JPH1180224A - Catalyst component for olefin polymerization, catalyst for olefin polymerization and method for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst component which, when combined with a transition metal compd. of the group 13 of the periodic table, gives a catalyst for olefin polymn. by forming an ionic compd. comprising a cation component and an anion component contg. an atom selected from group 13 elements of the periodic table. SOLUTION: This catalyst component comprises an ionic compd. represented by formula I (wherein A<+> is a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltriphenyl cation, or a ferrocenium cation having a transition metal; Q is an atom selected from group 13 elements of the periodic table; R<0> is a divalent org. group selected from among groups represented by formula II; and R<1> to R<4> are each H, halogen, a 1-20C hydrocarbon group, a 1-20C halogenated hydrocarbon group, an oxygen- cotg. hydrocarbon group or a silicon-contg. group provided adjacent two groups may be linked). A catalyst for olefin polymn. is formed from a transition metal compd. of the group 3-12 of the periodic table and an ionic compd. represented by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer, a propylene polymer or an ethylene / propylene copolymer, a titanium catalyst comprising a titanium compound and an organoaluminum compound,
A vanadium catalyst comprising a vanadium compound and an organoaluminum compound is known.

[0003] Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, single-site catalysts such as metallocene catalysts, including geometrically constrained catalysts, are known. These catalysts and organic catalysts such as aluminoxane are known. It is generally known that when used in combination with a compound containing a boron atom such as an aluminum oxy compound or triphenylcarbenium tetrakis (pentafluorophenyl) borate, high activity is exhibited.

[0004] Under such circumstances, the emergence of a new co-catalyst component that exhibits catalytic performance when used in combination with a metallocene compound or the like is desired.

[0005]

An object of the present invention is to provide a novel catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, and a method for polymerizing olefins using the catalyst.

[0006]

The catalyst component for olefin polymerization according to the present invention comprises an ionic compound represented by the following general formula (Ia):

[0007]

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(In the formula, A ⁺ represents a cation, Q represents an atom selected from Group 13 of the periodic table, and R ⁰ represents a divalent organic group.) A in the general formula (Ia) Examples of ⁺ include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. Examples of the divalent organic group represented by R ⁰ include the following group a. There are groups shown below.

[0009]

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(Wherein R ¹ to R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms.
Represents a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a silicon-containing group, and two adjacent groups among the groups represented by R ¹ to R ⁴ are linked to each other and cooperate with a carbon atom to which each is bonded. May form a ring having 4 to 16 carbon atoms. As the ionic compound represented by the general formula (Ia), a compound represented by the following general formula (Ib) is preferable.

[0011]

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(Where A ⁺ has the same meaning as in the above formula (Ia), Q represents an atom selected from Group 13 of the periodic table, and R ¹ and R ⁴ are the same or different. May have a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms.
A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, or a silicon-containing group, and these groups are connected to each other to form a carbon atom It may form a ring of Formulas 4 to 16, and R ² represents a group having an aromatic ring. The olefin polymerization catalyst component according to another embodiment of the present invention includes:
It is characterized by comprising a compound represented by the following general formula (II-a) (hereinafter sometimes referred to as “group 13 compound”);

[0013]

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(In the formula, Q represents an atom selected from Group 13 of the periodic table, and R ⁰ represents a divalent organic group.) In the general formula (II-a), the divalent organic group represented by R ⁰ Examples of the group include the groups shown in the aforementioned group a.

The compound represented by the general formula (II-a) is preferably a compound represented by the following general formula (II-b).

[0016]

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(Wherein Q represents an atom selected from Group 13 of the periodic table, R ¹ and R ⁴ may be the same or different and each have a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms. A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, or a silicon-containing group, and these groups are connected to each other to form a carbon atom may C 4 to form a 16 ring, R ² represents a group having an aromatic ring.) the olefin polymerization catalyst according to the present invention, (a) the periodic table transition metal compound of groups 3 to 12 And (B) the general formula (I)
-A) or (B ') a compound represented by the general formula (II-a) and, if necessary, (C) an organometallic compound. .

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

[0019]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst component, the olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

The olefin polymerization catalyst component according to the present invention comprises an ionic compound represented by the following general formula (Ia).

[0021]

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In the formula, A ⁺ is a cation, specifically, a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, and the like.

Specific examples of the carbonium cation include:
And 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-diethylanili Nium cation, N,
N, N- such as N-2,4,6-pentamethylanilinium cation
Dialkylanilinium cation; di (isopropyl)
Examples thereof include an ammonium cation and a dialkylammonium cation such as a dicyclohexylammonium cation.

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

Q is an atom selected from Group 13 of the periodic table, and is preferably boron or aluminum. R ⁰ is 2
A divalent organic group, for example, a divalent organic group whose main chain is formed from carbon atoms and / or nitrogen atoms, in particular, the main chain contains at least two carbon atoms, and has a nitrogen atom in the main chain. And a divalent organic group which may be used.

Specific examples include groups as shown in the following group a.

[0028]

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In the formula, R ¹ to R ⁴ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. It represents a hydrocarbon group, an oxygen-containing hydrocarbon group or a silicon-containing group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl,
Alkyl groups such as propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cyclopentyl,
Cycloalkyl groups such as cyclohexyl, norbornyl, and adamantyl; and alkenyl groups such as vinyl, propenyl, and cyclohexenyl. Examples of the hydrocarbon group having an aromatic ring include arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, naphthyl, methylnaphthyl, and anthryl Aryl groups such as phenanthryl; pentafluorobiphenyl;
6- such as a substituted aryl group such as nonafluorophenyl;
Groups having 20 carbon atoms are mentioned.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a group in which the hydrocarbon group is substituted with halogen. Examples of the oxygen-containing hydrocarbon group include an alkoxy group and an alkoxyalkyl group, and specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, i-
Propoxy, n-butoxy, tert-butoxy and the like are mentioned, and specific examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl and the like.

