JP2001316414A - Catalyst for olefin polymerization and method for manufacturing olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst that is highly suitable for a process for manufacturing an olefinic polymer, making it possible to manufacture an olefinic polymer having high qualities at a high productivity, and to provide a method for manufacturing an olefinic polymer using the catalyst. SOLUTION: A catalyst for olefin polymerization is used for this polymerization that is obtained by making a catalyst component comprising a transition metal complex (a), a modified clay compound (b) and an organic aluminum compound (c) contact with a reaction product composed of a titanium compound (e) supported by minute carrier particles (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound,
An olefin polymerization catalyst comprising a modified clay compound and an organoaluminum compound, a catalyst prepared by adding a reaction product in which a titanium compound is supported on a fine particle carrier and, if necessary, a system in which an organoaluminum compound is mixed, and The present invention relates to a method for producing an olefin polymer using the same.

[0002]

2. Description of the Related Art As a method for producing a polyolefin by polymerization of an olefin, the use of a catalyst system comprising a combination of a transition metal compound and an organometallic compound is already known. Kaminski et al. Disclose in JP-A-58-19309 and the like that a catalyst using metallocene and methylaluminoxane exhibits high activity in producing an olefin polymer containing propylene.

However, the catalyst system disclosed herein has excellent polymerization activity, but since the catalyst system is soluble in the reaction system, a solution polymerization system is often employed, and the production process is limited. Alternatively, in order to produce a polymer having industrially useful physical properties, it was necessary to use a relatively expensive methylaluminoxane in a large amount. For this reason,
When these catalyst systems are used, there are problems such as cost and a problem that a large amount of aluminum remains in the polymer.

On the other hand, a catalyst system in which the above-mentioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in
No. 5006 discloses this. However,
Even when olefins were polymerized according to the methods described therein, the polymerization activity per methylaluminoxane was not sufficient.

[0005] As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604,
JP-A-4-213305 discloses that when a gas phase polymerization is carried out using a catalyst system prepolymerized with a small amount of methylaluminoxane, a polymer having excellent polymerization activity and good particle properties can be obtained. I have. However, although the amount of methylaluminoxane used is small, the polymerization activity is still not satisfactory, and high activation of the catalyst system has been desired.

Japanese Patent Application Laid-Open No. 1-503788 describes a method for producing an ethylene / α-olefin polymer by a high-pressure high-temperature method using a transition metal compound and an aluminoxane as a catalyst. However, regarding the industrial use of these catalysts on a large scale, it is difficult to synthesize methylaluminoxane in a reproducible form, and despite the fact that methylaluminoxane is expensive,
The problem is that in order to obtain sufficient activity, the ratio of methylaluminoxane to the transition metal compound must be significantly increased.

Further, catalyst systems utilizing a clay compound or the like as a solid catalyst can be found in JP-A-5-295022 and JP-A-7-309907, but those which are sufficiently satisfactory in terms of polymerization activity are disclosed. Was not.

Japanese Patent Application Laid-Open No. 7-224106 also discloses a catalyst system using a clay compound and using a clay modified with a cationic compound as a cocatalyst, but it is not sufficient in terms of process suitability. For example, hydrogen generated as a by-product in the polymerization system becomes a chain transfer agent, and a phenomenon occurs in which the molecular weight of the obtained polymer is reduced, so that there has been a problem that the catalyst performance is not sufficiently exhibited.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerization catalyst for obtaining a polyolefin having excellent process suitability and high quality product properties in olefin polymerization.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a catalyst component comprising a transition metal compound, a modified clay compound and an organoaluminum compound, and a titanium compound on a fine particle carrier. It has been found that a high-quality polyolefin can be produced by using a catalyst prepared by contacting a reaction product loaded with and a component in which an organoaluminum compound is mixed, if necessary, to complete the present invention. Was. That is, the present invention provides a catalyst component comprising a transition metal compound (a), a modified clay compound (b), and an organoaluminum compound (c), a reaction product in which a titanium compound (e) is supported on a fine particle carrier (d), and The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst, which comprises contacting a component mixed with an organoaluminum compound (f) as necessary.

Hereinafter, the present invention will be described in detail.

The transition metal compound (a) used in the present invention
Is represented by the following general formula (8).

[0013]

