JPH10324710A - Olefin polymerization catalyst and polymerization of olefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst having high olefin polymerization activity by including a specific transition metal compound and an organometallic compound and/or organoaluminumoxy compound and/or the like. SOLUTION: This catalyst is obtained by including (A) a transition metal compound of the formula (M is a group 8-11 transition metal atom; R<1> to R<6> are each H, a hydrocarbon group, organic silyl, alkoxy or aryloxy; (n) is the valence of M, being 1-4; X is H, a halogen, hydrocarbon group, etc., wherein a plurality thereof may mutually linked into a ring) and (B) at least one compound selected from (i) groups 1 and 2 and groups 12 and 13 organometallic compounds (e.g. triethylaluminum), (ii) organoaluminumoxy compound (e.g. conventionally known aluminoxane) and (iii) compounds each reactive with the transition metal compound A to form a counter ion (e.g. Lewis acid, ionic compound, borane compound).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst for olefin polymerization.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymerization catalysts include:
So-called Kaminsky catalysts are well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution.

As a transition metal compound used for such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (JP-A-58-19)
No. 309) and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Unexamined Patent Publication No.
No. 1-130314) is known. It is also known that when the transition metal compound used for the polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different.

Recently, a transition metal compound having a ligand having a diimine structure (see International Publication No. WO9623010) has been proposed as a new catalyst for olefin polymerization.
By the way, polyolefins are generally used in various fields such as for various molded articles because of their excellent mechanical properties and the like.In recent years, however, demands for physical properties of polyolefins have been diversified, and polyolefins of various properties are desired. ing. It is also desired to improve productivity.

Under these circumstances, there is a demand for an olefin polymerization catalyst which is excellent in olefin polymerization activity and can produce a polyolefin having excellent properties.

[0006]

An object of the present invention is to provide a catalyst for olefin polymerization having excellent olefin polymerization activity and a method for polymerizing olefins using the catalyst.

[0007]

The catalyst for olefin polymerization according to the present invention comprises (A) a transition metal compound represented by the following general formula (I):

[0008]

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Wherein M is a transition gold of Group 8-11 of the periodic table
A genus atom;¹~ R⁶Are the same or different
Hydrogen atom, hydrocarbon group, organic silyl group,
Shows a lucoxy group or an aryloxy group.
Two or more of which may be linked to each other to form a ring,
n represents a valence of M, and Xs are the same or different
May be a hydrogen atom, a halogen atom, a hydrocarbon group,-
OR⁷, -SR⁸, -N (R⁹)_TwoOr -P (R^Ten)
_Two(However, R ⁷~ R^TenIs an alkyl group, cycloalkyl
Group, aryl group, aralkyl group or organic silyl group.
Then R⁹Each other or R^TenConnect with each other to form a ring
It may be. ), And when n is 2 or more, X
May be connected to each other to form a ring. (B) (B-1) Organometallic compound, (B-2) Organoaluminum
Oxy compound and (B-3) transition metal compound (A)
At least selected from compounds that form ion pairs in response
Are also characterized by comprising one kind of compound.

The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the above-mentioned catalyst.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the catalyst for olefin polymerization according to the present invention and a method for polymerizing olefins using the catalyst will be described in detail.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal compound, (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-
3) It is formed from at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (A).

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal compound The transition metal compound (A) used in the present invention is a transition metal compound represented by the following general formula (I).

[0015]

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In the formula, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table, and is preferably nickel, palladium, cobalt or rhodium. R ^{1 to} R ⁶ may be the same or different and represent a hydrogen atom, a hydrocarbon group, an organic silyl group, an alkoxy group or an aryloxy group.

Specific examples of the hydrocarbon group include a methyl group,
Either an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc. An alkyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; and a substituted aryl having 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms on the aryl group. And the like.

Specific examples of the organic silyl group include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group,
And a triphenylsilyl group.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,
Examples include an n-butoxy group, an isobutoxy group, a tert-butoxy group, and the like.

Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Further, R ^{1 to} R ⁶ may form a ring together with the carbon atom to which two or more of these, preferably adjacent groups are connected to each other and bonded to each other.

N represents the valence of the transition metal atom M, and is specifically an integer of 1 to 4. Xs may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, such as the aforementioned R ^{1 to} R ^6, and an aryl group and a benzyl group having 7 to 20 carbon atoms. And an aralkyl group. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group.

