autoclave was raised to 70 ° C., and polymerization was performed for 30 minutes. After that, the gas inside the autoclave was purged to obtain 286 g of a propylene polymer. The amount of polymer produced per 1 g of the transition metal catalyst component (ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride) is
It was 3.5 × 10 ⁵ g. The amount of propylene polymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride was 9900 g. The boiling heptane-insoluble portion (the value after refluxing for 6 hours) showing stereoregularity was 96%.

Comparative Example 2 0.82 mg of racemic ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride was added at room temperature under a nitrogen atmosphere to a 10.10 mM trimethylaluminum triene solution 1. Contact with 9 ml for 30 minutes, and then methylaluminoxane (manufactured by Tosoh Akzo) 12.5m in terms of Al atom
Polymerization of propylene was carried out using the one that had been pre-contacted with a mol solution of toluene.

In a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene at room temperature under a stream of nitrogen, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride and methylaluminoxane were mixed. The solution was added. Furthermore, 600 ml of liquid propylene was introduced. The temperature of the autoclave was raised to 70 ° C. and polymerization was carried out for 1 hour. After that, the gas inside was purged to obtain 115 g of a propylene polymer. The amount of the propylene polymer produced per 1 g of the transition metal catalyst component (ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride) was 1.4 × 10 ⁵ g.
In addition, aluminum 1 derived from methylaluminoxane
The amount of propylene produced per gram was 340 g. The boiling heptane-insoluble portion was 96%.

Example 8 (1) Synthesis of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride The above complex was synthesized in the same manner as the method described in JP-A-2-41305.

(2) Polymerization of Propylene 0.83 mg of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was pre-contacted with 1.9 ml of a toluene solution of 10.10 mM trimethylaluminum for 30 minutes at room temperature under a nitrogen atmosphere. Then, 1.3 ml of the catalyst component slurry prepared in Example 6 (1) above was pre-contacted.

Into a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene and the above catalytic component contact mixture were introduced at room temperature under a nitrogen stream.
Furthermore, 600 ml of liquid propylene was introduced. The temperature of the autoclave was raised to 70 ° C., and polymerization was performed for 30 minutes. Then, the gas inside the autoclave was purged to obtain 253 g of a propylene polymer. The amount of propylene polymer produced per 1 g of the transition metal catalyst component was 3.0 × 10 ⁵ g. The amount of polymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was 8800 g. The content of rrrr of the obtained polymer by ¹³ C-NMR, that is, the syndiotactic polymer content was 90%.

<Comparative Example 3> 0.83 mg of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride at room temperature under nitrogen atmosphere in methylaluminoxane (manufactured by Tosoh Akzo) converted into Al atoms.
It was pre-contacted with a 5 mmol toluene solution for 30 minutes.

To a 2-liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene was added at room temperature under a nitrogen stream, and a mixed solution of the isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride and methylaluminoxane was added. did. Furthermore, 600 ml of liquid propylene was introduced. The temperature of the autoclave was raised to 70 ° C. and polymerization was carried out for 1 hour. After that, the gas inside the autoclave was purged, and the propylene polymer 10
8 g was obtained. The amount of propylene polymer produced per 1 g of the transition metal catalyst component was 1.3 × 10 ⁵ g. The amount of propylene polymer produced per 1 g of aluminum derived from methylaluminoxane was 320 g. The rrrr of the obtained polymer by ¹³ C-NMR was 89%.

Example 9 (1) Synthesis of catalyst component Commercially available montmorillonite 1 was placed in a 300 ml round bottom flask.
After collecting 8.1 g and thoroughly replacing the inside of the flask with nitrogen,
80 ml of n-heptane was added to make a slurry. Separately, 6.25 g of trimethylaluminum was dissolved in 20 ml of n-heptane. While stirring the trimethylaluminum solution vigorously, the montmorillonite slurry was slowly added dropwise thereto at room temperature. It generated heat with the generation of gas. After the completion of dropping, stirring was continued for 2 hours to obtain a gray slurry.

(2) Copolymerization of ethylene-propylene 0.59 mg of biscyclopentadienyl zirconium dichloride was added to 2.0 ml of a toluene solution of 0.0102 M trimethylaluminum at room temperature under a nitrogen atmosphere and 30 ml.
It was pre-contacted for 1.2 minutes and further pre-contacted with 1.2 ml of the catalyst component slurry prepared in Example 9 (1) above for 20 minutes.