Embedded image

Wherein M ¹ is a zirconium atom or a hafnium atom, and X ¹ is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 alkoxy groups, alkylamide groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms, 1 to 1 carbon atoms
A nitrogen-containing hydrocarbon group of 20 or a silicon-containing hydrocarbon group of 1 to 20 carbon atoms, R ¹ is a cyclopentadienyl group, at least one of the 2 to 5 positions is a halogen atom, and a hydrocarbon of 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms
A cyclopentadienyl group substituted with an oxygen-containing hydrocarbon group having 0, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an indenyl group,
At least one of positions 2 to 7 is a halogen atom and has 1 to 1 carbon atoms
20 hydrocarbon groups, C1-20 alkoxy groups, C1-20 alkylamide groups, C1-20 oxygen-containing hydrocarbon groups, C1-20 nitrogen-containing hydrocarbon groups or carbon R ² is an indenyl group substituted with a silicon-containing hydrocarbon group of 1 to 20, R ² is an indenyl group, at least one of the 2 to 7 positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 nitrogen-containing hydrocarbon group or C1-C20 silicon An indenyl group substituted with a containing hydrocarbon group, a fluorenyl group,
At least one of positions 1 to 8 is a halogen atom and has 1 to 1 carbon atoms.
20 hydrocarbon groups, C1-20 alkoxy groups, C1-20 alkylamide groups, C1-20 oxygen-containing hydrocarbon groups, C1-20 nitrogen-containing hydrocarbon groups or carbon A kind selected from a fluorenyl group substituted by a silicon-containing hydrocarbon group represented by Formulas 1 to 20, R ³ is carbon, silicon or germanium, and R ⁴ and R ⁵ are each independently the same or different Well, carbon number 1-2
0 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 nitrogen-containing hydrocarbon group or carbon A silicon-containing hydrocarbon group of numbers 1 to 20,
At least one is an aryl group having 6 to 20 carbon atoms, an oxygen-containing aryl group having 6 to 20 carbon atoms, a nitrogen-containing aryl group having 6 to 20 carbon atoms, or a silicon-containing aryl group having 6 to 20 carbon atoms.] Examples of the compound represented by the formula (8) include isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (2,7-
Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7- Di-n-propyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-iso-propyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2 7-di-
neo-pentyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-dibenzyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di (dimethylphenyl) ) Methyl-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-methyl-9
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-t-butyl-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-ethyl-9
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-benzyl-9
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (4-methyl-9-
Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (4-t-butyl-9
-Fluorenyl) zirconium dichloride, isopropylidene (1-indenyl) (9-fluorenyl) zirconium dichloride, isopropylidene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, isopropylidene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-methyl-1
-Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (2-methyl-4,5-benzo-1-indenyl) (9
-Fluorenyl) zirconium dichloride, isopropylidene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (2-methyl-4- Phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2
-Methyl-4-phenyl-1-indenyl) (2,7-
Di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (3-methyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-benzyl-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, isopropylidene (3-iso-propyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-trimethylsilyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3, 4-
Dimethyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-dimethylamino-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-diethylamino-9)
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-dibenzylamino-9-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (4-dimethylamino-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (4
-Diethylamino-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (4-dibenzylamino-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-dimethylamino- 9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-methoxy-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-methoxy-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (4-methoxy-
9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,4,7-tri-methoxy-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Phenylmethylmethylene (cyclopentadienyl)
(2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-diethyl-9-
Fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di-
n-propyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di-iso-propyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2 7-di-neo-pentyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl)
(2,7-dibenzyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di (dimethylphenyl) methyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) ) (2-methyl-9-fluorenyl) zirconium dichloride,
Phenylmethylmethylene (cyclopentadienyl) (2
-T-butyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-ethyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-benzyl-9-fluorenyl) ) Zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (4-methyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (4-t-butyl-9-fluorenyl) zirconium dichloride, phenylmethyl Methylene (1-indenyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl)
Zirconium dichloride, phenylmethylmethylene (2-methyl-1-indenyl) (9-fluorenyl)
Zirconium dichloride, phenylmethylmethylene (2-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,
Phenylmethylmethylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (2-methyl-
4,5-benzo-1-indenyl) (2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (2-methyl-4-phenyl-1-indenyl) ( 2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (3-methyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (3-benzyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride , Phenylmethylmethylene (3-iso-
Propyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (3-trimethylsilyl-cyclopentadienyl)
(9-fluorenyl) zirconium dichloride, phenylmethylmethylene (3,4-dimethyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-dimethylamino-9-fluorenyl) Zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-diethylamino-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-dibenzylamino-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (Cyclopentadienyl) (4-dimethylamino-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (4-diethyl Mino-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (4-dibenzylamino-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di-dimethylamino) -9-Fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl)
(2,7-di-methoxy-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2-methoxy-9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (4-methoxy -9-fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,4,7-tri-methoxy-9-fluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-
9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-
t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-n-propyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-di-iso-propyl-9-fluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7
-Di-neo-pentyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dibenzyl-9-fluorenyl)
Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di (dimethylphenyl)
Methyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2
-Methyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2
-T-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2-ethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2-benzyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-methyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-t-butyl-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride,
Diphenylmethylene (1-indenyl) (2,7-di-
t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride,
Diphenylmethylene (2-methyl-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl- 4,5-benzo-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- Phenyl-1-indenyl) (2,
7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-benzyl-cyclopentadienyl) (9- Fluorenyl) zirconium dichloride, diphenylmethylene (3-iso-propyl-cyclopentadienyl) (9-fluorenyl)
Zirconium dichloride, diphenylmethylene (3-
Trimethylsilyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-cyclopentadienyl) (9
-Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2-dimethylamino-9-fluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2-diethylamino-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2-dibenzylamino-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-dimethylamino-9-fluorenyl)
Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-diethylamino-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-dibenzylamino-
9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-
Dimethylamino-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-methoxy-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2-methoxy-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-methoxy-9-fluorenyl)
Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,4,7-tri-methoxy-9
-Fluorenyl) zirconium dichloride, those in which the dichloro form of the above transition metal compound is substituted with a dimethyl form, diethyl form, dihydro form, diphenyl form, dibenzyl form and the like, and those in which the above zirconium compound is replaced with a hafnium compound. It is possible, but not limited to these.

The modified clay compound (b) used in the present invention
Is a reaction product of a layered clay compound (b-1) and a compound (b-2) capable of introducing a cation between layers of the layered clay compound.

The layered clay compound (b-
1) are fine particles mainly composed of microcrystalline silicate. The layered clay compound has a layered structure as a structural feature, and many have negative charges of various sizes in a layer. In this respect, it is significantly different from a metal oxide having a three-dimensional structure such as silica, alumina or zeolite. When the clay compound is classified according to the magnitude of the negative charge described above, pyrophyllite, kaolinite, dickite and talc groups having a negative charge of 0 per chemical formula, and smectite groups having a negative charge of 0.25 to 0.6 are included. , 0.
It can be divided into a vermiculite group of 6 to 0.9, a mica group of about 1, and a brittle mica group of about 2. Each group shown here includes various compounds, respectively, as clay compounds belonging to smectite,
Montmorillonite, beidellite, saponite, hectorite and the like. In addition, these clay compounds exist naturally, but can be obtained with less impurities by artificial synthesis. In the present invention, all of the natural clay compounds shown here and the clay compounds obtained by artificial synthesis can be used, and even if not exemplified above, all those belonging to the definition of clay compounds can be used. it can.

As the compound (b-2) capable of introducing a cation between the layers of the layered clay compound, a proton is coordinated with a lone electron pair of an acid, a salt compound or an element represented by the following general formula (9). An onium compound is used.

[R ⁶ _n GH] ⁺ [A] ^- (9) In the formula, G is an element selected from Group 15 or 16 of the periodic table, and specifically, an ammonium compound wherein G is a nitrogen atom; A phosphonium compound which is a phosphorus atom, an oxonium compound which is an oxygen atom or a sulfonium compound which is a sulfur atom. R ⁶ may be each independently the same or different, and include a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
An aryl group, an alkylaryl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, wherein at least one R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and each R ⁶ is They may be connected to each other. Specific hydrocarbon groups include methyl, ethyl, propyl,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,
C1-C30 alkyl groups such as hexadecyl, octadecyl, isopropyl, isobutyl, s-butyl, t-butyl and cyclohexyl; C1-C30 alkenyl groups such as vinyl, propenyl and cyclohexenyl; phenyl, methylphenyl, Examples thereof include an aryl group having 6 to 30 carbon atoms such as ethylphenyl, biphenyl, and naphthyl, and an arylalkyl group having 7 to 30 carbon atoms such as benzyl and phenylethyl. At least one R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and each R ⁶ may be bonded to each other. When G belongs to group 15, n = 3, and when G belongs to group 16, n = 2. [A] ^- is a counter anion, fluorine ion, chlorine ion, a bromine ion, an inorganic anion of halide ion or sulfate ion such as iodide ion are exemplified, but not limited thereto.