Further, as X, -OR ⁷ , -SR ⁸ ,-
A group represented by N (R ⁹ ) ₂ or —P (R ¹⁰ ) ₂ is also shown. R ^{7 to} R ¹⁰ are the same as R ^{1 to} R ^{6, such} as an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms; and 6 to 2 carbon atoms such as a cyclohexyl group.
A cycloalkyl group of 0; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group; and an organic silyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, and a triethylsilyl group. The aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. R ⁹ and R ¹⁰ may be connected to each other to form a ring.

When n is 2 or more, the Xs may be connected to each other to form a ring. Hereinafter, specific examples of the transition metal compound represented by the general formula (I) are shown, but the invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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In the above examples, Me represents a methyl group, i-Pr represents an i-propyl group, t-Bu represents a tert-butyl group, and Et represents an ethyl group. In the present invention, in the above compounds, a transition metal compound in which nickel metal is replaced with a metal of Groups 8 to 11 of the periodic table other than nickel, such as iron, cobalt, copper, rhodium, and palladium, can also be used.

Among these transition metal compounds, the following general formula (II) constituting the transition metal compound:

[0031]

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(Wherein, R ^{1 to} R ⁶ are the same as those of the general formula (I)
Is the same as ^{1 ~R 6.} MOPA of the ligand represented by)
C VERSION 6.00, Hamiltonian PM3
Orbit (highest occupied molec)
ular orbital (HOMO) and lowest unoccupied orbit (lowest unocc)
It preferably has an energy difference of 9.00 or less, more preferably 8.50 or less, with respect to an upied molecular orbital (LUMO). When the energy difference between HOMO and LUMO is within the above range, an olefin polymerization catalyst using such a transition metal compound has excellent polymerization activity.

(B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specifically, the following Periodic Table Groups 1, 2 and 12, 1
A group 3 organometallic compound is used.

[0034] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3 and m + n + p + q = 3. The organoaluminum compound represented by).

[0035] (B-1b) Formula M ² AlR ^a ₄ (wherein, M ² represents Li, Na, and K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula:

(B-1c) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a Group 2 or Group 12 metal represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

Examples of the organoaluminum compound belonging to (B-1a) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, the aluminum compounds belonging to (B-1a) include tri-n-alkylaluminums such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-tert-aluminum -Butylaluminum, tri-2-methylbutylaluminum, tri3-
Methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-
Methylpentyl aluminum, Tri 2-methylhexyl aluminum, Tri 3-methylhexyl aluminum, Tri
Tri-branched alkyl aluminum such as 2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triisoprenyl aluminum and the like Trialkenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide;
Portion having an average composition represented by like _{^{R a 2.5 Al (OR b)}} 0.5; diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide Alkylaluminum which has been partially alkoxylated; diethylaluminum (2,6-
Di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide),
Diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di
alkyl aluminum aryloxides such as -t-butyl-4-methylphenoxide); dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Diethyl aluminum hydride;
Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxy Partially alkoxylated and halogenated alkylaluminums such as bromide can be mentioned.

Compounds similar to (B-1a) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the above (B-1b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) _{4 and the} like.

In addition, as the organometallic compound (B-1), a compound represented by the general formula (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive Is an integer and z ≧ 2x).

Furthermore, (B-1) the organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium can also be used.

The (B-1) organometallic compound as described above has 1
These are used alone or in combination of two or more. (B-2) Organoaluminum oxy compound (B-2) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-aluminum.
Butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., trialkylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, etc. Dialkylaluminum halides such as tricycloalkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dimethylaluminum methoxide, diethylaluminum ethoxy And dialkylaluminum aryloxides such as diethylaluminum alkoxide and diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y, and z are positive numbers and z ≧ 2x). The compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Yes, insoluble or poorly soluble in benzene.

As the organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (III) can also be mentioned.

[0053]

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In the formula, R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹² may be the same or different, and represents a hydrogen atom, a halogen atom, a siloxy group, a lower alkyl-substituted siloxy group, or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy compound containing boron represented by the above general formula (III) is represented by the following general formula (I)
The alkylboronic acid represented by V) and R ¹¹ -B- (OH) ₂ ... (IV) (in the formula, R ¹¹ represents the same group as described above). It can be produced by reacting in an inert solvent at a temperature of -80C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-aluminum.
Butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., trialkylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, etc. Dialkylaluminum halides such as tricycloalkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dimethylaluminum methoxide, diethylaluminum ethoxy And dialkylaluminum aryloxides such as diethylaluminum alkoxide and diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned organoaluminum oxy compounds (B-2) are used alone or in combination of two or more. (B-3) Reaction with transition metal compound to form ion pair
Compound capable of reacting with the transition metal compound used in the compound the present invention to form an ion pair (B-3) (hereinafter, referred to as "ionizing ionic compound".) Is reacted with the transition metal compound (A) These compounds form an ion pair. Examples of such a compound are described in JP-A-1-501950 and JP-A-1-501950.
JP-5020236, JP-A-3-179005, JP-A-3-179006, JP-A-3-207
703, JP-A-3-207704, USP
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 5,321,106.

