JP3452525B2 - Method for producing catalyst for olefin polymerization - Google Patents

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).
No. 9, JP-A-2-167307, etc.).

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, and 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 not only uneconomical. , It was necessary to remove the catalyst residue from the produced polymer. On the other hand, a method has also been proposed in which one or both of the above transition metal compound and an aluminoxane are supported on an inorganic oxide such as silica or alumina to polymerize an olefin (Japanese Patent Laid-Open No. 61-108610). 60-135408
JP-A No. 61-296008 and JP-A-3-74
No. 412, No. 3-74415, etc.).

A method has also been proposed 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 to polymerize an olefin (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 was not negligible.

[0006]

As a result of studies to solve the above-mentioned problems, the present inventors have found a catalyst having sufficiently high polymerization activity per transition metal and per aluminum, and arrived at the present invention. That is, the present invention relates to a [A] metallocene-based transition metal compound, wherein the transition metal is selected from the group consisting of titanium, zirconium, and hafnium, and [B] clay or clay mineral and [C] tritium A method for producing an olefin polymerization catalyst is characterized in that an alkylaluminum compound is contacted with a product obtained.

The present invention will be described in detail below. The metallocene-based transition metal compound, which is the component (A) used in the method for producing the catalyst of the present invention, is one in which the transition metal is selected from the group consisting of titanium, zirconium, and hafnium, and preferably even if substituted. Good cyclopentadienyl-based ligands, that is, cyclopentadienyl ring-containing ligands in which substituents may combine to form a condensed ring, and transition metals selected from the group consisting of titanium, zirconium, and hafnium It is an organometallic compound consisting of

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], (Cp
R 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 in} which two R ² are 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, halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent,
An alkoxy group, an aryloxy group, m is 0 or 1, each n is an integer such that n + m = 5, M is a metal selected from the group consisting of titanium, zirconium, and hafnium, and R ⁴ Is a neutral ligand coordinating to M, and R ⁵ represents a counter anion capable of stabilizing the metal cation. )

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, alkylphosphine, amine 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, halogen 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 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 especially preferred are hydrogen, a methyl group, and two R
²Are bound to each other to form 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 a metal selected from the group consisting of titanium, zirconium, and 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 metallocene-based transition metal compounds described above are, for example, bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclo) corresponding to the formula [1] when zirconium is taken as an example. Pentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dihydride, bis (ethylcyclopentadienyl) Zirconium dihydride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (eth Rutetramethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) zirconium Dimethyl, bis (ethyltetramethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dihydride, bis (trimethylcyclopentadienyl) zirconium dihydride, bis ( Ethyltetramethylcyclopentadienyl) zirconium dihydride, bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, bis (trimethyl) Rusilylcyclopentadienyl) zirconium dihydride, bis (trifluoromethylcyclopentadienyl) zirconium dichloride, bis (trifluoromethylcyclopentadienyl) zirconium dimethyl, bis (trifluoromethylcyclopentadienyl) zirconium dichloride Hydride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dimethyl, isopropylidene-pis (indenyl) zirconium dihydride, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, Pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, pentamethylcyclopentadienyl (cyclopentadienyl) zirco Dihydrogen, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl , Dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dihydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl , Bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium dipropyl, bis (cyclopentadienyl) zirconium Phenyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, ethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, ethylcyclopentadienyl ( Cyclopentadienyl) zirconium dimethyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, dimethylcyclopentadienyl (cyclopentadienyl) ) Zirconium dichloride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (cyclopentadienyl) )
Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, indenyl (cyclopentadienyl) zirconium dichloride, dimethylcyclopentadienyl (cyclopentadienyl) ) Zirconium dimethyl, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, ethyl tetramethylcyclopenta Dienyl (cyclopentadienyl) zirconium dimethyl, indenyl (cyclopentadienyl) zirconium dimethyl, dienyl Tylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, bis (pentamethylcyclopentadienyl) zirconium dihydride, indenyl (cyclopenta Dienyl) zirconium dihydride, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trifluoromethylcyclopentadienyl (cyclopentadienyl) ) Zirconium dichloride,
Trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl)
(Trimethylsilyl) (methyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, bis (cyclopentadienyl)
[Tris (dimethylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl) [bis (methylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis ( Cyclopentadienyl) (trimethylsilyl) (benzyl) zirconium, methylene-bis (cyclopentadienyl) zirconium dichloride, ethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene-
Bis (cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (cyclopentadienyl) zirconium dichloride, methylene-bis (cyclopentadienyl) zirconium dimethyl, ethylene-bis (cyclopentadienyl) zirconium dimethyl, isopropylidene- Bis (cyclopentadienyl) zirconium dimethyl, dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, methylene-bis (cyclopentadienyl) zirconium dihydride, ethylene-bis (cyclopentadienyl) zirconium dihydride , Isopropylidene-bis (cyclopentadienyl)
Zirconium dihydride, dimethylsilyl-bis (cyclopentadienyl) zirconium dihydride and the like.