In the above compounds, G is a nitrogen atom, [A]
^- Specifically with regard chlorine ions, methylamine hydrochloride, ethylamine hydrochloride, propylamine hydrochloride, isopropylamine hydrochloride, butylamine hydrochloride, hexylamine hydrochloride, decylamine hydrochloride, dodecylamine hydrochloride, allylamine hydrochloride , Cyclopentylamine hydrochloride, cyclohexylamine hydrochloride and other aliphatic primary amine hydrochlorides; dimethylamine hydrochloride, diethylamine hydrochloride, diamylamine hydrochloride, didecylamine hydrochloride, diallylamine hydrochloride, etc. hydrochloric acid of aliphatic secondary amines Salts: trimethylamine hydrochloride, tributylamine hydrochloride, triamylamine hydrochloride, triallylamine hydrochloride, N, N
-Dimethylethylamine hydrochloride, N, N-dimethylpropylamine hydrochloride, N, N-dimethylbutylamine hydrochloride, N, N-dimethylpentylamine hydrochloride, N, N-
Dimethylhexylamine hydrochloride, N, N-dimethylpentylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylnonylamine hydrochloride, N, N-
Dimethyldecylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyltetradecylamine hydrochloride,
N, N-dimethylhexadecylamine hydrochloride, N, N-
Hydrochlorides of aliphatic tertiary amines such as dimethyloctadecylamine hydrochloride, N, N-dimethylicosylamine hydrochloride;
Aniline hydrochloride, N-methylaniline hydrochloride, N, N-
Dimethylaniline hydrochloride, N-ethylaniline hydrochloride,
N, N-diethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N-methyl-o-toluidine hydrochloride, N-methyl-m- Toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N, N-dimethyl-o-
Toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, benzylamine hydrochloride, dibenzylamine hydrochloride, tribenzylamine hydrochloride, N-benzyl-N -Ethylaniline hydrochloride, diphenylamine hydrochloride, α-naphthylamine hydrochloride, β-naphthylamine hydrochloride, N, N-dimethyl-α-naphthylamine hydrochloride, N, N-dimethyl-β
-Naphthylamine hydrochloride, o-anisidine hydrochloride, m-
Anisidine hydrochloride, p-anisidine hydrochloride, N, N,
2,6-tetramethylaniline hydrochloride, N, N, 3,5
-Tetramethylaniline hydrochloride, N, N, 2,4,6-
Pentamethyl anilinium chloride, 2,3,4,5,6-hydrochloride salt of an aromatic amine such as pentafluoroaniline hydrochloride or [A] of the ammonium compound, ^- is fluorine ions in place of the chloride, bromide , Iodine ions or sulfate ions, and the like, examples of which include, but are not limited to, hydrofluoric acid, hydrobromide, hydroiodide and sulfate amine compounds . G is a phosphorus atom, [A] ^- is with respect to bromine ions, specifically triphenylphosphine hydrobromide, tri (o-tolyl) phosphine hydrobromide,
Examples thereof include phosphonium compounds such as tri (p-tolyl) phosphine hydrobromide and tri (mesityl) phosphine hydrobromide, but are not limited thereto. G is an oxygen atom, [A] ^- with respect to chlorine ions, specifically the hydrochloride salt of methyl ether, hydrochloride ethyl ether, but oxonium compounds such as hydrochloride phenyl ether can be exemplified, are limited to Not something. Other examples include sulfonium compounds in which G is a sulfur atom.

When the compound (b-2) is an acid, examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, benzoic acid and oxalic acid, but are not limited thereto.

When the compound (b-2) is a salt compound,
A cation containing at least one atom from group 2 to 14 of the periodic table and a halogen atom or hydrochloric acid, nitric acid, acetic acid, propionic acid, butyric acid, carbonic acid, sulfuric acid, chlorite, chlorate, perchlorate, chromate, Nichrome acid, phosphoric acid, sulfonic acid,
It is a compound comprising an anion derived from an acid such as sulfurous acid and periodate.

The compound (b-2) is preferably an onium compound represented by the general formula (9).

The layered clay compound (b-1) and a compound (b) capable of introducing a cation between the layers of the layered clay compound
The reaction conditions for the reaction of -2) are not particularly limited, but water or an organic solvent generally used, specifically, ethyl alcohol, methyl alcohol, acetone, 1,4
-Dioxane, acetonitrile, benzene, toluene,
The contact is preferably performed in xylene, pentane, hexane, methylene chloride or the like. At this time, (b-2) may be prepared as a solid and dissolved in a solvent, or may be prepared as a solution of (b-2) by causing a chemical reaction in a liquid phase. There is no particular limitation on the reaction amount ratio between (b-1) and (b-2). However, when an exchangeable cation is present in (b-1), an equivalent mole or more of (b) -2).

The organoaluminum compound (c) used in the present invention is represented by the following general formula (10).

[0025]

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[Wherein, R ⁷ may be each independently the same or different, and include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group, an aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an arylalkoxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an alkylaryl having 6 to 20 carbon atoms An oxy group, and at least one of R ⁷ is an alkyl group having 1 to 20 carbon atoms]. Specific examples thereof include trimethylaluminum, triethylaluminum, tri (normalpropyl) aluminum, tri (isopropyl) Aluminum, tri (normal butyl) aluminum, tri (isobutyl) aluminum, tri (t-butyl) aluminum, Trialkylaluminums such as rearylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di (t-butyl) aluminum chloride and diamylaluminum chloride; Examples thereof include alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, t-butylaluminum dichloride and amylaluminum dichloride; and dialkylaluminum alkoxides such as diethylaluminum ethoxide, but are not limited thereto. Absent. Of these, trialkyl aluminum is preferred.

The fine particle carrier (d) used in the present invention includes inorganic carriers such as magnesium chloride, silica, alumina and zeolite, organic carriers, pyrophyllite, kaolinite, dickite, talc group, smectite group and vermiculite group. , Mica group, brittle mica group and the like, but are not limited thereto.

The titanium compound (e) used in the present invention includes a compound represented by the following general formula (11) or (12).

[0029]

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[In the formula, X ² may be independently the same or different and each represents a hydrogen atom, a halogen atom, a carbon atom
20 hydrocarbon groups, C1-20 alkoxy groups, C1-20 alkylamide groups, C1-20 oxygen-containing hydrocarbon groups, C1-20 nitrogen-containing hydrocarbon groups or carbon A silicon-containing hydrocarbon group of the formulas 1 to 20, wherein R ⁸ and R ⁹ may be independently the same or different, a cyclopentadienyl group, at least one of the 2- to 5-positions is a halogen atom, A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms Or 1 to 20 carbon atoms
A cyclopentadienyl group substituted with a silicon-containing hydrocarbon group, an indenyl group, at least one of the 2- to 7-positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 alkoxy groups, alkylamide groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms, 1 to 1 carbon atoms
An indenyl group substituted with a nitrogen-containing hydrocarbon group of 20 or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a fluorenyl group, at least one of the 1 to 8 positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C1
20 oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms, or fluorenyl groups substituted with silicon-containing hydrocarbon groups having 1 to 20 carbon atoms]

[0031]