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl;
Trihydrosilyl substituted silyls such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyls of hydrocarbon substituted silyls such as trimethylsilyl ether Ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

Two adjacent groups represented by R ¹ to R ⁴ may be linked to each other to form a ring having 4 to 16 carbon atoms in cooperation with the carbon atoms to which they are bonded; Examples of an embodiment in which adjacent groups form a ring include groups having a naphthyl skeleton, an indenyl skeleton, a fluorenyl skeleton, and the like.

The ionic compound represented by the general formula (Ia) is preferably a compound represented by the following general formula (Ib).

[0035]

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In the formula, A ⁺ and Q represent the above-mentioned general formula (I-
It has the same meaning as a). R ¹ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
0 represents a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a silicon-containing group, and specifically includes the same atoms or groups as described above.

R ¹ and R ⁴ are linked to each other, and together with the carbon atom to which they are bonded, have 4 to 16 carbon atoms.
May be formed. Examples of forming the ring include groups having a naphthyl skeleton, an indenyl skeleton, a fluorenyl skeleton, and the like.

R ² represents a group having an aromatic ring, and specific examples include groups having 6 to 20 carbon atoms as described above. Examples of the anion portion of the ionic compound represented by the general formula (Ia) include the following anions.

[0039]

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[0040]

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Although these are examples of boron compound anions, anions obtained by replacing boron in these anions with aluminum are also exemplified. The ionic compound as described above can be used as a catalyst component for olefin polymerization, and when combined with a transition metal compound as described below,
Has olefin polymerization activity. Among these ionic compounds, the compound represented by the general formula (I-b) is
When used in combination with a transition metal compound, the olefin polymerization activity is high, which is preferable.

Another embodiment of the catalyst component for olefin polymerization according to the present invention is a compound (1) represented by the following general formula (II-a):
Group 3 compound).

[0043]

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In the formula, Q is an atom selected from Group 13 of the periodic table, and is preferably boron or aluminum. R
⁰ represents a divalent organic group, for example, a divalent organic group whose main chain is formed from a carbon atom and / or a nitrogen atom, particularly a main chain containing at least two carbon atoms, and a nitrogen atom in the main chain. And a divalent organic group which may have Specific examples include groups as shown in the above-mentioned group a.

The compound represented by the general formula (II-a) is preferably a compound represented by the following general formula (II-b).

[0046]

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In the formula, Q has the same meaning as in the above formula (II-a). R ¹ and R ⁴ may be the same or different from each other, and have a hydrogen atom, a halogen atom, and 1 carbon atom.
-20 hydrocarbon groups, halogenated hydrocarbon groups having 1-20 carbon atoms, oxygen-containing hydrocarbon groups or silicon-containing groups, specifically the same atoms or groups as described above.

R ¹ and R ⁴ are linked to each other, and together with the carbon atom to which they are bonded, have 4 to 16 carbon atoms.
May be formed. Examples of forming the ring include groups having a naphthyl skeleton, an indenyl skeleton, a fluorenyl skeleton, and the like.

R ² represents a group having an aromatic ring, and specific examples are the same as described above. Examples of the Group 13 compound represented by the general formula (II-a) include the following compounds.

[0050]

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[0051]

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These are examples of boron compounds, but compounds in which boron in these compounds is replaced with aluminum are also exemplified. The group 13 compound as described above can be used as an olefin polymerization catalyst component, and has olefin polymerization activity when combined with a transition metal compound as described below. Among these group 13 compounds, the compound represented by the general formula (II-b) is preferable because it has a high olefin polymerization activity when used in combination with a transition metal compound.

Next, an olefin polymerization catalyst using the ionic compound or the group 13 compound as a catalyst component and a method for polymerizing olefins using the catalyst will be described. The catalyst for olefin polymerization of the present invention comprises (A) a transition metal compound belonging to Groups 3 to 12 of the periodic table and (B) a compound represented by the general formula (I)
an ionic compound represented by -a) or (B ') a Group 13 compound represented by the general formula (II-a), if necessary,
(C) It is formed from an organometallic compound.

First, each component forming the olefin polymerization catalyst of the present invention will be specifically described. (A) Transition metal compounds of Groups 3 to 12 of the periodic table (A) Examples of the transition metal compound include compounds represented by the following general formula (III-1) or (IV).

M ¹ L ¹ _x (III-1) (wherein M ¹ represents a transition metal atom belonging to Group 4 of the periodic table;
¹ represents a ligand coordinated to a transition metal atom M ¹ , and at least one L ¹ is a ligand having a cyclopentadienyl skeleton, and L ¹ other than a ligand having a cyclopentadienyl skeleton ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom, and x Is the valence of the transition metal atom M ¹ . M ³ L ³ _x (IV) (wherein, M ³ represents a transition metal atom belonging to Groups 3 to 12 of the periodic table, and L ³ has a cyclopentadienyl skeleton coordinated to the transition metal atom M ³ ) A neutral or anionic ligand other than a ligand, wherein the ligand L ³ is a transition metal atom M ³ , B,
At the atoms such as C, N, O, P, S, and halogen, the charge state is bonded in a neutral or anionic form. x is a valence of the transition metal atom M ^3. In the general formula (III-1), M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.

X is a transition metal atom M¹The valence of
Transfer metal atom M¹L coordinated to ¹Indicates the number of L
¹Represents a ligand coordinated to a transition metal atom, and at least
One L¹Is a ligand having a cyclopentadienyl skeleton
Other than a ligand having a cyclopentadienyl skeleton
L¹Is a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 atoms, an oxygen-containing group,
Ow-containing groups, silicon-containing groups, halogen atoms or hydrogen sources
I am a child.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

When the compound represented by the general formula (III-1) contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton The two may be linked via a divalent linking group such as a (substituted) alkylene group or a (substituted) silylene group. Such a transition metal compound in which a ligand having a cyclopentadienyl skeleton is bonded through a divalent bonding group is represented by a general formula (III-
The transition metal compound represented by 3) is mentioned.