Specifically, as the Lewis acid, BR is used.
₃ (R is a phenyl group or a fluorine atom which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group.), For example, trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o- Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (V).

[0062]

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In the formula, R ¹³ includes H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

R ^{14 to} R ¹⁷ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanily Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ¹³ , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

As ionic compounds, trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include, for example, di (1-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex and boron compounds represented by the following formulas (VI) and (VII) can also be mentioned.

[0073]

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(In the formula, Et represents an ethyl group.)

[0075]

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Specific examples of the borane compound include, for example, decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium) ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The above-mentioned (B-3) ionized ionic compounds are used alone or in combination of two or more. Further, the catalyst for olefin polymerization according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2)
A particulate carrier (C) as described below can be used, if necessary, together with at least one compound (B) selected from the organic aluminum oxy compound and (B-3) an ionized ionic compound.

(C) Particulate Carrier The (C) particulate carrier used as required in the present invention is an inorganic or organic compound having a particle size of 10 to 3
A granular or particulate solid of 00 μm, preferably 20-200 μm, is used. Of these, a porous oxide is preferable as the inorganic compound, specifically, SiO ₂ ,
Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
aO-, ZnO, BaO, etc. ThO _2, or a mixture containing them, for example, SiO ₂ -MgO, SiO ₂ -Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Examples thereof include Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , M
g (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O,
It may contain carbonate, sulfate, nitrate and oxide components such as Li ₂ O.

Although the properties of the (C) particulate carrier vary depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g,
Preferably, it is in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The carrier is optionally at 100 to 1000 ° C,
Preferably, it is used by firing at 150 to 700 ° C.

Further, examples of the particulate carrier (C) that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size in the range of 10 to 300 μm. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

The catalyst for olefin polymerization according to the present invention comprises the above-mentioned transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-
3) At least one selected from ionized ionic compounds
Seed compound (B) and, if necessary, finely divided carrier (C)
Consists of FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) Component (A) and at least one component (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound Simply referred to as "component (B)") in any order. (2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (4) A method in which the catalyst component in which the component (A) is supported on the fine-particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on the fine particle carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the fine particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the components (B) may be the same or different. (7) A method in which the catalyst component in which the component (B) is supported on the fine particle carrier (C) and the component (A) are added to the polymerization reactor in an arbitrary order. (8) A method in which the catalyst component in which the component (B) is supported on the particulate carrier (C), the component (A), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the component (C) may be preliminarily polymerized with an olefin. In the olefin polymerization method according to the present invention, in the presence of the olefin polymerization catalyst as described above,
An olefin polymer is obtained by polymerizing or copolymerizing an olefin.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specifically as the inert hydrocarbon medium used in the liquid phase polymerization method, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof, and olefin itself can be used as a solvent.

In conducting olefin polymerization using the olefin polymerization catalyst as described above, component (A)
The amount is usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per 1 liter of the reaction volume.

The component (B-1) has a molar ratio [(B-1) / M] between the component (B-1) and the transition metal atom (M) in the component (A) of usually 0.01 to 0.01. 5000, preferably 0.05 to 2000
It is used in such an amount that Component (B-2) is replaced by component (B-
2) The molar ratio [(B-2) / M] of the aluminum atom in the component (A) to the transition metal atom (M) in the component (A) is usually 10 to 50.
00, preferably 20-2000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1
-10, preferably 1-5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to 200 ° C.
Preferably it is in the range of 0 to 170C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 k
g / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the transition metal compound (A) used. For example, when a transition metal compound represented by the following formula (VIII) is used, an olefin low polymer is obtained,

[0091]

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When a transition metal compound represented by the following formula (IX) or (X) is used, a high olefin polymer can be obtained.

