JP2000063415A - Catalyst for olefin polymerization and olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization which gives a polymer excellent in polymerization activity and has a wide range of molecular weight distribution, and to provide a method for olefin polymerization by use of this catalyst. SOLUTION: A catalyst for olefin polymerization comprises (A) a transition metal compound containing a ligand having a cyclopentadienyl skeleton, (B) a transition metal compound represented by the following formula and (C) an organic metallic compound, an organic aluminum oxy compound or an ionized ionic compound. In the formula, M is a transition metal of the 3-11 groups of the Periodic Table; (m) is 1-6; R1 is a hydrocarbon and the like; R2, R3, R4 and R5 are H, a halogen, a hydrocarbon group and the like; R6 is a halogen, a hydrocarbon group and the like; (n) is a number fulfilling a valence number of M; and X is a halogen, a hydrocarbon and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for olefin polymerization using this catalyst, and more specifically to an olefin (co) polymer having a high polymerization activity and a wide molecular weight distribution. The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, and a vanadium compound Vanadium-based catalysts composed of and an aluminum compound are known.

A Ziegler type catalyst comprising a metallocene compound such as zirconocene and an organoaluminumoxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

As a newer olefin polymerization catalyst, the applicant of the present invention has filed Japanese Patent Application No. 10-132706.
A transition metal compound having a salicylaldimine ligand represented by the general formula (I) has been proposed. This complex shows high olefin polymerization activity.

[0005]

[Chemical 2]

By the way, polyolefins such as ethylene polymers are excellent in mechanical strength and chemical resistance.
It is used as various molding materials. However, a catalyst composed of a transition metal compound having a salicylaldoimine ligand as described above has a high polymerization activity, but an olefin polymer obtained using this catalyst has a narrow molecular weight distribution and does not necessarily have moldability. Not good. For this reason,
It is desired to improve a catalyst containing a transition metal compound having a salicylaldoimine ligand so that an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained without impairing high polymerization activity.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides an olefin (co) polymer having a high polymerization activity, a broad molecular weight distribution and excellent moldability. It is intended to provide such a catalyst for olefin polymerization.

Another object of the present invention is to provide a method for polymerizing olefins using a catalyst having such good properties.

[0009]

SUMMARY OF THE INVENTION The catalyst for olefin polymerization according to the present invention is
(A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, (B) a transition metal compound represented by the following general formula (I), and (C) (C- 1) at least one selected from organometallic compounds, (C-2) organoaluminumoxy compounds, and (C-3) transition metal compounds (A) or compounds that react with the transition metal compounds (B) to form ion pairs It is characterized by being composed of a compound of a kind.

[0010]

[Chemical 3]

(In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and R ^{1 to} R ^1
6 may be the same or different from each other, a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group,
It represents a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring, and when m is 2 or more, Two of the groups represented by R ^{1 to} R ⁶ may be linked together, n is a number satisfying the valence of M, and X is X.
Is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group , A germanium-containing group, or a tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X are bonded to each other. You may form a ring. )

The olefin polymerization catalyst according to the present invention comprises the transition metal compound (A), the transition metal compound (B),
(C-1) an organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3) a compound which reacts with a transition metal compound (A) or a transition metal compound (B) to form an ion pair. In addition to at least one compound (C), the carrier (D) may be included.

The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned catalyst.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst of the present invention and the olefin polymerization method using this catalyst will be specifically described below.

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymerization but also homopolymerization. In some cases, it is used in the sense of including a copolymer.

The olefin polymerization catalyst according to the present invention is
(A) a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, (B) a transition metal compound represented by the following general formula (I), and (C) (C- 1) at least one selected from organometallic compounds, (C-2) organoaluminumoxy compounds, and (C-3) transition metal compounds (A) or compounds that react with the transition metal compounds (B) to form ion pairs It is formed from a seed compound.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Includes a ligand having a cyclopentadienyl skeleton
Transition metal compound of Group 4 of the periodic table A transition metal compound of Group 4 of the periodic table (A) containing a ligand having a cyclopentadienyl skeleton used in the present invention is
It is a transition metal compound represented by the following general formula (II-1).

M ¹ L _x (II-1) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. is there.

[0019] x is the valence of the transition metal atom M ^1, illustrating a coordinated number of ligands L to the transition metal atom M ^1. L represents a ligand coordinated to a transition metal atom, at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton
Is a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms or hydrogen atoms.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and tetramethylcyclopentadienyl group. 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 (halogenated) hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms and the like.

When the compound represented by the general formula (II-1) contains two or more ligands having a cyclopentadienyl skeleton, a ligand having two cyclopentadienyl skeletons among them Are (substituted) alkylene groups, (substituted)
It may be bound via a divalent linking group such as a silylene group. As a transition metal compound in which such a ligand having two cyclopentadienyl skeletons is bonded via a divalent bonding group, a transition represented by the general formula (II-3) described below is used. Metal compounds may be mentioned.