To a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of n-hexane and the above catalytic component contact mixture were introduced at room temperature under a nitrogen stream. Furthermore, 600 ml of liquid propylene was introduced. After heating the mixed solution to 70 ° C., the ethylene partial pressure was 7.6 kgf / c.
Ethylene was introduced so as to be m ² and polymerization was carried out for 20 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Thereafter, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 311 g of an ethylene-propylene copolymer. The amount of the copolymer produced per 1 g of the transition metal catalyst component is 5.3 × 10 ⁵ g
Met. The amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and biscyclopentadienyl zirconium dichloride was 11000 g.

Example 10 (1) Synthesis of catalyst 15.1 mg of commercially available biscyclopentadienylzirconium dichloride was placed in a 300 ml round-bottomed flask, the inside of the flask was replaced with nitrogen, and n-heptane 50 m was added.
1 was added to make a slurry. Separately, 1.99 g of trimethylaluminum and 6.21 g of commercially available montmorillonite
Respectively, 10 ml each of n-heptane,
40 ml was added. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, a trimethylaluminum solution was added dropwise thereto at room temperature, and then a montmorillonite slurry was added dropwise. It generated heat with the generation of gas. After the completion of dropping, stirring was continued for 2 hours to obtain a gray slurry. The zirconium concentration in the catalyst slurry was 0.49 μmol / ml.

(2) Polymerization of ethylene In a 2-liter induction stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and the catalyst slurry 3.9 ml were sequentially introduced. After raising the temperature of the mixed solution to 70 ° C., ethylene was introduced so that the ethylene partial pressure became 9 kgf / cm ^2, and 1
Polymerization was carried out for 5 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Then, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 244 g of powdered polyethylene. The amount of polymer produced per 1 g of the transition metal catalyst component is 4.4 × 10 ⁵ g
Met. The amount of polymer produced per 1 g of aluminum derived from trimethylaluminum was 8800 g.

(3) Copolymerization of ethylene-propylene In a 2-liter induction-stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and the catalyst slurry 3.9 ml were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After raising the temperature of the mixed liquid to 70 ° C., the ethylene partial pressure was 7.6.
Ethylene was introduced so that the pressure would be kgf / cm ^2, and polymerization was carried out for 16 minutes. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Then, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 302 g of an ethylene-propylene copolymer. The amount of the copolymer produced per 1 g of the transition metal catalyst component was 5.4.
It was × 10 ⁵ g. In addition, the amount of copolymer produced from 1 g of aluminum derived from trimethylaluminum is 1
It was 1000 g.

Example 11 (1) Synthesis of catalyst 3.12 g of vermiculite having a pore volume of 0.791 cc / g with a radius of 20 Å or more measured by mercury porosimetry was sampled in a 200 ml round bottom flask, and the inside of the flask was taken. After substituting with nitrogen, 50.8 ml of n-hexane was added to form a slurry. Separately, 1.25 g of trimethylaluminum was dissolved in 20.6 ml of n-hexane. While stirring the vermiculite slurry, the trimethylaluminum solution was slowly added dropwise thereto at room temperature. While appropriately cooling, stirring was continued for 2 hours to obtain a slurry.

(2) Copolymerization of ethylene-propylene 1.40 mg of biscyclopentadienylzirconium dichloride was preliminarily contacted with a toluene solution of trimethylaluminum (23.8 μmol as trimethylaluminum) for 30 minutes at room temperature in a nitrogen atmosphere. Furthermore, 5.0 ml of the catalyst component slurry prepared in Example 11 (1) above was pre-contacted for 20 minutes.

300 ml of n-hexane and the above catalytic component contact mixture were introduced into a 2 liter induction-stirring autoclave substituted with purified nitrogen at room temperature under a nitrogen stream.
Furthermore, 600 ml of liquid propylene was introduced. Mix 7
After the temperature was raised to 0 ° C, the ethylene partial pressure was 7.6 kgf / cm ²
And ethylene was introduced so that the polymerization was carried out for 1 hour.
Then, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. Then autoclave contents 30
After lowering the temperature to ℃, purge the gas inside and
55.6 g of a propylene copolymer was obtained. Zirconium 1
The amount of copolymer produced per g was 1.3 × 10 ⁵ g. The amount of the copolymer produced was 1700 g per 1 g of aluminum derived from trimethylaluminum brought into contact with vermiculite and biscyclopentadienyl zirconium dichloride.