Further, those 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) tetrahydro Lan 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 Chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethyl tetramethylcyclopentadienyl) zirconium (hydride)
(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 (trifluoromethylcyclopentadienyl)
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, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex , Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (chloride) (tetraphenylborate) tetra Drofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (Cyclopentadienyl) zirconium (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 (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate ) Tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) te Lahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, ethyl Cyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (Cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclo Pentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenyl Borate) Tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl ) (Tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, cyclopentadienyl (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) ) Tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, indenyl ( Cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trimethylsilane Rucyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trifluoromethylcyclo Pentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (triphenyl (Silyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) [tris (dimethylsilyl) Lil] 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) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride)
(Tetraphenylborate) tetrahydrofuran complex,
Methylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadiene) (Enyl) 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) tetrahydro Run complex, isopropylidene - bis (cyclopentadienyl) zirconium (hydride)
(Tetraphenylborate) tetrahydrofuran complex,
Dimethylsilyl-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex and the like.

Further, as the titanium compound and the hafnium compound, the same compounds as mentioned above can be mentioned. Further, a mixture of these compounds may be used. In the present invention, clay or clay mineral is used as the component [B]. Clay is usually composed mainly of clay minerals. Most clay minerals are ion-exchangeable layered compounds. Further, these clays and clay minerals are not limited to naturally occurring ones and may be artificially synthesized ones.

Specific examples of the component [B] include kaolin,
Bentonite, kibushi clay, gyrome clay, allophane,
Hissingelite, pyrophyllite, talc, ummo group,
Examples include montmorillonite group, vermiculite, ryokdee stone group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like.

The component [B] preferably has a pore volume of 20 cc or more in radius measured by mercury porosimetry of 0.1 cc / g or more, particularly 0.3 to 5 cc / g.

Here, the pore volume is measured by the mercury porosimetry using a mercury porosimeter, and the pore radius is 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. If 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 thereof 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, resulting in a change in clay structure. 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 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 water or adsorbing it, or after performing heat dehydration treatment. Further, they may be used alone or in combination 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.

The organoaluminum compound used as the component [C] in the present invention is a trialkylaluminum compound such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum.

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.

The contact is carried out in an inert gas such as nitrogen, pentane,
It may be carried out in an inert hydrocarbon solvent such as hexane, heptane, toluene or xylene. The contact temperature is -20 ℃ ~
It is preferably carried out between the boiling points of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

Further, in the present invention, as the organoaluminum compound [D] used as necessary, [C]
The same compounds as the components can be mentioned. 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.

Usually, the component [A] is added after the components [B] and [C] are contacted. 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, an inorganic oxide such as silica or alumina may be coexistent or contacted.

The olefins used for the polymerization include ethylene, propylene, 1-butene, 1-hexene and 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 generally known random copolymerization and block copolymerization as well as homopolymerization.

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.

<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 a pore volume of 1.04 cc / g or more having a radius of 20 Å or more measured by the mercury porosimetry method was taken, and the inside of the flask was replaced with nitrogen, and 50 ml of toluene was added to obtain a slurry. Separately, 7.21 g of trimethylaluminum was dissolved in 50 ml of toluene. While stirring the montmorillonite slurry vigorously, 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 gray-green slurry.