Specific examples of the ligand L 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 and an aryl group, and more specifically, methyl, ethyl, propyl, butyl and hexyl. , Octyl, nonyl, dodecyl, eicosyl, and other alkyl groups; cyclopentyl, cyclohexyl, norbornyl, adamantyl, and other cycloalkyl groups; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, etc. An aryl group is mentioned.

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

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrocarbon-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl of hydrocarbon-substituted silyl such as trimethylsilyl ether Ethers; silicon-substituted alkyl groups such as trimethylsilylmethyl; 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 a transition metal compound has, for example, a transition metal valence of 4
And more specifically, it is represented by the following general formula (II-2).

R ³¹ R ³² R ³³ R ³⁴ M ¹ (II-2) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table similar to the above, and preferably a zirconium atom. .

R ³¹ represents a group (ligand) having a cyclopentadienyl skeleton, and R ³² , R ³³ and R ³⁴ may be the same or different from each other and are groups having a cyclopentadienyl skeleton. (Ligand), 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, the compound represented by the above general formula (II-2)
In the transition metal compound, R³², R ³³And R³⁴Out of
Group having at least one cyclopentadienyl skeleton
A compound which is a (ligand), eg R³¹And R³²Is
A group (ligand) having a clopentadienyl skeleton
Compounds are preferably used. Also, R³¹And R³²Is
When it is a group (ligand) having a clopentadienyl skeleton
If R³³And R³⁴Has a cyclopentadienyl skeleton
Group, alkyl group, cycloalkyl group, alkenyl group,
Arylalkyl group, aryl group, alkoxy group, ant
-Roxy group, trialkylsilyl group, sulfonate
It is preferably a group, a halogen atom or a hydrogen atom.
Yes.

The following is represented by the general formula (II-1), and M
^A specific compound is illustrated about the transition metal compound whose ¹ is zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) )
Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, Bis (cyclopentadienyl) phenyl zirconium monochloride, Bis (cyclopentadienyl) benzyl zirconium monochloride, Bis (cyclopentadienyl) zirconium monochloride, Bis (Cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium Methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), Bis (cyclopentadienyl) zirconium bis (p-toluene sulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethane sulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclo) Pentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride Chloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),
Bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclo) Pentadienyl) zirconium dichloride and the like.

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

Further, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can also be mentioned. Examples of the transition metal compound in which two ligands having a cyclopentadienyl skeleton are bound via a divalent linking group include compounds represented by the following formula (II-3).

[0033]

[Chemical 4]

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 ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group. Represents a group, a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen atom or a hydrogen atom. R ³⁵ ,
Of the groups represented by R ³⁶ , R ³⁷ and R ³⁸ , some of the groups adjacent to each other may be bonded to each other to form a ring together with the carbon atom to which those groups are bonded. R ³⁵ , R ³⁶ ,
R ³⁷ and R ³⁸ are shown at two positions, but R ³⁵ and R ^{35, for} example, may be the same group or different groups. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group and aryl group as those described above for L.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples thereof 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 above hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. As the oxygen-containing group, a hydroxy group and an alkoxy group similar to the above L,
Examples thereof include aryloxy group and arylalkoxy group.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur. As the silicon-containing group, the same monohydrocarbon-substituted silyl, dihydrocarbon-substituted silyl, trihydrocarbon-substituted silyl as in the above L,
Examples thereof include silyl ethers of hydrocarbon-substituted silyl, silicon-substituted alkyl groups, and silicon-substituted aryl groups.

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Examples of the halogen atom are the same as those described above for L.

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

X ³ and X ⁴ may be the same or different from each other, and are 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 hydrogen atom or a halogen atom is shown.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group and aryl group as those described above for L.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group, an alkoxy group similar to the above L, an aryloxy group, an arylalkoxy group, and the like.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, and the same sulfonate group and sulfinate group as those in L above. Examples of the silicon-containing group include the same silicon-substituted alkyl groups and silicon-substituted aryl groups as those described above for L.

As the halogen atom, the same groups and atoms as the above L can be mentioned. Of 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
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO₂-, -Ge-, -Sn-, -NR³⁹
-, -P (R³⁹)-, -P (O) (R³⁹)-,-BR ³⁹
-Or-AlR³⁹-[However, R³⁹Are identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups 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 and 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Examples include 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 halogenated groups of the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylylene groups such as chlorophenyl) silylene; Alkylarylsilylene groups; Arylsilylene groups; Tetramethyl-1,2-disilirene, tetraphenyl-1,2-disilylene and other alkyldisilylene groups; Alkylaryldisilylene groups; Aryldiyl Examples thereof include a silylene group.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Examples of the divalent tin-containing group include groups obtained by substituting tin for silicon in the divalent silicon-containing group.

R ³⁹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom similar to L. Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene are particularly preferable.