[0093]

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The olefin that can be polymerized with such an olefin polymerization catalyst is one having 2 carbon atoms.
~ 20 α-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-
Hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

A polar monomer can be used together with the olefin. Examples of the polar monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo (2,2,1). -
Α, β-unsaturated carboxylic acids such as 5-heptene-2,3-dicarboxylic acid and α, β-unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium and calcium salts thereof Metal salts; methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Α, β-unsaturated carboxylic esters such as isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, trifluoro Vinyl esters such as vinyl acetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; Further, styrene, vinylcyclohexane, diene and the like can be used.

[0096]

The olefin polymerization catalyst according to the present invention has a high polymerization activity, a narrow molecular weight distribution, and an olefin (co) polymer having a narrow composition distribution when two or more olefins are copolymerized. be able to.

According to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity, a narrow molecular weight distribution, and a narrow composition distribution when two or more olefins are copolymerized can be obtained. .

[0098]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the molecular weight distribution (Mw
/ Mn) is 140 using o-dichlorobenzene as a solvent.
It measured and determined by gel permeation chromatography (GPC) at ° C.

[0100]

Example 1 Synthesis of Compound (A-1) In a 100 ml three-necked flask, 50 ml of ethanol, 2.79 g (30.0 mmol) of aniline and pyridine were added.
3.21 g (30.0 mmol) of -2-aldehyde was charged and stirring was continued at room temperature for 20 hours. The reaction solution was concentrated under reduced pressure to obtain a compound represented by the following formula (a). M of this compound
The energy difference between HOMO and LUMO calculated by OPAC VERSION 6.00 and Hamiltonian PM3 method was 8.28 eV.

[0101]

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Under a nitrogen atmosphere, 0.85 g (2.75 mmol) of (DME) NiBr ₂ (DME = 1,2-dimethoxyethane) and 40 ml of anhydrous acetone were charged into a 100 ml three-necked flask. To this, the compound obtained above
(a) 0.56 g (3.07 mmol) of anhydrous acetone 1
The solution diluted with 0 ml was added dropwise at room temperature over 10 minutes, and the stirring was further continued for 4 hours. The obtained slurry was filtered through a glass filter to collect a solid part, and the solid part was washed three times with 10 ml of anhydrous acetone, and then dried under vacuum to obtain 0.55 g of a compound (A-1) represented by the following formula. .

[0103]

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Polymerization A 250 ml glass autoclave having an internal volume of 500 ml which was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and the gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane was converted to aluminum atom, and then the nickel compound (A-1) obtained above was added in an amount of 0.005 mmol.
The polymerization was started by adding mmol. The reaction was carried out at 25 ° C. for 1 hour in a normal pressure ethylene gas atmosphere. After completion of the polymerization, liquid and gas phase products were analyzed by gas chromatography. As a result, 24 mole% of ethylene dimer and 60 mole of trimer
Mol%, tetramer with a selectivity of 16 mol%. 21800 moles of ethylene had reacted per mole of nickel compound (A-1).

[0105]

Example 2 Synthesis of Compound (A-2) In a 100 ml three-necked flask, 50 ml of ethanol, 2, 2
3.64 g (30.0 mmol) of 6-dimethylaniline and 3.21 g (30.0 mm) of pyridine-2-aldehyde
ol) and stirring was continued at room temperature for 20 hours. The reaction solution was concentrated under reduced pressure to obtain a compound represented by the following formula (b). HOMO and LUMO of this compound calculated by MOPAC VERSION 6.00, Hamiltonian PM3 method
Was 8.29 eV.

[0106]

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0.97 g (3.14 mmol) of (DME) NiBr _{2 was} placed in a 100 ml three-necked flask under a nitrogen atmosphere.
l) and 40 ml of anhydrous acetone were charged. To this, 0.725 g (3.45 mmol) of the compound (b) obtained above was added.
l) was diluted with 10 ml of anhydrous acetone.
The mixture was added dropwise over 0 minutes, and stirring was further continued for 4 hours. The obtained slurry was filtered with a glass filter to remove a solid portion. The solution part was concentrated under reduced pressure, and the solid part obtained was extracted and crystallized with methylene chloride. The obtained solid is washed with hexane 10
After washing three times with ml, vacuum drying was performed to obtain 0.81 g of a compound (A-2) represented by the following formula.