Specific examples of the ligand L ¹ other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group,
An arylalkyl group, an aryl group, and the like; more specifically, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; a cycloalkyl such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl And aryl groups such as phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. A hydroxy group as the oxygen-containing group; methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

The sulfur-containing group includes a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate and p-toluene sulfonate. , Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

As the silicon-containing group, monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl;
Trihydrosilyl substituted silyls such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyls of hydrocarbon substituted silyls such as trimethylsilyl ether Ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Such transition metal compounds are, for example, those having a transition metal valence of 4
Is more specifically represented by the following general formula (III-2).

R ¹¹ R ¹² R ¹³ R ¹⁴ M ¹ (III-2) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table as described above, and is preferably a zirconium atom. .

R ¹¹ represents a group (ligand) having a cyclopentadienyl skeleton, and R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and represent a group having a cyclopentadienyl skeleton. (Ligand) represents a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

In the present invention, in the transition metal compound represented by the above general formula (III-2), at least one of R ¹² , R ¹³ and R ¹⁴ is a group (ligand) having a cyclopentadienyl skeleton. Certain compounds, for example, compounds in which R ¹¹ and R ¹² are groups (ligands) having a cyclopentadienyl skeleton are preferably used. When R ¹¹ and R ¹² are groups having a cyclopentadienyl skeleton (ligand), R ¹³ and R ¹⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an alkenyl group, Arylalkyl group, aryl group, alkoxy group,
It is preferably an aryloxy group, a trialkylsilyl group, a sulfonate group, a halogen atom or a hydrogen atom.

Hereinafter, the compound represented by the general formula (III-1)
Specific compounds of the transition metal compound in which M ¹ is zirconium are exemplified. Bis (cyclopentadienyl)
Zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) zirconium phenoxymonochloride , Bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopenta Dienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, Scan (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) Zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium Bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadienyl) zirconiumbi (Trifluoromethanesulfonato), bis (butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) zirconium Bis (trifluoromethanesulfonato), bis (methylethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylpropylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylbutylcyclopentane) Dienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) di Ruconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylhexylcyclopentadienyl) zirconium dichloride, bis (ethylbutylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride , Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylbenzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, bis ( Methylcyclohexylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ethylzirconium monochloride , Bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (Cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (methylethyl) Cyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bichloride (Methanesulfonate), bis (trimethylsilylcyclopentadienyl) zirconium dichloride and the like.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted includes 1,2,3- and 1,2,4 -Including substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert
-Including isomers.

Further, in the above-mentioned zirconium compounds, compounds in which zirconium is replaced by titanium or hafnium can also be mentioned. Examples of the transition metal compound compound in which a ligand having two cyclopentadienyl skeletons are bonded via a divalent bonding group include a compound represented by the following formula (III-3).

[0070]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, preferably zirconium.
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different from each other, and include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and silicon-containing. Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, hydrogen atom or halogen atom. R ¹⁵ ,
Of the groups represented by R ¹⁶ , R ¹⁷ and R ¹⁸ , some of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. Note that R ¹⁵ , R ¹⁶ ,
Although R ¹⁷ and R ¹⁸ are respectively shown at two places, for example, each of R ¹⁵ and R ¹⁵ may be the same group or different groups. Among the groups represented by R, those having the same suffix represent a preferable combination when forming a ring by inheriting them.

[0072] Examples of the hydrocarbon group having 1 to 20 carbon atoms, the general formula (III-1) same alkyl group as L ¹ in, cycloalkyl group, alkenyl group, arylalkyl group, an aryl group And so on.

The ring formed by combining these hydrocarbon groups includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples include a condensed ring group such as an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl, and butyl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Specific examples of the silicon-containing group include the same monohydrocarbon-substituted silyl, dihydrocarbon-substituted silyl, trihydrocarbon-substituted silyl, silyl ether of hydrocarbon-substituted silyl, and silicon as described for L ¹ in formula (III-1). Examples include a substituted alkyl group and a silicon-substituted aryl group.

Oxygen-containing group More specifically, the above-mentioned general formula (III-
Similar hydroxy group and L ¹ in 1), an alkoxy group, an aryloxy group, and arylalkoxy group.

Examples of the sulfur-containing group include substituents in which oxygen in the above-mentioned oxygen-containing group has been replaced by sulfur. An amino group as the nitrogen-containing group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino;
Phenylamino, diphenylamino, ditolylamino,
Examples thereof include an arylamino group such as dinaphthylamino and methylphenylamino, or an alkylarylamino group.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and in particular, a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, and a hydrocarbon group are bonded. A hydrogen atom on the benzene ring formed by bonding a benzene ring and a hydrocarbon group formed by methyl, ethyl, n-propyl, iso-propyl, n-butyl, is
It is preferably a group substituted with an alkyl group such as o-butyl and tert-butyl.

X ¹ and X ² may be the same or different from each other, and include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, the oxygen-containing group and the halogen atom include the same groups and atoms as those described above for R ^{15 to} R ^18. be able to.

Examples of the sulfur-containing group include the same groups as those described above for R ^{15 to} R ¹⁸ , methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl Sulfonate groups such as benzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenes Examples thereof include sulfinate groups such as ruffinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl group and silicon-substituted aryl group as those described above for R ^{15 to} R ¹⁸ . Among these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydride group, divalent silicon-containing group, divalent germanium-containing
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR¹⁹
-, -P (R¹⁹)-, -P (O) (R¹⁹)-, -BR ¹⁹
-Or -AlR¹⁹-[However, R¹⁹Are identical to each other
May also be different, and hydrocarbons having 1 to 20 carbon atoms
Elemental group, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene, 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Alkylene groups such as cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene;

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

As the divalent silicon-containing group, silylene,
Methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; alkyldisilylene groups such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; alkylaryldisilylene groups; And a silylene group.

Examples of the divalent germanium-containing group include groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Examples of the divalent tin-containing group include a group in which silicon of the divalent silicon-containing group is substituted with tin.

Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene are particularly preferred. R ¹⁹ is the same as R ^{15 to} R ¹⁸
And a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

The following are specific examples of the transition metal compound represented by the formula (III-3). Ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene
-Bis (indenyl) zirconium bis (p-toluenesulfonate), ethylene-bis (indenyl) zirconium bis (p-chlorobenzenesulfonato), ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride , Isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-
Bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) zirconium Dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylene
-Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) Zirconium dichloride, rac-dimethylsilylene-bis (2,
3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl)
Zirconium dichloride, dimethylsilylene (3-tert-
Butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3-methyl Indenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium Dichloride,
Dimethylsilylene (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-tert-butylcyclopentadienyl)
(3-tert-butylindenyl) zirconium dichloride,
Dimethylsilylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Another specific example of the transition metal compound represented by the general formula (III-3) is a transition metal compound represented by the following general formula (III-4) or (III-5).

[0091]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium. R
²¹ may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl Alkyl groups such as tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl;
And alkenyl groups such as vinyl and propenyl.

Of these, a primary alkyl group having carbon atoms bonded to the indenyl group is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group and an ethyl group are particularly preferred.

R ²² , R ²⁴ , R ²⁵ and R ²⁶ may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ²¹ . R ²³ may be the same or different, and represent a hydrogen atom or an aryl group having 6 to 16 carbon atoms;
Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl and phenanthryl are preferred.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and other hydrocarbon groups having 1 to 20 carbon atoms. It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

[0096] X ¹ and X ² may be the same or different from each other, are the same as X ¹ and X ² in the general formula (III-3). Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.

Y ¹ is a group represented by the formula (III-3):
Y ¹ is the same as that. Of these, a divalent silicon-containing group and a divalent germanium-containing group are preferable,
It is more preferably a divalent silicon-containing group, more preferably an alkylsilylene, an alkylarylsilylene or an arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (III-4) are shown below. rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
Methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (1-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2-methyl-4-
(2-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-
Anthryl) indenyl)｝ zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (p-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (o-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
-(2-methyl-4- (p-bromophenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-methyl-4- (p-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (m-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis ｛1- (2-methyl-4- (o
-Tolyl) indenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-
(p-benzylphenyl) indenyl) ニ ル zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (p-biphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (m
-Biphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis ｛1-
(2-methyl-4-phenylindenyl) zirconium dichloride, rac-di- (i-propyl) silylene-bis ｛1- (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis} 1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl) zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )｝ Zirconium dichloride, rac-ethylene-bis ｛1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me,

Rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-) Naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4 -(9-Anthril)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-phenanthryl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (o-methylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (m-methylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (p-methylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl- 4- (2,4-dimethylphenyl) indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (o -
Chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4 -(p-chlorophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,3-
Dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,
6-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(3,5-dichlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4
-(3-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(4-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(4-biphenylyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (4-
Trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl -Four
-(α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4-
(β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4-
(2-methyl-1-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl
-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- ( 2-i-propyl-4-
(α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4-
(β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4-
(8-methyl-9-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl
-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl
-4-phenylindenyl)｝ zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β- Naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-anthryl) Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl -4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- ( 2-n-butyl-4-phenylindenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-n-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-
Butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4- (α
-Naphthyl) indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2- Methyl-1-
Naphthyl) indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4- (α-naphthyl) ) Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-hexyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-methylphenylsilylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-methylphenylsilylene
-Bis {1- (2-ethyl-4- (9-anthryl) indenyl)}
Zirconium dichloride, rac-methylphenylsilylene
-Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenyl Silylene-bis ｛1
-(2-ethyl-4- (α-naphthyl) indenyl) デ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-
Ethyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1 -(2-ethyl-4- (4-biphenylyl) indenyl) デ zirconium dichloride, rac-methylene-bis-1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl) {zirconium dichloride, rac-ethylene-bis} 1
-(2-Ethyl-4-phenylindenyl) コ zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-
Ethylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-
n-propyl-4-phenylindenyl) zirconium dichloride.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, when polymerizing an olefin having 3 or more carbon atoms, a racemic transition metal compound represented by the general formula (III-4) is preferably used as a catalyst component.

The transition metal compound represented by the general formula (III-4) is described in Journal of Organometallic Chem.
(1985), pp. 63-67, European Patent Application 0,320,
It can be produced according to the specification and examples of the Patent No. 762.

Next, the transition metal compound represented by the general formula (III-5) will be described.

[0103]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium. R
³¹ and R ³² may be the same or different from each other,
Hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, specifically, the R ¹⁵ to R
The same atoms or groups as those in ¹⁸ are exemplified.

Of these, R ³¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group of 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms of methyl, ethyl and propyl.

R ³² has a hydrogen atom or a carbon atom number of 1 to 1.
The hydrocarbon group is preferably 20 hydrocarbon groups, and particularly preferably a hydrogen atom or methyl, ethyl or propyl having 1 carbon atom.
It is preferably from 3 to 3 hydrocarbon groups.

R ³³ and R ³⁴ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl and the like.

Among them, R ³³ is preferably a secondary or tertiary alkyl group. X ¹ and X ² may be the same or different from each other, and may have the general formula (III-3)
And X ¹ and X ² are the same.