Specific examples of the transition metal compound represented by the general formula (II-3) are shown below. 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-toluene sulfonate), ethylene-bis (indenyl) zirconium bis (p-chlorobenzene sulfonate), ethylene-bis (4,5,6,7-tetrahydroindenyl) ) Zirconium dichloride, isopropylidene-bis (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) Zirconium dichloride, dimethyl silylene
-Bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, Dimethylsilylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylene-bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, dimethylsilylene-bis (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) di Ruconium dichloride, isopropylidene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) 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, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. In the present invention, more specifically, the transition metal compound represented by the formula (II-3) is represented by the following general formula (II
-4) or a transition metal compound represented by (II-5).

[0055]

[Chemical 5]

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
^{41, which} may be the same or different, each represents a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl. , Alkyl groups such as tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl;
Examples thereof include alkenyl groups such as vinyl and propenyl.

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

R ⁴² , R ⁴⁴ , R ⁴⁵ and R ^{46, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ⁴¹ . R ⁴³ may be the same or different from each other, 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, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferable.

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, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
Hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

[0060] X ³ and X ⁴ may be the same or different from each other, X ³ and X ⁴ in the general formula (II-3)
Is the same as. Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.

[0061] Y ¹ is the same as Y ¹ in the general formula (II-3). Of these, a divalent silicon-containing group, a divalent germanium-containing group are preferable, a divalent silicon-containing group is more preferable, and an alkylsilylene, alkylarylsilylene or arylsilylene is more preferable. preferable.

Specific examples of the transition metal compound represented by the above general formula (II-4) are shown below. rac-dimethyl silylene
-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 {1
-(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)} 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- Dimethyl silylene
-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, rac-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-anthryl) 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)} 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-4- (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-dimethyl Silylene-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-dimethyl Silylene-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, rac-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, r
ac-Dimethylsilylene-bis {1- (2-n-pentyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-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, rac-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, rac-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, r
ac-Methylphenylsilylene-bis {1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-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-
Diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} 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)} 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)} 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 and the like.

In addition, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. In the present invention, a racemic transition metal compound represented by the general formula (II-4) is usually used as a catalyst component, but an R type or an S type may be used.

Such a transition metal compound represented by the general formula (II-4) is described in Journal of Organometallic Chem.
985), pages 63-67, European Patent Application Publication No. 0,320,76.
It can be produced according to the specification and Example.

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

[0066]

[Chemical 6]

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
⁵¹ and R ⁵² may be the same or different from each other,
Hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen atom or a hydrogen atom, specifically, R ^{35 to} R
The same atom or group as ³⁸ can be mentioned.

Of these, R ⁵¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group having 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ⁵² has a hydrogen atom or a carbon atom number of 1 to
20 hydrocarbon groups are preferred, and particularly hydrogen atom or methyl, ethyl, propyl having 1 to 10 carbon atoms.
It is preferably a hydrocarbon group of 3.

R ⁵³ and R ^{54, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples thereof include alkyl groups such as isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl and eicosyl; and cycloalkyl groups such as norbornyl and adamantyl.

Of these, R ⁵³ is preferably a secondary or tertiary alkyl group. X ³ and X ⁴ may be the same or different from each other is the same as X ³ and X ⁴ in the general formula (II-3).

[0072] Y ¹ is the same as Y ¹ in the general formula (II-3). Specific examples of the transition metal compound represented by the general formula (II-5) are shown below. rac-dimethyl silylene-
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 {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2,7-dimethyl-4-
sec-Butylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)} zirconium dichloride, rac-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-phenylethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-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, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} 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, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-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 , R
ac-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-dimethylsilyl Ren-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindene) Nyl)} 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-chloromethylindenyl)} 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-diphenylsilylene-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-bis {1
-(2,3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propyl) Indenyl)} 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, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methyl Indenyl)} zirconium-bis (methanesulfonate), 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, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. Among these, i-propyl and sec- in the 4th position
Those having a branched alkyl group such as a butyl or tert-butyl group are particularly preferable.

In the present invention, the racemate of the transition metal compound represented by the general formula (II-5) is usually used as the catalyst component, but R type or S type can also be used. The transition metal compound represented by the general formula (II-5) as described above is
A known method from an indene derivative, for example, JP-A-4-26
It can be synthesized by the method described in Japanese Patent No. 8307.

Further, in the present invention, a compound represented by the following formula (III-1) can be used as the transition metal compound (A) of Group 4 of the periodic table. L ² M ¹ X ⁵ ₂ (III-1) In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table.

L ² is a derivative of a delocalized π-bonding group, which imparts a constrained geometry to the metal M ¹ active site, and X ^{5 s} may be the same or different from each other, a hydrogen atom, A hydrocarbon group, a silyl group or a germyl group containing a halogen atom or 20 or less carbon atoms, a silicon atom or a germanium atom.

Among the compounds represented by the general formula (III-1), the compound represented by the following formula (III-2) is preferable.

[0078]

[Chemical 7]

In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. Cp is
A substituted cyclopentadienyl group or a derivative thereof which is π-bonded to M ¹ and has a substituent Z is shown.