[0108]

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Polymerization To a glass autoclave having an internal volume of 500 ml, which had been sufficiently purged with nitrogen, 250 ml of toluene was charged, and ethylene was passed through the autoclave at 100 liter / hour, and the mixture was allowed to stand at 25 ° C. for 10 minutes. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atoms, and subsequently, the nickel compound (A-2) obtained above was added in an amount of 0.005 mmol to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was performed at 25 ° C. for 1 hour under normal pressure, and then a small amount of methanol was added to stop the polymerization.
The polymer solution was added to a large excess of methanol to precipitate the polymer, which was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 1.97 g of a polymer having Mw of 700 and Mw / Mn of 1.92 was obtained.

[0110]

Example 3 Synthesis of Compound (A-3) In a 100 ml three-necked flask, 50 ml of ethanol, 2, 2
5.32 g of 6-diisopropylaniline (30.0 mmol
l) and 3.21 g of pyridine-2-aldehyde (30.
0 mmol) and stirring was continued at room temperature for 20 hours.
The reaction solution was concentrated under reduced pressure to obtain a compound represented by the following formula (c). MOPAC VERSION 6.0 for this compound
0, the energy difference between HOMO and LUMO calculated by the Hamiltonian PM3 method was 8.24 eV.

[0111]

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Under a nitrogen atmosphere, 0.91 g of (DME) NiBr ₂ (2.95 mmol) was placed in a 100 ml three-necked flask.
l) and 40 ml of anhydrous acetone were charged. To this, 0.870 g (3.27 mmol) of the compound (c) obtained above was added.
l) was diluted with 10 ml of anhydrous acetone.
The mixture was added dropwise over 0 minutes, and stirring was further continued for 4 hours. The obtained slurry was filtered with a glass filter to remove a solid portion. The solution part was concentrated under reduced pressure, and the solid part obtained was extracted and crystallized with methylene chloride. The obtained solid is washed with hexane 10
After washing three times with ml, vacuum drying was performed to obtain 0.86 g of a compound (A-3) represented by the following formula.

[0113]

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Polymerization The polymerization of Example 2 was repeated except that the nickel compound (A-3) obtained above was used in place of the nickel compound (A-2). Was polymerized. As a result, Mw was 670, and Mw / Mn was 1.
3.67 g of polymer 68 were obtained.

[0115]

Example 4 In the same manner as in the polymerization example of Example 2, except that 0.5 mmol of diethylaluminum chloride in terms of aluminum atom was used instead of 1.25 mmol of methylaluminoxane. Ethylene was polymerized. As a result, 1.27 g of a polymer was obtained.

[0116]

Example 5 In the same manner as in the polymerization example of Example 2, except that 0.5 mmol of ethyl aluminum dichloride in terms of aluminum atom was used instead of 1.25 mmol of methylaluminoxane in the polymerization example of Example 2, Ethylene was polymerized. As a result, 0.05 g of a polymer was obtained.

[0117]

Example 6 In the same manner as in the polymerization example of Example 3, except that 1.25 mmol of methylaluminoxane was replaced by 0.5 mmol of diethyl aluminum chloride in terms of aluminum atom in the polymerization example of Example 3, Ethylene was polymerized. As a result, 3.58 g of a polymer was obtained.

[0118]

Example 7 In the same manner as in Example 3, except that 1.25 mmol of methylaluminoxane was replaced by 0.5 mmol of ethyl aluminum dichloride in terms of aluminum atom. Ethylene was polymerized. As a result, 1.32 g of a polymer was obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (2)

[Claims] (A) A transition metal represented by the following general formula (I):
A genus compound, and(In the formula, M represents a transition metal atom of Groups 8 to 11 of the periodic table.
Then R¹~ R⁶May be the same or different from each other,
Atom, hydrocarbon group, organic silyl group, alkoxy group or
Represents an aryloxy group, two or more of which are
N may represent a valence of M; X may be the same or different from each other; and may represent a hydrogen atom,
Halogen atom, hydrocarbon group, -OR⁷, -SR⁸, -N
(R⁹)_TwoOr -P (R^Ten)_Two(However, R ⁷~ R^Ten
Represents an alkyl group, a cycloalkyl group, an aryl group,
A kill group or an organic silyl group;⁹Each other or R^Ten
The two may be connected to each other to form a ring. )
And when n is 2 or more, Xs are connected to each other to form a ring
May be formed. (B) (B-1) Organometallic compound, (B-2) Organoaluminum
Oxy compound and (B-3) transition metal compound (A)
At least selected from compounds that form ion pairs in response
Characterized by comprising one kind of compound
Catalyst for polymerization. 2. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.