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

Into 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 as to be ^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. Thereafter, the contents of the autoclave were cooled to 30 ° C., and then the internal gas was purged to obtain 170 g of powder polyethylene. The amount of polyethylene produced per 1 g of the transition metal catalyst component (biscyclopentadienyl zirconium dichloride, the same unless otherwise noted) is 6.80 × 10 ⁴ g, and the polymerization activity is 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 added at room temperature under a nitrogen atmosphere in an amount of 0.018M trimethylaluminum toluene solution 0.48 ml and 3%.
It was pre-contacted for 0 minutes, and further pre-contacted with 0.47 ml of the catalyst component slurry prepared in Example 1 (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 above catalyst contact mixture were introduced. Furthermore, 600 ml of liquid propylene was introduced. After the temperature of the mixed liquid 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 copolymer produced per unit 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 biscyclopentadienyl zirconium 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 for 20 minutes.

In a 2-liter induction-stirring autoclave substituted with purified nitrogen, toluene 3 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, the autoclave contents are heated to 30 ° C.
After lowering the temperature to 0, 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 collected, 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 at room temperature under a nitrogen atmosphere to a solution of 0.44 ml of 0.196 M trimethylaluminum in toluene and 30 parts of toluene.
It was pre-contacted for 14 minutes, and further pre-contacted with 14 ml of the catalyst component slurry produced in Example 3 (1) above for 20 minutes.

A 2 liter induction-stirring autoclave replaced with purified nitrogen was charged with toluene 3 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 ℃, 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. After that, the autoclave contents 3
After the temperature was lowered to 0 ° C, 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 was 3.9 × 10 ⁴ g. In addition, 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 sampled in a 300 ml round-bottomed flask, 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.
Stir for minutes. Then the solvent was evaporated and the remaining solid
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 from tetrahydrofuran three times 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 (4) of Example 4 above. The complex at room temperature under 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. The mixture 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.
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 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 ⁴ 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 biscyclopentadienylzirconium dichloride was mixed with a toluene solution containing 5.00 mmol of Al in terms of methylaluminoxane (molecular weight: 1232; manufactured by Tosoh Akzo) under nitrogen atmosphere at room temperature 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 content of the autoclave was 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 . In addition, the amount of polyethylene produced per 1 g of aluminum derived from methylaluminoxane was 86 g.

Example 5 (1) Synthesis of catalyst 8.9 mg of commercially available biscyclopentadienyl zirconium dichloride was placed in a 100 ml round bottom flask,
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 n-heptane was 5 ml 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 and purification of ethylene In a 2-liter induction-stirring autoclave substituted with 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 obtained in Example 5 (1) above were sequentially 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 powder 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 1 g of aluminum derived from trimethylaluminum was 8500 g.

(3) Copolymerization of ethylene-propylene Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, n-hexane 300 m at room temperature under a nitrogen stream.
1, toluene solution of trimethylaluminum (10.1
(8 mM) 1.9 ml and the above catalyst slurry 2.6 ml were sequentially introduced. Furthermore, 600 ml of liquid propylene was introduced. After heating the mixed solution 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. After that, 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 was 92.
It was 00 g.

Example 6 (1) Synthesis of catalyst component A 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 vigorously stirring the trimethylaluminum solution, 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 concentration 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 biscyclopentadienylzirconium dichloride was added to 1.8 ml of a toluene solution of 9.50 mM triethylaluminum in a nitrogen atmosphere at room temperature and 30 ml.
It was pre-contacted with the catalyst component slurry prepared in Example 6 (1) above for 1.1 minutes.

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 concentration 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 brought into contact with montmorillonite and triethylaluminum brought into contact with biscyclopentadienylzirconium dichloride was 13000 g.

<Example 7> (1) Synthesis of ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride The synthesis of the above complex was carried out in 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 carried out 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 contacted with montmorillonite and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride was 9900 g. The boiling heptane-insoluble portion (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 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 by using the one that had been preliminarily contacted with a mol solution of toluene.