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[In the formula, X ³ may be each independently the same or different and each represents a hydrogen atom, a halogen atom, a carbon atom
20 hydrocarbon groups, C1-20 alkoxy groups, C1-20 alkylamide groups, C1-20 oxygen-containing hydrocarbon groups, C1-20 nitrogen-containing hydrocarbon groups or carbon A silicon-containing hydrocarbon group of the formulas 1 to 20, wherein R ¹⁰ and R ¹¹ may be each independently the same or different; a cyclopentadienyl group, at least one of the 2 to 5 positions is a halogen atom, A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms Or carbon number 1-2
A cyclopentadienyl group or an indenyl group substituted with a silicon-containing hydrocarbon group of 0, a halogen atom in at least one of positions 2 to 7, a hydrocarbon group of 1 to 20 carbon atoms, and a carbon number of 1
Alkoxy group having 1 to 20 carbon atoms, alkylamide group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
An indenyl group substituted with a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a fluorenyl group, at least one of the 1 to 8 positions is a halogen atom,
C1-C20 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C1
To 20 oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a fluorenyl group substituted with a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, wherein R ¹² is carbon, Silicon or germanium;
¹³ and R ¹⁴ may be each independently the same or different;
C1-C20 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C1
Or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹³ and R ¹⁴ has 6 to 6 carbon atoms. An aryl group having 20 carbon atoms, an oxygen-containing aryl group having 6 to 20 carbon atoms, a nitrogen-containing aryl group having 6 to 20 carbon atoms, or a silicon-containing aryl group having 6 to 20 carbon atoms]. (Pentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride,
Bis (indenyl) titanium dichloride, methylenebis (cyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride , Ethylenebis (indenyl) titanium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, ethylenebis (2-methyl-1)
-Indenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl)
Titanium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentane) Dienyl) (2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (cyclopentane) Dienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) titanium dichloride, dimethyl Silanediylbis (2,4,5-trimethyl cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethyl cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2
-Methyl-1-indenyl) titanium dichloride,
Dimethylsilanediylbis (tetrahydroindenyl)
Titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadiyl) Enyl) (2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl)
Titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t-butyl-2-) Methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-1-indenyl) titanium dichloride, Diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride Ride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, Diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) ) Titanium dichloride, diphenylsilanediylbis (4-t-
Butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride,
Diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2-methyl-indenyl) titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium Dichloride, diphenylsilanediyl (cyclopentadienyl-
2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, and the like, but are not limited thereto. is not.

Also, titanium alkoxide compounds such as titanium tetraethoxide, titanium tetraisopropoxide, and titanium tetrabutoxide; and titanium amide compounds such as titanium tetrakis (dimethylamide) and titanium tetrakis (dibenzylamide) can be used.

The titanium compound can be used as it is, but it is also possible to use a reaction product obtained by reacting with a transition metal salt of Groups 3 to 12 of the periodic table. Specific examples of the transition metal salts of Groups 3 to 12 of the periodic table include copper, silver, gold, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, chromium, molybdenum,
Acetate, propionate, butyrate, carbonate, sulfate, and the like of transition metals such as tungsten, zirconium, and hafnium
Chlorite, chlorate, perchlorate, chromate, dichromate, phosphate, sulfonate, sulfite, periodate, etc., but are not limited thereto Not something.

The organoaluminum compound (f) used in the present invention is represented by the following general formula (13).

[0036]

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[Wherein, R ¹⁵ may be independently the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms. Group, an aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an arylalkoxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an alkylaryl having 6 to 20 carbon atoms An oxy group, and at least one of R ¹⁵ is an alkyl group having 1 to 20 carbon atoms.] Specific examples thereof include trimethylaluminum, triethylaluminum, tri (normalpropyl) aluminum, tri (isopropyl) Aluminum, tri (n-butyl) aluminum, tri (isobutyl) aluminum, tri (t-butyl) aluminum, Trialkylaluminums such as triamylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di (t-butyl) aluminum chloride and diamylaluminum chloride; Examples thereof include alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, t-butylaluminum dichloride and amylaluminum dichloride; and dialkylaluminum alkoxides such as diethylaluminum ethoxide, but are not limited thereto. Absent. Of these, trialkyl aluminum is preferred.

The transition metal compound (a), the modified clay compound (b) and the organoaluminum compound (c) may be used alone or in combination of two or more.

The method or order of addition of the transition metal compound (a), the modified clay compound (b) and the organoaluminum compound (c) is not particularly limited, however, in order to reduce the influence of impurities and the like in the modified clay compound. Preferably, the modified clay compound (b) and a part or all of the organoaluminum compound (c) are brought into contact in advance.

The above three components are contacted in an inert gas atmosphere in a solvent inert to each component. Specifically, butane, pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclopentane,
Examples thereof include aliphatic hydrocarbon compounds such as cyclohexane and aromatic hydrocarbon compounds such as benzene, toluene and xylene. In addition to the above organic solvents, it is also possible to use halogen-containing compounds such as chloroform, methylene chloride and chlorobenzene. The temperature at the time of contact can be in the range of −50 ° C. to the boiling point of the solvent. Preferably it is above room temperature.

The amount of the modified clay compound (b) relative to the transition metal compound (a) in the catalyst system may be an amount of the modified clay compound (b) sufficient for the reaction of the transition metal compound (a). Although there is no particular limitation, the amount of cations in the modified clay compound (b) with respect to the transition metal compound (a) is preferably from 0.01 to 10000 times, more preferably from 0.1 to 1000 times by mole. Furthermore, the amount of the organoaluminum compound (c) is not particularly limited, but is preferably 100,000 times or less the molar amount of the transition metal compound. If the amount is more than this, it is necessary to consider the demineralization step. Considering the viewpoints of catalyst stabilization and elimination of catalyst poisons, it is preferable to use the organoaluminum compound in a range of 1 to 10000 times mol.

Incidentally, as the transition metal compound (a) used in the present invention, two or more transition metal compounds can be used for polymerization.

Similarly, the fine particle carrier (d), the titanium compound (e) and the organoaluminum compound (f) may be used alone or in combination of two or more.

The method or order of adding the fine particle carrier (d), the titanium compound (e) and the organoaluminum compound (f) is not particularly limited.

The above three components are contacted in an inert gas atmosphere in a solvent inert to each component. Specifically, butane, pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclopentane,
Examples thereof include aliphatic hydrocarbon compounds such as cyclohexane and aromatic hydrocarbon compounds such as benzene, toluene and xylene. In addition to the above organic solvents, it is also possible to use halogen-containing compounds such as chloroform, methylene chloride and chlorobenzene. The temperature at the time of contact can be in the range of −50 ° C. to the boiling point of the solvent. Preferably it is above room temperature.

The amount of the fine particle carrier (d) with respect to the titanium compound (e) is not particularly limited as long as the amount of the fine particle carrier (d) is sufficient to support the titanium compound (e). (E) The amount of the fine particle carrier (d) per 1 mmol is 0.001 to 1000 g.
And more preferably 0.01 to 100 g.

Further, the amount of the organoaluminum compound (f) relative to the titanium compound (e) is not particularly limited.
The organoaluminum compound (f) may not be used. However, in consideration of elimination of catalyst poisons and more effective use of the titanium compound (e), it is preferable to use the organoaluminum compound (f) in a molar amount of 0.1 times or more the titanium compound (e). Further, in consideration of the decrease in the activity of the main catalyst and the amount of ash in the polymer, it is preferably not more than 10,000 times the molar amount of the titanium compound (e).

The catalyst component comprising the transition metal compound (a), the modified clay compound (b) and the organoaluminum compound (c) is added to the fine particle carrier (d) and the titanium compound (e) is added.
There is no particular limitation on the method of adding the reaction product supporting the and the component obtained by mixing the organoaluminum compound (f) if necessary, or the order of addition is not particularly limited. It may be supplied into the polymerization vessel.