Z¹Is an oxygen atom, sulfur atom, boron atom
A child or a ligand containing an element of Group 14 of the periodic table
For example -Si (R⁵⁵ ₂)-, -C (R⁵⁵ ₂)-, -Si
(R⁵⁵ ₂) Si (R⁵⁵ ₂)-, -C (R⁵⁵ ₂) C (R⁵⁵ ₂)
-, -C (R⁵⁵ ₂) C (R⁵⁵ ₂) C (R⁵⁵ ₂)-, -C
(R⁵⁵) = C (R⁵⁵)-, -C (R⁵⁵ ₂) Si (R⁵⁵ ₂)
-, -Ge (R⁵⁵ ₂)-And so on.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, --N (R
⁵² )-, -O-, ^-S- , -P ( ^R52 )-and the like.
Further, Z ¹ and Y ² may form a condensed ring.

R ⁵⁵ is a hydrogen atom or a group selected from alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups and combinations thereof having up to 20 non-hydrogen atoms, and R ⁵² is a carbon atom. Alkyl having 1 to 10 atoms, aryl group having 6 to 10 carbon atoms or aralkyl group having 7 to 10 carbon atoms, or condensation of one or more R ⁵⁵ and up to 30 non-hydrogen atoms. It may form a ring system.

The transition represented by the above general formula (III-2) is shown below.
Specific examples of the metal transfer compound will be shown. (Tert-butylami
De) (Tetramethyl-η^Five-Cyclopentadienyl) -1,2-
Ethanediyl zirconium dichloride, (tert-butyl
Amide) (Tetramethyl-η ^Five-Cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (methylamide)
(Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethane
N-diylzirconium dichloride, (methylamide)
(Tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethane
N-diyl titanium dichloride, (ethylamide) (tetra
Methyl-η^Five-Cyclopentadienyl) -methylene titanium di
Chloride, (tert-butylamido) dimethyl (tetrame
Chill-η^Five-Cyclopentadienyl) silane titanium dichloride
Lido, (tert-butylamido) dimethyl (tetramethyl-
η^Five-Cyclopentadienyl) silane zirconium dichloride
Lido, (benzylamido) dimethyl- (tetramethyl-η
^Five-Cyclopentadienyl) silane titanium dichloride,
(Phenylphosphide) dimethyl (tetramethyl-η^Five-
Cyclopentadienyl) silane zirconium dibenzyl
Such.

The transition metal compound (A) as described above is 1
They may be used alone or in combination of two or more. (B) Transition Metal Compound The (B) transition metal compound used in the present invention is a compound represented by the following general formula (I).

[0085]

[Chemical 8]

(Note that N ... M generally indicates coordination, but in the present invention, it may or may not coordinate.) In the general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (group 3 also includes lanthanoids), preferably a metal atom of groups 3 to 9 (group 3 also includes lanthanoids), and more preferably Is a metal atom of Groups 3 to 5 and 9 and particularly preferably a metal atom of Group 4 or Group 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium and the like, more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like are preferable, and titanium, zirconium and hafnium are particularly preferable.

M represents an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, of which 2
One or more may be linked to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like having 1 to 30 carbon atoms, preferably 1-20 linear or branched alkyl groups; vinyl, allyl, isopropenyl, etc., having 2 carbon atoms
30, preferably 2 to 20 straight or branched alkenyl groups; ethynyl, propargyl, etc., having 2 carbon atoms
-30, preferably 2-20, straight-chain or branched alkynyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc., having 3-30, preferably 3-20, cyclic saturated hydrocarbon groups. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl,
6 carbon atoms such as phenanthryl and anthracenyl
To 30, preferably 6 to 20 aryl groups; tolyl, is
Examples thereof include alkyl-substituted aryl groups such as o-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl.

In the above hydrocarbon group, the hydrogen atom may be substituted with halogen, and for example, trifluoromethyl, pentafluorophenyl, chlorophenyl or the like having 1 to 30 carbon atoms, preferably 1 to 20 halogenated carbon atoms. A hydrogen group is mentioned.

The above hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic acid anhydride groups; amino groups, imino groups, amide groups, imide groups,
Hydrazino group, hydrazono group, nitro group, nitroso group,
Nitrogen-containing groups such as cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups converted to ammonium salts; boron-containing groups such as boranediyl groups, boranetriyl groups, and diboranyl groups; mercapto groups,
Thioester group, dithioester group, alkylthio group,
Arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothiocyanate ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group,
Sulfur-containing groups such as sulfinyl group and sulfenyl group;
It may have a phosphorus-containing group such as a phosphido group, a phosphoryl group, a thiophosphoryl group, and a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, in particular, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as butyl, t-butyl, neopentyl, n-hexyl; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; Preferably, 6 to 20 substituents such as aryl group or aryloxy group are 1 to 5
Substituted aryl groups that are individually substituted are preferred.