In a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 300 ml of toluene, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride and methylaluminoxane were mixed at room temperature under a nitrogen stream. 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, it was pre-contacted with 1.3 ml of the catalyst component slurry prepared in Example 6 (1) above.

300 ml of toluene and the above catalyst component contact mixture were introduced into a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen 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 carried out 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 was converted into methylaluminoxane (manufactured by Tosoh Akzo) as Al atom in a nitrogen atmosphere at room temperature.
It was pre-contacted with a 5 mmol toluene solution for 30 minutes.

To a 2-liter induction-stirring autoclave sufficiently substituted with purified nitrogen, 300 ml of toluene was added at room temperature under a nitrogen stream, and the mixed solution of 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 to obtain 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 vigorously stirring the trimethylaluminum solution, 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 0.0102 M solution of trimethylaluminum in toluene at room temperature under a nitrogen atmosphere.
It was pre-contacted with the catalyst component slurry prepared in Example 9 (1) above (1.2 ml) 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. After that, 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. In addition, 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 bottom flask, and the inside of the flask was replaced with nitrogen, and then 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 and Purification of Ethylene A 2-liter induction-stirring autoclave substituted with nitrogen was charged with 300 m of n-hexane 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 Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, n-hexane 300 m 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 heating the mixed solution 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 performed 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. Moreover, the amount of the copolymer produced per 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 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 1.40 mg of biscyclopentadienylzirconium dichloride was preliminarily contacted with a toluene solution of trimethylaluminum (23.8 μmol as trimethylaluminum) for 30 minutes at room temperature under a nitrogen atmosphere. Further, 5.0 ml of the catalyst component slurry prepared in the above Example 11 (1) was pre-contacted for 20 minutes.

300 ml of n-hexane and the above catalyst 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 the copolymer produced per g was 1.3 × 10 ⁵ g. In addition, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with vermiculite and biscyclopentadienyl zirconium dichloride was 1700 g.

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 bottom 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 form 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 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 biscyclopentadienyl zirconium dichloride was preliminarily contacted with a toluene solution of trimethylaluminum (21.9 μmol as trimethylaluminum) for 30 minutes at room temperature in 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 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 bottom flask which 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, and then 63.9 ml of n-hexane. Was added to form a slurry. 4.9 ml of this slurry was added to the above-mentioned contact product of biscyclopentadienyl zirconium dichloride and trimethylaluminum at room temperature. 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 Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, under a nitrogen stream at room temperature, n-hexane 300 m.
1, toluene solution of trimethylaluminum (10.1
8 mM) 2.4 ml, and then the whole amount of the above 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. Then, 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 6.0 g of montmorillonite was added to form a slurry. After stirring at 70 ° C. for 1 hour, it was filtered and washed with 500 ml of hot pure water. 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 bottom flask, and the inside of the flask was replaced with nitrogen, and then 10 m of n-heptane was collected.
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 biscyclopentadienylzirconium 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 and purification of ethylene In a 2-liter induction-stirring autoclave sufficiently substituted with nitrogen, n-hexane 500 was added at room temperature under a nitrogen stream.
ml, a 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. In addition, the amount of polyethylene produced per gram of aluminum derived from trimethylaluminum was 7,000 g.

(4) Copolymerization of ethylene-propylene Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, 300 m of n-hexane 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 heating the mixed solution 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 was 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 biscyclopentadienyl zirconium dichloride was sampled, and the inside of the flask was sufficiently replaced with nitrogen, and then 10 ml of n-heptane was used.
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 thereto. While vigorously stirring the biscyclopentadienylzirconium 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, 40 ml of the above catalyst slurry was dispensed into another 100 ml round bottom flask 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, a solid catalyst containing 35.8 μmol of zirconium derived from biscyclopentadienylzirconium dichloride, 4.25 mmol of aluminum derived from trimethylaluminum, and 3.8 g of polyethylene was obtained with respect to 1 g of the zirconium-montmorillonite intercalation compound. It was

(2) Polymerization and Purification of Ethylene In a 2 liter induction-stirring autoclave sufficiently replaced with 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 contents of the autoclave were 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) above 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 Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, 300 m of n-hexane 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 heating the mixed solution 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-bottomed flask, the inside of the flask was replaced with nitrogen, and then 10 m of n-heptane was collected.
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 thereto. While vigorously stirring the biscyclopentadienyl zirconium dichloride slurry, 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 Purified in a 2-liter induction-stirring autoclave substituted with nitrogen, n-hexane 300 m 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 heating the mixed solution 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. The amount of the copolymer produced from 1 g of aluminum derived from trimethylaluminum was 1500 g.