Y ¹ is represented by the formula (III-3):
Y ¹ is the same as that. Specific examples of the transition metal compound represented by the general formula (III-5) are shown below. rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-n-propylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis
(2,7-dimethyl-4-n-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-
Dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2,7-dimethyl-4-
n-pentylindenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-methylcyclohexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-phenyl Ethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-phenyldichloromethylindenyl)｝ zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl) ｝ Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindene) Nil)｝ zirconium dichloride, rac-di (i-propyl) silylene-bis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (n-butyl) silylene-bis ｛1- (2,7-
Dimethyl-4-i-propylindenyl) {zirconium dichloride, rac-di (cyclohexyl) silylene-bis} 1
-(2,7-dimethyl-4-i-propylindenyl) {zirconium dichloride, rac-methylphenylsilylene-bis} 1
-(2,7-dimethyl-4-i-propylindenyl) {zirconium dichloride, rac-methylphenylsilylene-bis} 1
-(2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2,7
-Dimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-diphenylsilylene-bis} 1- (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, r
ac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4)
-i-propylindenyl) zirconium dichloride, r
ac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
i-propyl-7-ethylindenyl) zirconium dibromide, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,3,7-trimethyl-4-n-propylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl -4-sec-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,3,7-trimethyl-4-n-pentylindenyl) Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl 4-cyclohexylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2,3,7-trimethyl-4-trimethylsilylmethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethyl) Indenyl)｝ zirconium dichloride, rac-diethylsilylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (i-propyl) silylene-bis ｛1 -(2,
3,7-trimethyl-4-i-propylindenyl) {zirconium dichloride, rac-di (n-butyl) silylene-bis} 1
-(2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl) )｝ Zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2,3 , 7-Trimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenyl Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl) )｝ Zirconium dichloride, rac-di (p-tolyl) silylene- 1- (2,3,7-trimethyl-4-i-propylindenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis レ ン 1- (2,3,7-trimethyl-4- i-
Propylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7)
-Methylindenyl)｝ zirconium dimethyl, rac-dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl-7-
Methylindenyl) zirconium methyl chloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4-i-propyl)
-7-methylindenyl)｝ zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl-7-methylindenyl)｝ zirconium
-Bis (p-phenylsulfinato), rac-dimethylsilylene-bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene- Bis {1- (2-methyl-4,6-di-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-phenyl-4-i-propyl-7-methylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methylindenyl) )｝ Zirconium dichloride, rac-ethylene-bis ｛1- (2,4,7-trimethylindenyl)｝ zirconium dichloride, rac-
Isopropylidene-bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Of these, i-propyl and sec-
Those having a branched alkyl group such as butyl and tert-butyl are particularly preferred.

In the present invention, when polymerizing an olefin having 3 or more carbon atoms, a racemic transition metal compound represented by the above general formula (III-5) is preferably used as a catalyst component.

The transition metal compound represented by the general formula (III-5) can be synthesized from an indene derivative by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a compound represented by the following general formula (III-6) can also be used as the transition metal compound (A). L in _{^{2 M 2 X 3 2 ... (}} III-6) expression, M ² represents a periodic table group IV transition metal atom.

L ² is a derivative of a delocalized π-bonded group, imparts a constrained geometry to the metal M ² active site, and X ³ may be the same or different from each other, It is a halogen atom or a hydrocarbon group containing not more than 20 carbon atoms, silicon atoms or germanium atoms, a silyl group or a germyl group.

Among the compounds represented by the general formula (III-6), a compound represented by the following general formula (III-7) is preferable.

[0116]

Embedded image

In the formula, M ² represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium. Cp is
A substituted cyclopentadienyl group having a π bond to M ² and having a substituent Z or a derivative thereof.

[0118] Z represents an oxygen atom, a ligand containing a sulfur atom, a boron atom or the periodic table Group 14 atoms, for example, _{^{-Si (R 41 2) -,}} - C (R 41 2) -, - Si (R
^{_{41 2) Si (R 41 2}} ) -, - C (R 41 2) C (R 41 2) -,
_{^{-C (R 41 2) C (}} R 41 2) C (R 41 2) -, - C
^{(R 41) = C (R} 41) -, - C (R 41 2) Si (R 41 2)
_{^{-, - Ge (R 41 2}} ) - , and the like.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, —N (R
⁴² )-, -O-, ^-S- , -P ( ^R42 )-and the like.
Z and Y ² may form a condensed ring.

R ⁴¹ is a group selected from a hydrogen atom or an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group and combinations thereof. ⁴² is an alkyl having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, or one or more R ⁴¹ and up to 30 May form a fused ring system of non-hydrogen atoms.

X ³ is the same as defined in the above formula (III-6). Specific examples of the transition metal compound represented by the general formula (III-7) are shown below. (Tert-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tert-butylamide)
(Tetramethyl- eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (Tetramethyl-
η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -Cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) Silane titanium dichloride, (phenyl phosphide)
Dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane zirconium dibenzyl and the like.

In the general formula (IV), M ³ is the ^{third to} twelfth of the periodic table.
Represents a transition metal atom of the group IV, preferably from the fourth to tenth periodic table
Group transition metal atom, more preferably titanium, zirconium, hafnium, nickel, palladium, chromium, iron and cobalt. L ³ is a neutral or anionic ligand other than the ligand having a cyclopentadienyl skeleton coordinated to the transition metal atom M ^3, and the ligand L ³ is a transition metal atom M ^3, B, At the atoms such as C, N, O, P, S, and halogen, the charge state is bonded in a neutral or anionic form. The ligands represented by L ³ may be the same or different from each other. B among neutral ligands
Examples of the ligand bonded with C include alkyl borane, aryl borane, and the like.Examples of the ligand bonded with C include a conjugated diene compound residue,
Examples of ligands bonded at N include amino, amide, sulfonamide, imide, imino, and the like;
Examples of the ligand bonded by O include alkoxy, carbonyl, ester, amide and the like, and examples of the ligand bonded by P include phosphine, phosphite and the like. Examples of the ligand bonded by are thiophenol, sulfide, thioketone, thioketoester and the like. Among the anionic ligands, examples of the ligand bonded at B include alkyl borates, aryl borates, and borabenzene, and examples of the ligand bonded at C include π Examples of ligands bonded at N, including aryl and the like, include amide, amidine, imidazole, amidate, imidate, and the like. Examples of ligands bonded at O include phenoxide , Alkoxides, carboxyls, oximes, ketoalkoxys and the like.
Examples of the ligand bonded by S include phosphate and the like. Examples of the ligand bonded by S include:
And thiophenoxide, thiocarboxyl group, dithiocarbamate group and the like. Such a general formula (IV)
Examples of the compound represented by are as follows. Such transition metal compounds can be used alone or in combination of two or more. (B) Ionic compound or (B ′) group 13 compound The (B) ionic compound or (B ′) group 13 compound is an ionic compound represented by the above general formula (Ia) or the above general formula (Ia). Group 13 compounds represented by (II-a) are mentioned. Of these, ionic compounds are preferred.