An oxygen-containing group, a nitrogen-containing group, a boron-containing group,
Examples of the sulfur-containing group and phosphorus-containing group include the same as those exemplified above. Examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include groups in which the number of carbon atoms is 1 to 30, preferably 1 to 20 and further substituted with a substituent such as an alkyl group and an alkoxy group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and the like, specifically, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethyl. Examples thereof include silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl (pentafluorophenyl) silyl. Of these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the germanium-containing group and the tin-containing group include those in which silicon in the silicon-containing group is replaced with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy, and aryloxy groups include phenoxy and 2,6-dimethylphenoxy. , 2,4,6-trimethylphenoxy, etc., the acyl groups include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, etc., and the ester groups include acetyloxy, benzoyl group. Preferred examples include oxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Among the nitrogen-containing groups, amide groups include acetamide, N-methylacetamide, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include: Preferred examples of the imino group include acetoimide and benzimide, and methylimino, ethylimino, propylimino, butylimino, phenylimino, and the like.

Among the sulfur-containing groups, the alkylthio group is methylthio, ethylthio, etc., the arylthio group is phenylthio, methylphenylthio, nartylthio, etc., and the thioester group is acetylthio, benzoylthio, methylthiocarbonyl, phenylthio. Carbonyl and the like, sulfone ester groups such as methyl sulfonate, ethyl sulfonate, and phenyl sulfonate, and sulfonamide groups such as phenyl sulfonamide, N-methyl sulfonamide, N-methyl-p-toluene sulfonamide. Are preferred.

R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. Particularly, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. It is preferably a group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and further a halogen atom, a hydrocarbon group or a hydrocarbon-substituted silyl group. Preferably there is.

Preferred hydrocarbon groups for R ⁶ are:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc., having 1 to 30 carbon atoms, preferably 1 to 20 straight or branched -Like alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc., having 3 to 30 carbon atoms, preferably 3 to 20 cyclic saturated hydrocarbon groups; carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, triphenylyl, etc. An aryl group having a number of 6 to 30, preferably 6 to 20; and an alkyl group or an alkoxy group having a carbon number of 1 to 30, preferably 1 to 20, a carbon atom number of 1 to 30, preferably Is a halogenated alkyl group of 1 to 20 and has 6 to 30 carbon atoms, preferably 6 to 2
Preferred examples thereof include aryl groups of 0 or aryloxy groups, halogens, cyano groups, nitro groups, hydroxy groups, and other groups further substituted.

Preferred hydrocarbon-substituted silyl groups for R ⁶ are methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Examples include dimethyl (pentafluorophenyl) silyl. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ has 3 to 30 carbon atoms, preferably 3 to 2 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl.
0 branched alkyl groups, and groups in which hydrogen atoms of these groups are substituted with aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as cumyl group, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, Number of carbon atoms such as cyclohexyl is 3 to 30, preferably 3 to 2
It is preferably a group selected from cyclic saturated hydrocarbon groups of 0, or phenyl, naphthyl, fluorenyl,
6 to 3 carbon atoms such as anthranil and phenanthryl
It is also preferably 0, preferably 6-20 aryl groups, or hydrocarbon-substituted silyl groups.

R ^{1 to} R ⁶ are two or more of these groups, preferably adjacent groups connected to each other to form an alicyclic ring, an aromatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, R ^{1 to} R ⁶
Two of the groups represented by may be linked.
Further, when m is 2 or more, R ^1's , R ^2's , R
³ groups, R ⁴ groups, R ⁵ groups, and R ⁶ groups may be the same or different.

N is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, and more preferably 1 to 3.
Is an integer. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing group. Represents a group, a germanium-containing group, or a tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, the above R
^The same as those exemplified for ^{1 to} R ⁶ can be mentioned. Specifically, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; a cycloalkyl group having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,
Examples thereof include aryl groups such as methylnaphthyl, anthryl, and phenanthryl, but are not limited thereto. Further, these hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is replaced with halogen.

Of these, those having 1 to 20 carbon atoms are preferable. The heterocyclic compound residue may be the above R
^The same as those exemplified for ^{1 to} R ⁶ can be mentioned.

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples thereof include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; phenoxy and methyl. Aryloxy groups such as phenoxy, dimethylphenoxy and naphthoxy;
Examples thereof include arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like, but are not limited thereto.

Examples of the sulfur-containing group are the same as those exemplified above for R ^{1 to} R ⁶ , and specific examples thereof include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate and benzyl sulfonate. Sulfonate groups such as phonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methylsulfinate, phenylsulfinate Sulfonate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups; alkylthio groups; arylthio groups and the like, but are not limited thereto. .

Specific examples of the nitrogen-containing group include R ¹ to
Examples thereof include those similar to those exemplified for R ⁶ , specifically, amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino. , An arylamino group such as ditolylamino, dinaphthylamino, and methylphenylamino, or an alkylarylamino group, and the like.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triphenylphosphine,
Examples include, but are not limited to, triarylphosphine groups such as tritolylphosphine; phosphite groups (phosphide groups) such as methylphosphite, ethylphosphite, and phenylphosphite; phosphonic acid groups; phosphinic acid groups. is not.