The polymerization of olefin using the catalyst for olefin polymerization in the present invention can be used in any of ordinary polymerization methods. At the time of polymerization, when a solvent is used, any organic solvent generally used may be used, and specifically, benzene, toluene, xylene, butane, pentane,
Hexane, heptane, cyclohexane, methylene chloride and the like can be mentioned, and olefin itself provided at the time of polymerization such as propylene, 1-butene, 1-octene and 1-hexene can also be used as a solvent.

The olefin used for the polymerization in the present invention includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, Α-olefins such as styrene, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,
4-methyl-1,4-hexadiene, 7-methyl-1,
Examples thereof include conjugated and non-conjugated dienes such as 6-octadiene, and cyclic olefins such as cyclobutene. However, the present invention is not limited thereto. When performing polymerization, homopolymerization using one of these or 2 Copolymerization using more than one species can be performed, but ethylene (co) polymerization is preferred.

In producing a polyolefin using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, monomer concentration and the like are not particularly limited. For 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 3500 kg / cm ² G.

Specific examples of the polymerization process used include a gas phase method, a slurry method, a solution method and a high pressure method. The polymerization temperature of the gas phase method or the slurry method is not particularly limited, but is preferably 0 to 100 ° C. The polymerization pressure is not particularly limited either, but is from atmospheric pressure to 100 kg /
cm ² G is preferred.

The solution method is not particularly limited as long as the polymerization temperature is at least 120 ° C., but is preferably from 120 to 350 ° C. Also, the polymerization pressure is not particularly limited,
From atmospheric pressure to 300 kg / cm ² G is preferred.

The high-pressure method is not particularly limited as long as the polymerization temperature is at least 120 ° C., but is preferably from 120 to 350 ° C. Also, the polymerization pressure is not particularly limited,
300-3500 kg / cm < ² > G is preferable.

The polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system, and can be carried out in two or more stages by changing the polymerization conditions. Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0056]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The polymerization operation, reaction and solvent purification
All were performed under an inert gas atmosphere. The solvents used for the reaction were all purified, dried and deoxygenated by a known method in advance. Furthermore, the compound used for the reaction was synthesized and identified by a known method.

MF of olefin polymer obtained in the present invention
R (melt flow rate) was measured by a method according to ASTM D1238 condition E.

The amount of cations replaced by the modification reaction was estimated from the difference in the sodium content of the clay compound before and after the modification reaction.

Example 1 [Preparation of modified clay compound] Dimethylaniline (Me ₂ N)
Ph) 145 g and 37% hydrochloric acid (100 ml) were added to 10 l of deionized water to prepare an aqueous solution of dimethylaniline hydrochloride. 600 g of montmorillonite having an average particle size of 7.8 μm
(Prepared by pulverizing Kunimine F manufactured by Kunimine Kogyo Co., Ltd. with a jet pulverizer) was added to the aqueous solution of the hydrochloride and reacted for 6 hours. After the completion of the reaction, the reaction solution was filtered, and the obtained cake was dried under reduced pressure for 6 hours to obtain 640 g of a modified clay compound. Organic cation introduction amount is 1.0mmo
1 / g.

[Preparation of catalyst] 1 g of the modified clay compound synthesized according to [Preparation of modified clay compound] and 50.2 ml of n-heptane were added to a 100 ml Schlenk tube, and a heptane solution of triethylaluminum (10 wt.
% Diluted product) to 8 mmol (1
After adding 3.1 ml), the mixture was stirred for 1 hour (this is referred to as suspension A).

On the other hand, diphenylmethylene (cyclopentadienyl) was placed in a separately prepared 50 ml Schlenk tube.
(9-Fluorenyl) zirconium dichloride was added to 40
4 mol (6.56 ml) of an aluminum atom was added to a solution of μmol, 10 ml of n-heptane and a solution of triethylaluminum in heptane (10 wt% dilution), and the mixture was stirred for 1 hour (this is referred to as solution A).

The resulting solution A was added to the suspension A and stirred at room temperature for 24 hours to prepare a catalyst (concentration of zirconium 0.5 mmol / l).

[Reaction of Titanium Compound with Transition Metal Salt] Titanocene (Cp ₂₎ was placed in a 100 ml Schlenk tube.
149.4 mg of TiCl ₂ ) and 30 ml of acetone were added to obtain a homogeneous solution (this was referred to as solution B).

On the other hand, into another 100 ml Schlenk tube,
131.6 mg of silver perchlorate (AgClO ₄ ) and 30 ml of acetone were added to obtain a homogeneous solution. When the whole amount of the obtained solution was added to the solution B, a white precipitate was formed. After stirring for 1 hour, the supernatant was separated by decantation, and the remaining white precipitate was dried under reduced pressure to obtain a reaction product ([Cp ₂ TiCl] ⁺ ClO ₄ ⁻ ; yield 18).
5.3 mg / Yield 98.7%) [Reaction between layered clay mineral and obtained reaction product] 100
Using a ml flask, 0.244 g of lithium teniolite (manufactured by Topy Industries) was swollen by stirring in 10 ml of water for 30 minutes. [Cp ₂ TiCl] ⁺ C
lO ₄ ^- acetonitrile 0.6mmol solution (10 m
1) was added and stirred for 72 hours. After recovering the reacted teniolite by filtration and washing with acetonitrile,
The reaction product was obtained by drying under reduced pressure for 24 hours (yield; 0.2046 g).

The obtained reaction product was subjected to elemental analysis of carbon and hydrogen, and the increased amount was converted to [Cp ₂ TiCl] ⁺ introduced between the layers of teniolite to obtain [Cp ₂ TiCl] ⁺
Is introduced in an amount of 0.483 mmol Ti / teniolite 1
g (the obtained reaction product is [Cp ₂ Ti
Cl] ⁺ TN).

[Polymerization] After replacing 1 liter of the autoclave with nitrogen, 600 ml of a C ₉ -C ₁₃ saturated hydrocarbon solvent (IP Solvent 1620 (manufactured by Idemitsu Petrochemicals)) and 20 ml of 1-hexene were added, and the internal pressure of the autoclave was increased with ethylene. Was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 170 ° C.

Next, 0.5 μmol (1 ml) of the prepared catalyst and 10.4 mg of [Cp ₂ TiCl] ⁺ TN per diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride (5.0 μmol per Ti; A solution of triethylaluminum in heptane (10 wt%) was previously suspended in n-heptane (10 ml).
% Dilution) is 0.125mmo per aluminum atom
1 (0.20 ml) was added to the autoclave together with nitrogen pressure to carry out polymerization for 10 minutes.

After the completion of the polymerization reaction, the hydrogen concentration in the gas phase of the autoclave was measured to be 280 ppm. Thereafter, unreacted ethylene was removed, and the polymer in a solution state was extracted from the lower part of the autoclave. Ethanol was added thereto, and filtration and drying under reduced pressure at 100 ° C. were performed for 6 hours to obtain 43 g of a polymer. The MFR of the polymer was 2.96 g / 10 min. Met.

Comparative Example 1 [Preparation of modified clay compound] [Preparation of catalyst]

[Polymerization] The procedure of Example 1 was repeated except that [Cp ₂ TiCl] ⁺ TN was not supplied. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 17,500 ppm, and the polymer yield and MFR were 63 g and 1%.
1.2 g / 10 min. Met.