The above-mentioned ionic compounds can be used alone or in combination of two or more. The Group 13 compounds can be used alone or in combination of two or more. Further, two or more ionic compounds and 13 group compounds can be used in combination.

The olefin polymerization catalyst according to the present invention is formed from the (A) transition metal compound and the (B) ionic compound or (B ′) group 13 compound. C) An organometallic compound can be included.

(C) Organometallic Compound In the present invention, as the organometallic compound (C) used as necessary, specific examples of the following Periodic Table 1 are as follows:
Group 2 and Group 12 and Group 13 organometallic compounds are included.

[0126] In (C-1) the general 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).

[0127] (C-2) the general formula M ³ AlR ^a ₄ (wherein, M ³ 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:

(C-3) Formula R ^a R ^b M ⁴ (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 ⁴ is Mg, Zn or Cd.

Examples of the organoaluminum compound belonging to the above (C-1) 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 (C-1) include tri-n-alkylaluminums such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum -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 Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum 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.

Further, a compound similar to (C-1) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
_{(C 2 H 5) 2 AlN} (C 2 H 5) Al (C 2 H 5) 2
And the like.

Examples of the compound belonging to the above (C-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

In addition, as the organometallic compound (C), the general formula (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers) And z ≧ 2x.) Can also be used.

Furthermore, the organometallic compound (C)
As, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium 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 alkyllithium or a combination of aluminum halide and alkylmagnesium may be used.

As the organometallic compound (C) used in the present invention, a metal compound having a branched alkyl group is preferable, and a metal compound having an ethyl group, an isopropyl group and an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable. . Aluminum is preferred as the metal,
Triethyl aluminum and triisobutyl aluminum are most preferred.

These organometallic compounds can be used alone or in combination of two or more. Further, the olefin polymerization catalyst according to the present invention may contain the following (D) phenol derivative, if necessary.

(D) Phenol Derivative In the present invention, the phenol derivative (D) optionally used is a compound represented by the following formula (V).

[0139]

Embedded image

In the formula, R ^{44 to} R ⁴⁸ may be the same or different and each represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a triarylsilyl group, a hydrogen atom or a halogen atom. Alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propyl Phenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like have 6 to 2 carbon atoms. Aryl group; methoxy,
1 carbon atom such as ethoxy, propoxy, butoxy, etc.
An alkoxy group having 20 to 20 carbon atoms; an aryloxy group having 6 to 20 carbon atoms such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; a triarylsilyl group such as triphenylsilyl; and the same halogen atom as described above.

Specific examples of the phenol derivative represented by the general formula (V) include the following compounds. Monoalkyl-substituted phenols such as 2-t-butylphenol; 2,6-dimethylphenol, 2,4-di-t
-Butylphenol, 2,6-di-t-butylphenol, 3,5-
Dialkyl-substituted phenols such as di-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-diisopropylphenol;
2,6-dimethyl-4-t-butylphenol, 2,6-di-t-butyl
-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2-
Trialkyl-substituted phenols such as (1-methylcyclohexyl) -4,6-dimethylphenol, 2-methyl-4,6-dinonylphenol, 2,6-diisopropyl-4-methylphenol; 2-phenylphenol, 3-phenyl Monoaryl-substituted phenols such as phenol and 4-phenylphenol; diaryl-substituted phenols such as 2,6-diphenylphenol; dialkylmonoaryl-substituted phenols such as 2,6-dimethyl-4-phenylphenol; 2,6-diphenyl-4 Monoalkyldiaryl-substituted phenols such as -methylphenol; monoalkylmonoalkoxy-substituted phenols such as 2-t-butyl-4-methoxyphenol;
Dialkylmonoalkoxy-substituted phenols such as 2,6-di-t-butyl-4-methoxyphenol; monoarylmonoalkoxy-substituted phenols such as 2-phenyl-4-methoxyphenol; 2,6-di-triphenylsilylphenol 2,6-di- (triarylsilyl) -substituted phenols
-Alkyl di (triarylsilyl) -substituted phenols such as -triphenylsilyl-4-methylphenol.

Among these, a phenol derivative in which at least one of R ⁴⁴ , R ⁴⁶ and R ⁴⁸ is substituted by a hydrocarbon group having 1 to 12 carbon atoms is preferable. Such phenol derivatives can be used alone or in combination of two or more.

The catalyst for olefin polymerization according to the present invention comprises (A) a transition metal compound, (B) an ionic compound or a (B ′) group 13 compound, (C) an organometallic compound and (D) phenol. A part or all of the derivative can be used as a solid catalyst supported on a carrier as described below.

[0144](E) carrier (E) The carrier is an inorganic or organic compound.
Having a particle size of 10 to 300 μm, preferably 20 to 200 μm.
A μm granular or particulate solid is used. This
Among them, a porous oxide is preferable as the inorganic carrier,
In general, SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, Ti
O_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_TwoSuch
Or a mixture containing them, such as SiO_Two-MgO,
SiO_Two-Al _TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V
_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-MgO etc.
Can be exemplified. Of these, SiO_Twoand
Al_TwoO_ThreeAt least one member selected from the group consisting of
It is preferable that the main component is a component.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

The properties of such a carrier (E) vary depending on its kind and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. , Pore volume is 0.3 ~
Desirably, it is 2.5 cm ³ / g. The carrier is, if necessary, 100-1000 ° C., preferably 150-7 ° C.
It is used by firing at 00 ° C.