Specific examples of the silicon-containing group include R ¹
To R ⁶ are exemplified, and specific examples thereof include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl and tritolylsilyl. A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; and a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include groups in which silicon in the silicon-containing group is substituted with germanium. .

Specific examples of the tin-containing group include R ¹ to
Examples thereof are the same as those exemplified for R ⁶ , and more specifically, a group obtained by substituting tin for silicon in the silicon-containing group is exemplified.

Specific examples of the halogen-containing group include P
Examples thereof include, but are not limited to, fluorine-containing groups such as F ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .

Specifically as the aluminum-containing group, A
1R ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but is not limited thereto.

When n is 2 or more, the plural groups represented by X may be the same or different from each other, and X is
A plurality of groups represented by may combine with each other to form a ring. Transition Metal Compound (Ia) As the transition metal compound represented by the general formula (I), there is a compound represented by the following general formula (Ia).

[0117]

[Chemical 9]

(In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , and R ^{1 to} R ⁶
May be the same or different from each other, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group. Group, a germanium-containing group, or a tin-containing group, two or more of them may be linked to each other to form a ring, and when m is 2 or more, R ^{1 to} R ⁶ are Two of the groups shown may be linked (provided that R ^{1 s} are not bonded to each other), n is a number satisfying the valence of M, X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or, it represents a tin-containing group, and n is 2 or more. In the above case, the groups represented by X may be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring. In the formula (Ia), M, m, R ^{1 to} R ⁶ , n and X have the same meaning as in the formula (I).

In the transition metal compound represented by the general formula (I), m is 2 and two groups (except R ^{1 s} ) of the groups represented by R ^{1 to} R ⁶ are linked. The compound described is, for example, a compound represented by the following general formula (Ia ').

[0120]

[Chemical 10]

In the formula (I-a '), M, R ^{1 to} R ⁶ and X are the same as those in the general formula (Ia-1), and R ¹¹
To R ¹⁶ are the same as R ^{1 to} R ⁶ . The following groups are particularly preferable.

R ^{1 to} R ¹⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, or a sulfur-containing group. A group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group or the like is shown, and specifically, the same atom or group as R ^{1 to} R ⁶ is shown. R ¹ ~R ^{1 6}
Two or more of these groups, preferably adjacent groups, may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom.

Y'bonds at least one group selected from R ^{1 to} R ⁶ and at least one group selected from R ^{11 to} R ¹⁶ (provided that R ¹ and R ¹¹ Except when is bonded.) A bonding group or a single bond.

Examples of the bonding group represented by Y'include a group containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. the -O -, - S -, - chalcogen atom-containing groups such as Se-; -NH -, - N ( CH 3) 2 -, -
_{PH -, - P (CH 3} ) 2 - a nitrogen or phosphorus atom-containing groups such _{as; -CH 2 -, - CH 2} -CH 2 -, - C (CH 3)
_2-, etc., hydrocarbon group having 1 to 20 carbon atoms; benzene, naphthalene, anthracene, etc., having 6 to 20 carbon atoms
20 cyclic unsaturated hydrocarbon residues; pyridine, quinoline,
Heterocyclic compound residue having 3 to 20 carbon atoms including a hetero atom such as thiophene and furan; -SiH ₂ -,-
Si (CH _{3) 2} - silicon atom-containing group such as, -SnH
_{2 -, - Sn (CH 3} ) 2 - tin atom-containing groups such as; -BH
Examples thereof include boron atom-containing groups such as —, —B (CH ₃ ) —, and —BF—, or a single bond.

Specific examples of the transition metal compound represented by the above general formula (Ia ') are shown below, but the invention is not limited thereto. In the following specific examples, M is a transition metal element, and Sc (III), Ti (III), T
i (IV), Zr (III), Zr (IV), Hf (IV), V (IV), N
b (V), Ta (V), Co (II), Co (III), Rh (II),
Rh (III) and Rh (IV) are shown, but not limited thereto. Among these, particularly Ti (IV), Zr
(IV) and Hf (IV) are preferred.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different.

N is determined by the valence of the metal M. For example, when two monoanion species are bound to a metal,
For divalent metals, n = 0, for trivalent metals n = 1, for tetravalent metals n = 2, for pentavalent metals n = 3. For example, n = 2 when the metal is Ti (IV), n = 2 when Zr (IV), and n = 2 when Hf (IV).