Example 12 (1) Synthesis of catalyst Smecton SA-1 (Kunimine Industries Co., Ltd.) having a pore volume of 0.712 cc / g with a radius of 20 Å or more measured in a 200 ml round-bottomed flask by mercury porosimetry. Made) 4.11g
Was collected, the inside of the flask was replaced with nitrogen, and then 81.2 ml of n-hexane was added to obtain a slurry. Separately, 1.92 g of trimethylaluminum and 20.2 m of n-hexane
It was dissolved in 1. While stirring the Smecton SA-1 slurry, the above trimethylaluminum solution was slowly added dropwise thereto at room temperature. While appropriately cooling, stirring was continued for 2 hours to obtain a slurry.

(2) Copolymerization of ethylene-propylene 1.28 mg of biscyclopentadienylzirconium dichloride was pre-contacted with a toluene solution of trimethylaluminum (21.9 μmol as trimethylaluminum) for 30 minutes at room temperature under a nitrogen atmosphere. Furthermore, 4.3 ml of the catalyst component slurry prepared in Example 12 (1) above was pre-contacted for 20 minutes.

Then, in the same manner as in Example 11 (2), 48.4 g of a polymer was obtained. The amount of the copolymer produced per 1 g of zirconium was 1.2 × 10 ⁵ g. The amount of the copolymer produced was 1600 g per 1 g of aluminum derived from trimethylaluminum brought into contact with Smecton SA-1 and biscyclopentadienyl zirconium dichloride.

Example 13 (1) Synthesis of catalyst A commercially available biscyclopentadienyl zirconium dichloride (0.1 ml) was added to a 100 ml round-bottomed flask that had been sufficiently replaced with nitrogen.
72 mg of a toluene solution was collected, and 1.3 mmol of trimethylaluminum was added while stirring at room temperature. Separately, 3.33 g of mica having a radius of 20 Å or more and a pore volume of 0.670 cc / g measured by the mercury injection method in a 100 ml round-bottomed flask was sampled, and the inside of the flask was replaced with nitrogen, followed by n-hexane 63.9 ml. Was added to form a slurry. 4.9 ml of this slurry was added at room temperature to the contact product of biscyclopentadienyl zirconium dichloride and trimethylaluminum. After the addition was completed, the mixture was stirred at room temperature for 1 hour to obtain a catalyst slurry.

(2) Copolymerization of ethylene-propylene In a 2-liter induction stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
2.4 ml of 8 mM), and then the whole amount of the catalyst slurry was introduced. Furthermore, 600 ml of liquid propylene was introduced. After heating the mixed solution to 70 ° C., the ethylene partial pressure was 7.6 kgf.
Ethylene was introduced so that the concentration would be / cm ^2, and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 42.9 g of an ethylene-propylene copolymer. The amount of copolymer produced per 1 g of zirconium is 1.9 × 10 ⁵ g
Met. In addition, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum was 1200 g.

Example 14 (1) Synthesis of zirconium-montmorillonite intercalation compound Zirconium oxychloride octahydrate (Wako Pure Chemical Industries; special grade) 6
4.45 g was dissolved in 1 liter of pure water, and montmorillonite (Aldrich: Montmorillonite) was added.
K-10; the same applies hereinafter) (6.0 g) was added to form a slurry. After stirring at 70 ° C. for 1 hour, the mixture is filtered, and hot pure water 500 is added.
Washed with ml. Then, it was air dried at room temperature overnight to obtain the title compound.

(2) Synthesis of catalyst 10.0 mg of commercially available biscyclopentadienylzirconium dichloride was placed in a 100 ml round-bottomed flask, the inside of the flask was replaced with nitrogen, and then 10 m of n-heptane was added.
1 was added to make a slurry. Separately, 1.21 g of trimethylaluminum and 3.0 g of the zirconium-montmorillonite intercalation compound synthesized in Example 14 (1) were collected, and 20 ml of n-heptane was added to each. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, a trimethylaluminum solution was added dropwise thereto at room temperature, and then a zirconium-montmorillonite intercalation compound slurry was added dropwise. It generated heat with the generation of gas. After completion of dropping, stirring was continued for 2 hours to obtain a gray catalyst slurry. The zirconium concentration derived from biscyclopentadienyl zirconium dichloride in the slurry was 0.65 μmol / ml.