Further, (E) the carrier has a particle size of 10
Granular or fine-grained solids of organic compounds having a size of about 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as 4-methyl-1-pentene or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound and (B) an ionic compound (or (B ′) group 13 compound), if necessary. (C)
It is formed from an organometallic compound and / or (D) a phenol derivative.

Hereinafter, the method of supplying and preparing the catalyst for olefin polymerization according to the present invention will be described with reference to the case of using the (B) ionic compound as an example. Can also be supplied and prepared in the same manner as in the case of using the ionic compound (B).

Each of the above components may be individually supplied to the polymerization vessel, or two or more arbitrary components selected from the above components may be brought into contact with the outside of the polymerization vessel in advance and then supplied to the polymerization vessel.
In this case, (A) a transition metal compound and (B) an ionic compound are previously contacted outside the polymerization vessel to prepare a pre-contact catalyst, and then the pre-contact catalyst, (C) an organometallic compound and (D) It is preferable to supply the phenol derivative to the polymerization vessel.

When the above components are separately supplied to the polymerization reactor, the supply order is not particularly limited, but (C) an organometallic compound, (D) a phenol derivative, (A) a transition metal compound, and (B) an ion It is preferable to supply in the order of the active compounds. When the pre-contact catalyst is prepared as described above, the supply order is not particularly limited, but it is possible to supply the (C) organometallic compound, (D) phenol derivative, and the pre-contact catalyst to the polymerization reactor in this order. preferable.

In preparing the pre-contact catalyst, organometallic compounds of Groups 1 to 3 and Groups 11 to 13 of the periodic table such as alkyllithium compounds, alkylmagnesium compounds and alkylaluminum compounds can be used.

Examples of the alkyl lithium compound include methyl lithium, ethyl lithium, propyl lithium, butyl lithium and the like. Examples of the alkyl magnesium compound include methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, and butyl magnesium bromide.

Examples of the alkylaluminum compound include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum and the like.

The catalyst for olefin polymerization according to the present invention may be a solid catalyst in which a part or all of each of the above components is supported on the carrier (E), and the olefin is prepolymerized on the solid catalyst (component). The pre-polymerized catalyst may be used.

The solid catalyst (component) is, for example, the above (E)
Preparation by mixing and contacting a carrier with (A) a transition metal compound and / or (B) an ionic compound, and if necessary, (C) an organometallic compound and / or (D) a phenol derivative in an inert solvent. Can be. Further, the prepolymerized catalyst is, for example, the (A) transition metal compound,
Preparation by introducing an olefin into an inert hydrocarbon solvent in the presence of (B) an ionic compound and (E) a carrier, and if necessary, (C) an organometallic compound and / or (D) a phenol derivative. Can be. When the solid catalyst (component) and the (C) organometallic compound and / or (D) phenol derivative were not used at the time of preparing the prepolymerized catalyst, the (C) organometallic compound and / or (D) phenol derivative were not used. Is added to the polymerization reactor together with the solid catalyst (component) or the prepolymerization catalyst.

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention. Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include α-olefins having 2 to 20 carbon atoms, for example, 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; a 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 and the like can be mentioned. Further, styrene, vinylcyclohexane and the like can be mentioned. In addition to olefins, chain or cyclic dienes such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 7-methyl-1,6-octadiene; 6,10-dimethyl-1 Linear or cyclic trienes such as 5,5,6-undecatriene and 5,9-dimethyl-1,4,8-decatriene; 6,10,14-trimethyl-1,5,9,13-pentadecatetraene Various polyenes such as linear or cyclic tetraenes such as 5,9,13-trimethyl-1,4,8,12-tetradecatetraene can also be copolymerized.

Olefin Polymerization Method In the present invention, olefin polymerization can be performed by any of a gas phase polymerization method or a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method. As the polymerization solvent, an inert hydrocarbon can be used, and the olefin itself can be used as the solvent.

Specific examples of such inert hydrocarbon solvents include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane, methylcyclopentane and cyclohexane. And alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

In the polymerization, (A) the transition metal compound is
The amount of the transition metal atom in the transition metal compound (A) in the polymerization system is 10 ^-8 to 10 ^-3 gram atom, preferably 10 ^-7 to 10 ^-4 gram atom per liter of polymerization volume. Used in (B) The ionic compound has a molar ratio [(B) / (A)] of the (B) ionic compound and (A) the transition metal compound of 0.01 to 10, preferably 0.5 to 5; Is used in such an amount as to fall within the range described above.

The organometallic compound (C) used as required may be a compound of (C) an atom (M) belonging to Group 13 of the periodic table in the organometallic compound and (A) a transition metal in the transition metal compound. It is used in such an amount that the atomic ratio (M / transition metal) is usually in the range of 5 to 50,000, preferably 10 to 20,000. In addition, the (D) phenol derivative used as required is added in an amount of 0.1 to 1 mol of the (B) ionic compound.
It is used in an amount of 1 to 2.9 mol, preferably 0.4 to 2.5 mol, particularly preferably 0.7 to 2 mol.

The amount of the (B ′) group 13 compound used is
(B) Same as the ionic compound. The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 180 ° C., and the polymerization pressure is usually from normal pressure to 100 kg / cm ² ,
Preferably, the pressure is from normal pressure to 50 kg / cm ² .

The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system, and the polymerization can be carried out in two or more stages under different reaction conditions.

[0164]

The catalyst component for olefin polymerization according to the present invention has olefin polymerization activity when combined with a metallocene compound or the like.

The olefin polymerization catalyst of the present invention has high olefin polymerization activity. The olefin polymerization method of the present invention has high olefin polymerization activity.

[0166]

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

[0167]

[Synthesis example] Synthesis of 4-methyl-3-pentafluorophenyl-imidazole
Success

[0168]

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In a 100-ml three-necked reactor sufficiently purged with nitrogen, 2-methylimidazole (12.18 mmol) and 1.70 ml of pentafluoroiodobenzene (12.18) were added.
Mmol) and 10 ml of anhydrous acetonitrile, and the mixture was irradiated with light for 72 hours while stirring. The solvent was distilled off, and diethyl ether was added to the residue. This solution was washed with an aqueous sodium hydrogen carbonate solution and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off to give a light orange solid
0 g (33% yield) was obtained. The structure was identified by FD-MS.