[0128]

[Chemical 11]

[0129]

[Chemical 12]

[0130]

[Chemical 13]

[0131]

[Chemical 14]

[0132]

[Chemical 15]

[0133]

[Chemical 16]

[0134]

[Chemical 17]

[0135]

[Chemical 18]

[0136]

[Chemical 19]

[0137]

[Chemical 20]

[0138]

[Chemical 21]

[0139]

[Chemical formula 22]

[0140]

[Chemical formula 23]

[0141]

[Chemical formula 24]

[0142]

[Chemical 25]

[0143]

[Chemical formula 26]

[0144]

[Chemical 27]

[0145]

[Chemical 28]

[0146]

[Chemical 29]

[0147]

[Chemical 30]

In the above example, Me is a methyl group, Et
Represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group. Further specific examples of the case where Ti is the central metal include the following. Further, compounds in which titanium is replaced with zirconium, hafnium, cobalt or rhodium in these compounds are also included.

[0149]

[Chemical 31]

[0150]

[Chemical 32]

[0151]

[Chemical 33]

[0152]

[Chemical 34]

[0153]

[Chemical 35]

[0154]

[Chemical 36]

[0155]

[Chemical 37]

[0156]

[Chemical 38]

[0157]

[Chemical Formula 39]

[0158]

[Chemical 40]

[0159]

[Chemical 41]

The transition metal compound (B) represented by the general formula (I) includes a transition metal compound represented by the following general formula (Ib).

[0161]

[Chemical 42]

(In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, R ^{1 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group or a hetero group. A cyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which are mutually They may be linked to each other to form a ring, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, Represents a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, is represented by X. Multiple groups may be the same or different It may have I, and a plurality of groups represented by X may be bonded to each other to form a ring, Y
Is oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium,
A divalent linking group containing at least one element selected from the group consisting of tin and boron is shown, and when it is a hydrocarbon group, it is a group consisting of 3 or more carbon atoms.

In the general formula (Ib), at least one of R ^{6 and} R ¹⁰ , especially both of them are a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It is preferably a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

In the general formula (Ib), as M, R ^{1 to} R ¹⁰ and X, the same groups as M, R ^{1 to} R ⁶ and X mentioned for the compound of the general formula (I) can be used.
As X, a halogen atom and a carbon atom number of 1 to 2 are particularly preferable.
Zero hydrocarbon or sulfonate groups are preferred. When n is 2 or more, the ring formed by connecting two or more X's to each other may be an aromatic ring or an aliphatic ring.

Y represents a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron, and is a hydrocarbon group. In some cases, it is a linking group consisting of 3 or more carbon atoms.

The bonding group Y preferably has a structure in which the main chain has 3 or more atoms, more preferably 4 or more and 20 or less atoms, and particularly preferably 4 or more and 10 or less atoms. In addition, these bonding groups may have a substituent.

Specifically as the divalent linking group (Y),-
Chalcogen atoms such as O-, -S-, and -Se-; -NH
_{-, - N (CH 3)} -, - PH -, - P (CH 3) - nitrogen or phosphorus atom-containing groups such _{as; -SiH 2 -, - Si (} C
H _{3) 2} - silicon atom-containing groups such as; -SnH ₂ -, - Sn
(CH _{3) 2} - tin atom-containing groups such as; -BH -, - B
(CH ₃₎ -, - BF- like boron atom-containing groups such as. The hydrocarbon group _{- (CH 2) 4 -,} - (C
Saturated hydrocarbon groups having 3 to 20 carbon atoms such as H ₂ ) ₅ —, — (CH ₂ ) ₆ —, cyclic saturated hydrocarbon groups such as cyclohexylidene group, cyclohexylene group, and saturated hydrocarbon groups thereof. A part of 1 to 10 hydrocarbon groups, fluorine, chlorine,
Residues of halogen such as bromine, groups substituted with heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin and boron, and benzene, naphthalene and anthracene having 6 to 20 carbon atoms. Examples thereof include a residue of a cyclic compound having 3 to 20 carbon atoms containing a hetero atom such as a group, pyridine, quinoline, thiophene, and furan.

Specific examples of the transition metal compound represented by the above general formula (Ib) are shown below, but the invention is not limited thereto.

[0169]

[Chemical 43]

[0170]

[Chemical 44]

In the above examples, Me represents a methyl group and Ph represents a phenyl group. In the present invention, a transition metal compound in which titanium metal is replaced with a metal other than titanium such as zirconium or hafnium in the above compounds can also be used.

The method for producing such a transition metal compound (B) is not particularly limited and can be produced, for example, as follows.

First, as the ligand constituting the transition metal compound (B), a salicylaldehyde compound is represented by the formula R ¹ -NH
Primary amines compound of ₂ (R ¹ is as defined above.), Obtained for example by reacting with aniline compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such reactions can be used, but among them, alcohol solvents such as methanol and ethanol, or hydrocarbon solvents such as toluene are preferable. Then, the obtained solution is stirred at room temperature to reflux conditions for about 1 to 48 hours to obtain the corresponding ligand in good yield.

As a catalyst when synthesizing a ligand compound,
An acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used. In addition, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent or dehydration is performed by Dean Stark, it is effective for the reaction progress.