(3) Polymerization of ethylene In a 2-liter induction-stirring autoclave sufficiently replaced with purified nitrogen, n-hexane 500 was added at room temperature under a nitrogen stream.
ml, toluene solution of trimethylaluminum (10.
1.9 ml of 18 mM) and 3.0 ml of the above catalyst slurry were sequentially introduced. After raising the temperature of the mixed liquid to 70 ° C., ethylene was introduced so that the ethylene partial pressure became 9 kgf / cm ² .
Polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped,
Polymerization was stopped by introducing ethanol. Then, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 42 g of powder polyethylene. The amount of polyethylene produced from 1 g of zirconium derived from biscyclopentadienyl zirconium dichloride is 1.0
It was × 10 ⁶ g. The amount of polyethylene produced per gram of aluminum derived from trimethylaluminum was 7,000 g.

(4) Copolymerization of ethylene-propylene In a 2-liter induction stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and 3.0 ml of the above catalyst slurry were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After raising the temperature of the mixed liquid to 70 ° C., the ethylene partial pressure was 7.6.
Ethylene was introduced so that the concentration would be kgf / cm ^2, and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged. As a result, ethylene with Mw / Mn of 2.2
217 g of a propylene copolymer was obtained. The amount of copolymer produced per 1 g of zirconium derived from biscyclopentadienyl zirconium dichloride is 1.2 × 10 ⁶ g
Met. In addition, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum was 8300 g.

Example 15 (1) Synthesis of catalyst Into a 100 ml round bottom flask, 50 mg of commercially available biscyclopentadienylzirconium dichloride was sampled, and the inside of the flask was sufficiently replaced with nitrogen, and then 10 ml of n-heptane.
Was added to form a slurry. Separately, 1.25 g of trimethylaluminum and 3.0 g of the zirconium-montmorillonite intercalation compound synthesized in Example 14 (1) were separately collected, and 20 ml of n-heptane was added. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, a trimethylaluminum solution was added dropwise thereto at room temperature, and then a zirconium-montmorillonite intercalation compound slurry was added dropwise. It generated heat with the generation of gas. After completion of dropping, continue stirring for 2 hours,
A gray slurry was obtained. The zirconium concentration in the catalyst slurry was 3.3 μmol / ml.

Further, in another 100 ml round bottom flask, 40 ml of the above catalyst slurry was dispensed at room temperature under a nitrogen atmosphere,
Toluene solution of trimethylaluminum (196 mM)
6.7 ml was added. Then, ethylene gas was introduced into the system, and prepolymerized at room temperature for 3 hours. After that, the supernatant was removed and washed with hexane. By this reaction, with respect to 1 g of the zirconium-montmorillonite intercalation compound, 35.8 μmol of zirconium derived from biscyclopentadienylzirconium dichloride, 4.25 mmol of aluminum derived from trimethylaluminum, and 3.8 g of polyethylene were obtained as a solid catalyst. It was

(2) Polymerization of ethylene In a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 150 g of sodium chloride dried at room temperature under a nitrogen stream, and the above solid catalyst was zirconium derived from biscyclopentadienyl zirconium dichloride. Around 8.
5 μmol and 8.4 ml of a toluene solution of trimethylaluminum (10.18 mM) were introduced. After heating the contents of the autoclave to 70 ° C, the ethylene partial pressure was 9
Ethylene was introduced so that the concentration would be kgf / cm ^2, and polymerization was carried out for 1 hour. Then, the content of the autoclave was washed with water to remove sodium chloride, and then the polymer was washed with hexane. As a result, powdered polyethylene 127 having a bulk specific gravity of 0.45 g / cm ³ and an Mw / Mn of 2.3.
g was obtained. The amount of polyethylene produced from 1 g of zirconium derived from biscyclopentadienylzirconium dichloride was 1.6 × 10 ⁵ g, and the amount of polyethylene produced from 1 g of aluminum derived from trimethylaluminum was 4300 g.

Example 16 (1) Synthesis of zirconium-bridged montmorillonite The zirconium-montmorillonite intercalation compound synthesized in Example 14 (1) was air-baked at 400 ° C. for 4 hours to obtain zirconium-bridged montmorillonite.

(2) Synthesis of catalyst 7.5 mg of commercially available biscyclopentadienylzirconium dichloride was collected in a 100 ml round bottom flask,
After replacing the inside of the flask with nitrogen, 10 ml of n-heptane was added to form a slurry. Separately, 0.93 g of trimethylaluminum and 2.9 g of zirconium-bridged montmorillonite synthesized in Example 16 (1) were collected, and 20 ml of n-heptane was added to each. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, a trimethylaluminum solution was added dropwise thereto at room temperature, and then a zirconium-bridged montmorillonite slurry was added dropwise. It generated heat with the generation of gas. After completion of dropping, stirring was continued for 2 hours to obtain a gray catalyst slurry. The concentration of zirconium derived from biscyclopentadienyl zirconium dichloride in the slurry was 0.5.
It was 0 μmol / l.