Lithium tetrakis (4-methyl-3-pentane
Synthesis of fluorophenyl-imidazole) boron

[0171]

Embedded image

1.00 g (4.03 mmol) of 4-methyl-3-pentafluorophenyl-imidazole synthesized above in a 100 ml three-necked reactor (with a stirrer chip, condenser, dropping funnel and thermometer) sufficiently purged with nitrogen. , Lithium tetrahydroborate 0.021 (0.9
(6 mmol) and stirred at 180 ° C. while heating. After 24 hours, the solid was filtered through a glass filter, and the residue was washed five times with 50 ml of anhydrous toluene. As a result, 0.8 g (83% yield) of a white solid was obtained.

N, N-dimethylanilinium (tetrakis
(4-methyl-3-pentafluorophenyl-imidazole)
Boron synthesis

[0174]

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A 50 ml eggplant flask was charged with 0.02 g (0.165 mmol) of N, N-dimethylaniline and 10 ml of water, stirred at room temperature, and added with 3.3 m aqueous 0.1N hydrochloric acid.
1 (0.33 mmol) was added and stirred at room temperature for 30 minutes to prepare N, N-dimethylaniline hydrochloride. On the other hand, 0.15 g (0.149 mmol) of lithium tetrakis (4-methyl-3-pentafluorophenyl-imidazole) boron and 10 ml of water are placed in a 50 ml eggplant flask, and the mixture is stirred at room temperature for 30 minutes. The N, N-dimethylaniline hydrochloride prepared above was added thereto, and the mixture was stirred at room temperature for 1 day. This white slurry is filtered with a glass filter,
The solid was washed with 50 ml of water and dried under reduced pressure to obtain 0.09 g of solid (yield 54%).

[0176]

Example 1 400 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
Ethylene is passed at a rate of 100 liters / hour,
C. for 10 minutes. To this, 0.800 mmol of triisobutylaluminum was added and then
0.0008 mmol of ethylenebis (indenyl) zirconium dichloride was added, and finally, 0.0016 mmol of N, N-dimethylanilinium (tetrakis (4-methyl-3-pentafluorophenyl-imidazole) boron) was added to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liters / hour, polymerization was performed at 75 ° C. under normal pressure for 6 minutes, and then a small amount of methanol was added to stop the polymerization. In addition, the polymer was precipitated and dried under reduced pressure at 80 ° C. for 12 hours, to obtain 2.0 g of the polymer.

[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 (12)

[Claims] An olefin polymerization catalyst component comprising an ionic compound represented by the following general formula (Ia): (In the formula, A ⁺ represents a cation, Q represents an atom selected from Group 13 of the periodic table, and R ⁰ represents a divalent organic group.) 2. In the general formula (Ia), A ⁺ is a cation selected from a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal. The catalyst component for olefin polymerization according to claim 1, which is: 3. The catalyst component for olefin polymerization according to claim 1, wherein R ⁰ in the general formula (Ia) is a group selected from the following group a: (Wherein R ¹ to R ⁴ may be the same or different from each other, and have a hydrogen atom, a halogen atom, and a carbon atom number of 1 to 1).
20 hydrocarbon groups, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group or a silicon-containing group, and two adjacent groups represented by R ¹ to R ⁴ are They may be linked to each other to form a ring having 4 to 16 carbon atoms in cooperation with the carbon atoms to which they are bonded. ) 4. The olefin polymerization catalyst component according to claim 3, wherein the ionic compound represented by the general formula (Ia) is a compound represented by the following general formula (Ib); Chemical formula 3] (In the formula, A ⁺ has the same meaning as in the general formula (Ia),
Q represents an atom selected from Group 13 of the periodic table; R ¹ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom A halogenated hydrocarbon group, an oxygen-containing hydrocarbon group or a silicon-containing group having a number of 1 to 20; these groups are connected to each other and form a ring having 4 to 16 carbon atoms in cooperation with the carbon atoms to which they are bonded; May form R
² represents a group having an aromatic ring. ) 5. An olefin polymerization comprising: (A) a transition metal compound belonging to Groups 3 to 12 of the periodic table; and (B) an ionic compound according to any one of claims 1 to 4. Catalyst. 6. A compound formed from (A) a transition metal compound of Groups 3 to 12 of the periodic table, (B) the ionic compound according to any one of claims 1 to 4, and (C) an organometallic compound. An olefin polymerization catalyst, characterized in that: 7. An olefin polymerization catalyst component comprising an elemental compound represented by the following general formula (II-a): (Wherein Q represents an atom selected from Group 13 of the periodic table;
R ⁰ represents a divalent organic group. ) 8. The catalyst component for olefin polymerization according to claim 7, wherein R ⁰ in the general formula (II-a) is a group selected from the group a according to claim 3. 9. The catalyst component for olefin polymerization according to claim 8, wherein the compound represented by the general formula (II-a) is a compound represented by the following general formula (II-b); ] (Wherein Q represents an atom selected from Group 13 of the periodic table;
R ¹ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and oxygen-containing. Represents a hydrocarbon group or a silicon-containing group,
These groups may be linked to each other to form a ring having 4 to 16 carbon atoms in combination with the carbon atoms to which they are bonded, and R ² represents a group having an aromatic ring. ) 10. An olefin polymerization catalyst formed from (A) a transition metal compound of Groups 3 to 12 of the periodic table and (B ') a compound according to any one of claims 7 to 9. . 11. A compound formed from (A) a transition metal compound belonging to Groups 3 to 12 of the periodic table, (B ′) the compound according to any one of claims 7 to 9, and (C) an organometallic compound. An olefin polymerization catalyst, comprising: 12. The claims 5 and 6 and claim 10.
12. A method for polymerizing olefins, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 11 and 11.