Example 2 [Preparation of modified clay compound]

[Preparation of catalyst] Instead of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-ethyl-9-fluorenyl) was used.
Example 1 was repeated except that zirconium dichloride was used.

[Reaction between Titanium Compound and Transition Metal Salt] [Reaction between Layered Clay Mineral and Obtained Reaction Product] The reaction was carried out according to Example 1.

[Polymerization] After replacing 1 liter of autoclave with nitrogen, 600 ml of a C ₉ -C ₁₃ saturated hydrocarbon solvent (IP Solvent 1620 (manufactured by Idemitsu Petrochemicals)) and 20 ml of 1-hexene were added, and the internal pressure of the autoclave was adjusted with ethylene. Was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 170 ° C.

Next, diphenylmethylene (cyclopentadienyl) (2,7-di-ethyl-9-fluorenyl)
0.5 μmol per zirconium dichloride (1m
l) The prepared catalyst and [Cp ₂ TiCl] ⁺ TN 1
A suspension in which 0.4 mg (5.0 μmol per Ti; suspended in 10 ml of n-heptane) of a heptane solution of triethylaluminum (10 wt% dilution) was added in advance to 0.125 mmol (0.20 ml) per aluminum atom in 0.4 mg (suspended in 10 ml of n-heptane) The autoclave is fed together with nitrogen pressure and
Polymerization was performed for 0 minutes.

After the completion of the polymerization reaction, the hydrogen concentration in the gas phase of the autoclave was measured to be 26 ppm. Thereafter, unreacted ethylene was removed, and the polymer in a solution state was extracted from the lower part of the autoclave. Ethanol was added thereto, and filtration and drying under reduced pressure at 100 ° C. were performed for 6 hours to obtain 61 g of a polymer. The MFR of the polymer was 0.72 g / 10 min. Met.

Comparative Example 2 [Preparation of Modified Clay Compound] [Preparation of Catalyst] The preparation was carried out according to Example 2.

[Polymerization] The procedure of Example 2 was repeated except that [Cp ₂ TiCl] ⁺ TN was not supplied. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 6,500 ppm, and the polymer yield and the MFR were 63 g and 1.
76 g / 10 min. Met.

Example 3 [Preparation of modified clay compound]

[Preparation of Catalyst] Instead of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was used. The procedure was carried out in accordance with Example 1 except that it was used.

[Reaction between Titanium Compound and Transition Metal Salt] The reaction was carried out according to Example 1.

[Reaction of Layered Clay Mineral with Obtained Reaction Product] Using a 100 ml flask, 0.7 g of sodium hectorite (manufactured by Topy Industries) was added to 30 ml of water in 20 ml of water.
It was swollen by stirring for minutes. To this, [Cp ₂ T
iCl] ⁺ ClO ₄ ^- was added to acetonitrile 0.6mmol solution (20 ml), and stirred for 72 hours. The hectorite after the reaction was collected by filtration, washed with acetonitrile, and dried under reduced pressure for 24 hours to obtain a reaction product (yield: 0.4896 g).

The obtained reaction product was subjected to elemental analysis of carbon and hydrogen, and the increased amount was converted into [Cp ₂ TiCl] ⁺ introduced between layers of the hectorite to obtain [Cp ₂ TiCl] ⁺
Is introduced in an amount of 0.433 mmol Ti / hectorite 1
g (the obtained reaction product is [Cp ₂ Ti
Cl] ⁺ HT).

[Polymerization] After 1 liter of the autoclave was replaced with nitrogen, 600 ml of a C ₉ -C ₁₃ saturated hydrocarbon solvent (IP Solvent 1620 (manufactured by Idemitsu Petrochemical)) and 20 ml of 1-hexene were added, and the internal pressure of the autoclave was increased with ethylene. Was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 170 ° C.

Next, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-fluorenyl)
0.5 μmol per zirconium dichloride (1m
l) The prepared catalyst and [Cp ₂ TiCl] ⁺ HT 1
A liquid obtained by suspending 1.5 mg (5.0 μmol per Ti) in 10 ml of n-heptane was supplied to an autoclave together under nitrogen pressure, and polymerization was carried out for 10 minutes.

After the completion of the polymerization reaction, the hydrogen concentration in the gas phase of the autoclave was measured and found to be 2480 ppm.
Thereafter, unreacted ethylene was removed, and the polymer in a solution state was extracted from the lower part of the autoclave. Ethanol was added thereto, and filtration and drying under reduced pressure at 100 ° C. were performed for 6 hours to obtain 57 g of a polymer. The MFR of the polymer was 0.64 g / 10 min. Met.

Example 4 All operations other than polymerization were carried out according to Example 3.

[Polymerization] [Cp ₂ TiCl] ⁺ HT
In 5 mg (suspended in 10 ml of n-heptane), a solution of triethylaluminum in heptane (diluted at 10 wt%) was previously dissolved in 0.5 mmol (0.8 wt%) per aluminum atom.
2 ml), except that it was added. The hydrogen concentration in the gas phase of the autoclave after the polymerization is 45 pp
m and the polymer yield and MFR were 54 g and 0.62 g / 10 min. Met.

Example 5 [Preparation of Modified Clay Compound] [Preparation of Catalyst] [Reaction of Titanium Compound with Transition Metal Salt] The reaction was carried out according to Example 3.

[Reaction between Layered Clay Mineral and Obtained Reaction Product] The reaction was carried out according to Example 1.

[Polymerization] [Cp ₂ TiCl] ⁺ HT
[Cp ₂ TiCl] ⁺ TN is 10.4 m instead of 5 mg
The procedure was as in Example 3, except that g was supplied. After the polymerization, the hydrogen concentration in the gas phase of the autoclave is 110 pp.
m and the polymer yield and MFR were 54 g and 0.40 g / 10 min. Met.

Example 6 All operations other than polymerization were carried out according to Example 5.

[Polymerization] [Cp ₂ TiCl] ⁺ TN
In 4 mg (suspended in 10 ml of n-heptane), a heptane solution of triethylaluminum (10 wt% dilution) was previously added to 0.5 mmol (0.8 wt%) per aluminum atom.
2 ml), except that it was added. The hydrogen concentration in the gas phase of the autoclave after the polymerization is 16 pp
m and the polymer yield and MFR were 46 g and 0.47 g / 10 min. Met.

Comparative Example 3 [Preparation of Modified Clay Compound] [Preparation of Catalyst] The preparation was carried out according to Example 3.

[Polymerization] The procedure of Example 3 was repeated, except that [Cp ₂ TiCl] ⁺ HT was not supplied. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 4600 ppm, and the polymer yield and MFR were 65 g and 1.
00g / 10min. Met.

Example 7 All operations other than polymerization were carried out according to Example 4.

[Polymerization] [Cp ₂ TiCl] ⁺ HT to be supplied
To 1.2 mg (suspended in 1 ml of n-heptane)
A solution of triethylaluminum in heptane (10 wt% dilution) previously mixed with [Cp ₂ TiCl] ⁺ HT is 0.05 mmol (0.08 ml) per aluminum atom.
And the amount of 1-hexene was 80 ml,
Performed according to Example 4. The hydrogen concentration in the gas phase of the autoclave after completion of the polymerization was 8880 ppm, and the yield and MFR of the polymer were 69 g and 4.73 g / 10 3
min. Met.