(4) Copolymerization of ethylene-propylene In a 2-liter induction-stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
2.2 ml of 8 mM) and 4.4 ml of the above catalyst slurry were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After raising the temperature of the mixed liquid to 70 ° C., the ethylene partial pressure was 7.6.
Ethylene was introduced so that the concentration would be kgf / cm ^2, and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged. As a result, ethylene with Mw / Mn of 2.2
199 g of a propylene copolymer was obtained. The amount of the copolymer produced from 1 g of zirconium derived from biscyclopentadienyl zirconium dichloride was 1.0 × 10 ⁶ g.
Met. In addition, the amount of the copolymer produced from 1 g of aluminum derived from trimethylaluminum was 6600 g.

Example 17 (1) Synthesis of aluminum-montmorillonite intercalation compound Aluminum chloride hexahydrate (Wako Pure Chemical Industries; special grade) 60.4
g was dissolved in 250 ml of pure water, and 54.0 g of metal aluminum powder (Wako Pure Chemical Industries, Ltd.) was added thereto. This was stirred while heating on a hot water bath, and hydrogen was gently generated. After the generation of hydrogen was completed, the unreacted aluminum powder was filtered off to obtain an aluminum chlorohydroxide complex solution.
20 g of montmorillonite was added to this solution, and the mixture was stirred at 70 ° C. for 1 hour. The resulting slurry is filtered and hot pure water 5
It was washed with 00 ml. Then, it was air dried at room temperature overnight to obtain the title compound.

(2) Synthesis of catalyst 21.2 mg of commercially available biscyclopentadienylzirconium dichloride was placed in a 100 ml round bottom flask, and the atmosphere in the flask was replaced with nitrogen.
1 was added to make a slurry. Separately, 2.61 g of trimethylaluminum and 3.1 g of the aluminum-montmorillonite intercalation compound synthesized in Example 17 (1) were collected, and 20 ml of n-heptane was added to each. While stirring the biscyclopentadienyl zirconium dichloride slurry vigorously, a trimethylaluminum solution was added dropwise thereto at room temperature, and then an aluminum-montmorillonite intercalation compound slurry was added dropwise. It generated heat with the generation of gas. After completion of dropping, stirring was continued for 2 hours to obtain a gray catalyst slurry. The zirconium concentration derived from biscyclopentadienyl zirconium dichloride in the slurry was 1.32 μmol / ml.

(4) Copolymerization of ethylene-propylene In a 2-liter induction-stirring autoclave substituted with purified nitrogen, 300 m of n-hexane was added at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 2.6 ml and 2.0 ml of the above catalyst slurry were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After raising the temperature of the mixed liquid to 70 ° C., the ethylene partial pressure was 7.6.
Ethylene was introduced so that the concentration would be kgf / cm ^2, and polymerization was carried out for 1 hour. After that, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged. As a result, ethylene with Mw / Mn of 2.2
54 g of a propylene copolymer was obtained. The amount of the copolymer produced per 1 g of zirconium derived from biscyclopentadienyl zirconium dichloride was 2.2 × 10 ⁵ g. In addition, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum was 1500 g.

[0097]

According to the method of the present invention, an olefin polymer having a narrow molecular weight distribution and a narrow composition distribution is obtained with extremely high polymerization activity when applied to the copolymerization of two or more kinds of olefins. Therefore, it is not necessary to remove the catalyst residue from the obtained polymer, which is industrially very useful.

[Brief description of drawings]

FIG. 1 is a flowchart showing one embodiment of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Fumihiko Shimizu 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Kasei Co., Ltd. (72) Eiji Isobe 1000 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Ryokasei Co., Ltd.

Claims (2)

[Claims] 1. An [A] metallocene-based transition metal compound,
[B] clay, clay mineral or ion-exchange layered compound,
And a catalyst obtained by bringing [C] an organoaluminum compound into contact with the catalyst for olefin polymerization. 2. A metallocene-based transition metal compound [A],
[B] clay, clay mineral or ion-exchange layered compound,
And a product obtained by contacting [C] an organoaluminum compound, and optionally a olefin homopolymerized or copolymerized in the presence of a catalyst consisting of an [A] organoaluminum compound. Manufacturing method.