Comparative Example 4 (1) Polymerization of ethylene Ethylene was polymerized by the same procedure as in Example 1 except that montmorillonite was not used. That is, 2.5 mg of biscyclopentadienyl zirconium dichloride was added at room temperature under a nitrogen atmosphere in an amount of 0.01
79M Toluene solution of trimethylaluminum 4.8m
L was pre-contacted with L for 30 minutes, and further, 4.7 mL of a solution in which 7.21 g of trimethylaluminum was dissolved in 100 mL of toluene was added and contacted for 20 minutes. Then, ethylene was polymerized under the same conditions as in Example 1 (2), and after stopping with ethanol, 0.29 g of a solid substance was recovered. Of these, the amount of the polymer produced excluding the inorganic solid derived from trimethylaluminum was 0.09 g. Therefore, the amount of polymer produced per 1 g of metallocene transition metal complex is 36 g. The amount of polymer produced per g of aluminum derived from trimethylaluminum was 0.76 g.

[0098]

EFFECTS OF THE INVENTION According to the method of the present invention, not only the polymerization activity per unit amount of aluminum is remarkably improved, but also the use of aluminoxane in the prior art is not required at all, which is superior to the use of aluminoxane. Polymerization activity per unit amount of metallocene-based transition metal compound is also obtained.
Further, when applied to the copolymerization of two or more kinds of olefins having a narrow molecular weight distribution, an olefin polymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained with extremely high polymerization activity. There is no need to remove the catalyst residue, which is extremely useful industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fumihiko Shimizu 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Corporation Research Institute (72) Eiji Isobe 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Mitsubishi Kasei (56) References JP-A-60-106808 (JP, A) JP-A-5-301917 (JP, A) JP-A-2000-103807 (JP, A) JP-A-2000-103808 (JP, A) Japanese Unexamined Patent Publication No. 5-252214 (JP, A) Patent 2972161 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (4)

(57) [Claims] 1. A process for producing an olefin polymerization catalyst, which comprises bringing the following [A] into contact with a reaction product obtained by contacting [B] and [C]. [A] Metallocene-based transition metal compound, wherein the transition metal is selected from the group consisting of titanium, zirconium, and hafnium. [B] Clay or clay mineral (provided that a filler is dispersed therein).
Excluding the use of mica in the production of such resin compositions. ) [C] Trialkylaluminum compound 2. The [B] is kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdee group, palygorskite, kaolinite, nacrite, The method for producing a catalyst for olefin polymerization according to claim 1, which is a substance selected from the group consisting of dickite and halloysite. 3. The method for producing a catalyst for olefin polymerization according to claim 1, wherein the [B] is a substance selected from the group consisting of kaolin, hummo group, montmorillonite group and vermiculite. 4. The method for producing an olefin polymerization catalyst according to claim 1, wherein the [A] is a compound represented by the following general formula [1] or [2]. 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] (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 represents It is a covalently bonded bridging group containing a Group 14 element of the long periodic table, such as carbon, silicon or germanium, and each R ² has hydrogen, halogen, a silicon-containing group or a halogen substituent which may be the same or different. A hydrocarbon group having 1 to 20 carbon atoms,
An alkoxy group or an aryloxy group, and when two R ^{2 s} are present on two adjacent carbon atoms of a cyclopentadienyl ring, they may be bonded to each other to form a C ₄ -C ₆ ring. Good. 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, an aryloxy group, m is 0 or 1, and each n is n + m = 5 And M is a metal selected from the group consisting of titanium, zirconium, and hafnium, R ⁴ is a neutral ligand that coordinates with M, and R ^5-
Represents a counter anion capable of stabilizing the above metal cation. )