Example 8 All operations other than polymerization were carried out in accordance with Example 5.

[Polymerization] [Cp ₂ TiCl] ⁺ TN to be supplied
To 1.0 mg (suspended in 1 ml of n-heptane)
A solution of triethylaluminum in heptane (10 wt% dilution) previously mixed with [Cp ₂ TiCl] ⁺ TN is 0.05 mmol (0.08 ml) per aluminum atom.
And the amount of 1-hexene was 80 ml,
Performed according to Example 6. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 7180 ppm, and the yield and MFR of the polymer were 65 g and 3.00 g / 10
min. Met.

Example 9 All operations other than polymerization were carried out in accordance with Example 5.

[Polymerization] [Cp ₂ TiCl] ⁺ TN to be supplied
To 2.1 mg (suspended in 1 ml of n-heptane)
Example 8 was carried out except that a heptane solution of triethylaluminum (10 wt% dilution) mixed with [Cp ₂ TiCl] ⁺ TN was changed to 0.1 mmol (0.16 ml) per aluminum atom in advance. The hydrogen concentration in the gas phase of the autoclave after the completion of the polymerization was 4840 ppm, and the yield and MFR of the polymer were 63 g and 3.
13 g / 10 min. Met.

Example 10 All operations other than polymerization were carried out according to Example 5.

[Polymerization] The procedure of Example 6 was repeated except that the amount of 1-hexene was changed to 80 ml. The hydrogen concentration in the gas phase of the autoclave after the polymerization was 106 ppm,
Polymer yield and MFR were 24 g and 0.53
g / 10 min. Met.

Comparative Example 4 [Preparation of Modified Clay Compound] [Preparation of Catalyst]

[Polymerization] The procedure of Comparative Example 3 was repeated except that the amount of 1-hexene was changed to 80 ml. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 9580 ppm, and the yield and MFR of the polymer were 69 g and 6.
22 g / 10 min. Met.

Example 11 All operations other than polymerization were carried out according to Example 5.

[Polymerization] [Cp ₂ TiCl] ⁺ TN to be supplied
To 5.1 mg (suspended in 1 ml of n-heptane)
A solution of triethylaluminum in heptane (10 wt% dilution) previously mixed with [Cp ₂ TiCl] ⁺ TN was 0.0625 mmol (0.10 m
The procedure was performed according to Example 8 except that l) was used. The hydrogen concentration in the gas phase of the autoclave after the polymerization is 6,000 pp
m and the polymer yield and MFR were 61 g and 2.68 g / 10 min. Met.

Example 12 All operations other than polymerization were carried out according to Example 5.

[Polymerization] A solution of triethylaluminum in heptane (10 watts) previously mixed with [Cp ₂ TiCl] ⁺ TN
0.125 mm per aluminum atom
ol (0.20 ml) was carried out according to Example 8. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 1480 ppm, and the polymer yield and MF
R is 44 g and 0.98 g / 10 min. Met.

Example 13 [Preparation of modified clay compound] In 500 ml of water, 37% hydrochloric acid was added.
0 ml and 29.7 g of N, N-dimethyl-octadodecylamine were added to prepare an aqueous solution of ammonium hydrochloride. 600 g of montmorillonite having an average particle size of 7.8 μm
(Prepared by pulverizing Kunimine F manufactured by Kunimine Kogyo Co., Ltd. with a jet pulverizer) was added to the aqueous solution of the hydrochloride and reacted for 6 hours. After the completion of the reaction, the reaction solution was filtered, and the obtained cake was dried under reduced pressure for 6 hours to obtain 120 g of a modified clay compound. Organic cation introduction amount is 1.0mmo
1 / g.

[Preparation of Catalyst] 1 g of the modified clay compound synthesized according to [Preparation of modified clay compound] and 50.2 ml of n-heptane were added to a 100 ml Schlenk tube, and a heptane solution of triethylaluminum (10 wt.
% Diluted product) to 8 mmol (1
After adding 3.1 ml), the mixture was stirred for 1 hour (this is referred to as a suspension B).

On the other hand, diphenylmethylene (cyclopentadienyl) was placed in a separately prepared 50 ml Schlenk tube.
40 μmol of (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, n-heptane 1
0 ml and a solution of triethylaluminum in heptane (diluted at 10 wt%) were added at 4 mm per aluminum atom.
ol (6.56 ml) was added, followed by stirring for 1 hour (this was referred to as solution C).

The resulting solution C was added to the suspension B and stirred at room temperature for 24 hours to prepare a catalyst (zirconium concentration 0.5 mmol / l).

[Reaction between Titanium Compound and Transition Metal Salt] [Reaction between Layered Clay Mineral and Obtained Reaction Product] The reaction was carried out according to Example 3.

[Polymerization] After 1 liter of the autoclave was replaced with nitrogen, 600 ml of a C ₉ -C ₁₃ saturated hydrocarbon solvent (IP Solvent 1620 (manufactured by Idemitsu Petrochemical)) and 80 ml of 1-hexene were added, and the internal pressure of the autoclave was increased with ethylene. Was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 170 ° C.

Next, 0.5 μmol per diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride
(1 ml) of the prepared catalyst and [Cp ₂ TiCl] ⁺ T
A suspension obtained by previously adding 0.5 mmol (0.82 ml) of triethylaluminum in a heptane solution (10 wt% diluted product) to 10.4 mg of N (5.0 μmol per Ti; suspended in 10 ml of n-heptane) per aluminum atom was added. , Fed together into the autoclave by nitrogen pressure,
Polymerization was performed for 10 minutes.

After the completion of the polymerization reaction, the hydrogen concentration in the gas phase of the autoclave was measured and found to be 263 ppm. Thereafter, unreacted ethylene was removed, and the polymer in a solution state was extracted from the lower part of the autoclave. Ethanol was added thereto, and filtration and drying under reduced pressure at 100 ° C. were performed for 6 hours to obtain 72 g of a polymer. The MFR of the polymer is 2.00 g / 10 min. Met.

Comparative Example 5 [Preparation of modified clay compound] [Preparation of catalyst]

[0120] ^{_{[Polymerization] [Cp 2 TiCl] + /}} TN heptane suspension and [Cp ₂ TiCl] ⁺ / advance added except for not using heptane solution of triethylaluminum in TN were carried out according to Example 13. After the polymerization, the hydrogen concentration in the gas phase of the autoclave was 9460 ppm, and the polymer yield and MFR were 80 g and 1 g, respectively.
0.5 g / 10 min. Met.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

As described above, the catalyst according to the present invention can obtain a high-quality olefin polymer with high productivity.

Continued on the front page F-term (reference) 4J011 AA01 AB02 AB04 HB02 HB04 JB02 JB03 MA15 MA16 4J028 AA02A AB01A AC01A AC07A AC08A AC09A AC10A AC26A AC27A AC28A BA01A BA01B BB00B BB01A BB01CA16BCAB BCB BCCA

Claims (11)

[Claims] (1) The following general formula (1): [Wherein, M ¹ is a zirconium atom or a hafnium atom, and X ¹ is each independently a hydrogen atom, a halogen atom,
C1-C20 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C1
A nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, wherein R ¹ is a cyclopentadienyl group, One is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms,
An alkylamide group having 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a cyclopentadienyl group substituted with a silicon-containing hydrocarbon group having 1 to 20 carbon atoms , An indenyl group, at least one of the 2- to 7-positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. An oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or an indenyl group substituted with a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, wherein R ² is an indenyl group;
At least one of positions 7 to 7 is a halogen atom and has 1 to 2 carbon atoms.
0 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 nitrogen-containing hydrocarbon group or carbon An indenyl group substituted with a silicon-containing hydrocarbon group having 1 to 20 atoms, a fluorenyl group, at least one of the 1 to 8 positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A fluorenyl substituted by an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms R ³ is carbon, silicon or germanium; R ⁴ and R ⁵ may be independently the same or different, and may have 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, ~ 20 An alkoxy group, an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. At least one is an aryl group having 6 to 20 carbon atoms, an oxygen-containing aryl group having 6 to 20 carbon atoms, a nitrogen-containing aryl group having 6 to 20 carbon atoms, or a silicon-containing aryl group having 6 to 20 carbon atoms]. A catalyst component comprising a transition metal compound (a), a modified clay compound (b) and an organoaluminum compound (c), and a titanium compound (e) on a fine particle carrier (d)
An olefin polymerization catalyst, which is obtained by contacting a reaction product loaded with olefin. 2. A catalyst component comprising a transition metal compound (a), a modified clay compound (b) and an organoaluminum compound (c) represented by the general formula (1), and a titanium compound (e) ). A catalyst for olefin polymerization, which is obtained by contacting a mixture comprising a reaction product supporting (a) and an organoaluminum compound (f). 3. The modified clay compound (b) according to claim 1, wherein the compound (b) is capable of introducing a cation between layers of the layered clay compound (b-1) and the layered clay compound (b-1).
An olefin polymerization catalyst, which is the reaction product of -2). 4. The layered clay compound according to claim 3 (b-
1) is pyrophyllite, kaolinite, dickite, talc group, smectite group, vermiculite group,
Mica group or brittle mica group, and a layered clay compound (b-
Compound (b-2) capable of introducing a cation between layers of 1)
Is represented by the following general formula (2) [R ⁶ _n GH] ⁺ [A] ⁻ (2) [wherein, G is an element selected from Group 15 or 16 of the periodic table, and R ⁶ is each independently May be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, or 7 to 30 arylalkyl groups, at least one R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and each R ⁶ may be bonded to each other. 3, when G is a group 16 group, n = 2, [A] ⁻ is a counter anion, and a proton is coordinated with a lone electron pair of the element]. A catalyst for olefin polymerization characterized by the following. 5. The layered clay compound according to claim 3 (b-
1) is pyrophyllite, kaolinite, dickite, talc group, smectite group, vermiculite group,
Mica group or brittle mica group, and a layered clay compound (b-
Compound (b-2) capable of introducing a cation between layers of 1)
Is an acid or salt compound. 6. The organoaluminum compound (c) according to claim 1, wherein the compound is represented by the following general formula (3): [Wherein, R ⁷ may be independently the same or different, and include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkoxy group having from 20 to 20; an aryl group having from 6 to 20 carbon atoms;
An aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an arylalkoxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an alkylaryloxy group having 6 to 20 carbon atoms And at least one of R ⁷ is an alkyl group having 1 to 20 carbon atoms]. 7. The fine particle carrier (d) according to claim 1, 2 or 3.
Is a layered clay compound. 8. A layered clay compound according to claim 7, which is a group consisting of pyrophyllite, kaolinite, dickite, talc, smectite, vermiculite, mica or brittle mica. catalyst. 9. The titanium compound (e) according to claim 1 or 2, wherein the titanium compound (e) is represented by the following general formula (4) or the following general formula (5): [In the formula, X ² may be independently the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
Is an alkylamide group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ and R ⁹ are each May be independently the same or different, a cyclopentadienyl group, at least one of the 2- to 5-positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 1 carbon atom Cyclopentadienyl substituted with an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms Group, indenyl group, at least one of the 2- to 7-positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms,
20 oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms or indenyl groups substituted with silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, fluorenyl groups, 1 to 8
At least one of the positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms,
Selected from an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a fluorenyl group substituted with a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. It is a kind of [In the formula, X ³ may be independently the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
Alkyl amide group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having a nitrogen-containing hydrocarbon group or a C1-20 having 1 to 20 carbon atoms, R ^10, R ¹¹
May each independently be the same or different, and a cyclopentadienyl group, at least one of the 2- to 5-positions is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Cyclopenta substituted with an alkylamide group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms A dienyl group, an indenyl group, at least one of positions 2 to 7 is a halogen atom,
C1-C20 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C1
To 20 oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms or indenyl groups substituted with silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, fluorenyl groups,
At least one of the 8-positions is a halogen atom and has 1 to 20 carbon atoms
Hydrocarbon group, C1-20 alkoxy group, C1-20 alkylamide group, C1-20 oxygen-containing hydrocarbon group, C1-20 nitrogen-containing hydrocarbon group or carbon number A fluorenyl group substituted with 1 to 20 silicon-containing hydrocarbon groups, R ¹² is carbon, silicon or germanium, and R ¹³ and R ¹⁴ may be independently the same or different , Carbon number 1-2
0 hydrocarbon group, C1-C20 alkoxy group, C1-C20 alkylamide group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 nitrogen-containing hydrocarbon group or carbon A silicon-containing hydrocarbon group of numbers 1 to 20,
And at least one of R ¹³ and R ¹⁴ is an aryl group having 6 to 20 carbon atoms, an oxygen-containing aryl group having 6 to 20 carbon atoms, a nitrogen-containing aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms.
Of the silicon-containing aryl group] or the titanium compound represented by the general formula (4) or the general formula (5) with a transition metal salt of Group 3 to 12 of the periodic table. An olefin polymerization catalyst, which is a product. 10. The organoaluminum compound (f) according to claim 1 or 2, which is represented by the following general formula (6): [Wherein, R ¹⁵ may be independently the same or different, and include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkoxy group having from 20 to 20; an aryl group having from 6 to 20 carbon atoms;
An aryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an arylalkoxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an alkylaryloxy group having 6 to 20 carbon atoms And at least one of R ¹⁵ is an alkyl group having 1 to 20 carbon atoms] 11. The following general formula (7) in the presence of the catalyst for olefin polymerization according to claim 1. [Wherein, R ¹⁶ and R ¹⁷ may each independently be the same or different and each is a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, or they can combine to form a ring] The olefin to be prepared is in solution, suspension or gas phase at a temperature of -60 to 300 ° C, 0.5 to 2000 bar.
A method for producing an olefin polymer, wherein the olefin polymer is polymerized or copolymerized under the following pressure.