Next, by reacting the ligand thus obtained with a transition metal M-containing compound, a corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand is dissolved in a solvent and, if necessary, brought into contact with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylated compound at a low temperature. , -78
Stir for about 1 to 48 hours under the conditions of ℃ to room temperature or reflux. As the solvent, those commonly used in such a reaction can be used, but among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. The base used when preparing the phenoxide salt is preferably a lithium salt such as n-butyllithium, a metal salt such as sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. Not as long.

Depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt.

Further, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

The transition metal compound (B) as described above is 1
They may be used alone or in combination of two or more. Also,
It is also possible to use it in combination with a transition metal compound other than the above transition metal compound (B), for example, a known transition metal compound composed of a ligand containing a hetero atom such as nitrogen, oxygen, sulfur, boron or phosphorus.

In addition to the above transition metal compound (A) and transition metal compound (B), a titanium catalyst component containing magnesium, titanium and halogen as essential components can be used.

Other Transition Metal Compounds As transition metal compounds other than the above transition metal compound (A) and transition metal compound (B), the following transition metal compounds can be specifically used. is not. (b-1) transition metal imide compound represented by the following formula (Ic)

[0181]

[Chemical formula 45]

In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, preferably nickel, palladium or platinum. R ^{21 to} R ²⁴ may be the same or different from each other, and are a hydrocarbon group having 1 to 50 carbon atoms and 1 to 5 carbon atoms.
A halogenated hydrocarbon group of 0, a hydrocarbon-substituted silyl group or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon is shown.

Two or more of these groups represented by R ^{21 to} R ²⁴ , preferably adjacent groups, may be linked to each other to form a ring. q shows the integer of 0-4.

X is 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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Is a group, and when q is 2 or more,
The plurality of groups represented by X may be the same as or different from each other. (b-2) transition metal amide compound represented by the following formula (Id)

[0185]

[Chemical formula 46]

In the formula, M represents a transition metal atom of Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium. R ′ and R ″ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen. Represents a substituent having at least one element selected from oxygen, phosphorus, sulfur and silicon.

M is an integer of 0-2. n is 1 to 5
Is an integer. A represents an atom of Group 13 to 16 of the periodic table, specifically, boron, carbon, nitrogen, oxygen, silicon,
Examples thereof include phosphorus, sulfur, germanium, selenium, and tin, and carbon or silicon is preferable. When n is 2 or more, the plurality of A may be the same or different from each other.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two E's may be the same or different from each other,
Alternatively, they may be linked to each other to form a ring.

P is an integer of 0-4. X is 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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Indicates. When p is 2 or more, the plurality of groups represented by X may be the same or different. Of these, X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group. (b-3) a transition metal diphenoxy compound represented by the following formula (I-
e)

[0190]

[Chemical 47]

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, and A and A ′ are hydrocarbon groups having 1 to 50 carbon atoms. A halogenated hydrocarbon having 1 to 50 carbon atoms, or a hydrocarbon group having a substituent containing oxygen, sulfur or silicon, or a halogenated hydrocarbon group having 1 to 50 carbon atoms, wherein A and A 'May be the same or different.

B is a hydrocarbon group having 0 to 50 carbon atoms,
Halogenated hydrocarbon group having 1 to 50 carbon atoms, R ¹ R ² Z
Is a group represented by or oxygen or sulfur, wherein R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having 1 to 20 carbon atoms and containing at least one hetero atom. And Z represents carbon, nitrogen, sulfur, phosphorus or silicon.

N is a number satisfying the valence of M. X is
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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, and n is In the case of two or more, the plural groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring. (b-4) Transition metal compound (If) containing a ligand having a cyclopentadienyl skeleton containing at least one hetero atom represented by the following formula

[0194]

[Chemical 48]

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table. X represents an atom of Group 13, 14 or 15 of the periodic table, and at least one of X is an element other than carbon.

A represents 0 or 1. R's may be the same or different from each other, and are a hydrogen atom, a halogen atom,
A hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon group-substituted silyl group, or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon, 2 More than one R may be linked to each other to form a ring.

B is an integer of 1 to 4, and when b is 2 or more, the respective [((R) _a ) ₅ -X ₅ ] groups may be the same or different, and R is crosslinked. May be. c
Is a number that satisfies the valence of M.

Y is 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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Indicates a group.

When c is 2 or more, the plurality of groups represented by Y may be the same or different from each other, and the plurality of groups represented by Y may be bonded to each other to form a ring. (b-5) a transition metal compound represented by the formula RB (Pz) ₃ MX _n , wherein M represents a transition metal compound of Group 3 to 11 of the periodic table,
R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and P
z represents a pyrazoyl group or a substituted pyrazoyl group.

N is a number satisfying the valence of M. X is
It represents 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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When n is 2 or more, the plural groups represented by X may be the same as or different from each other, or may be bonded to each other to form a ring. (b-6) transition metal compound represented by the following formula (Ig)

[0201]

[Chemical 49]

In the formula, Y ₁ and Y _{3, which} may be the same or different, are elements of Group 15 of the periodic table and Y ₂ is an element of Group 16 of the periodic table. R ²¹ ~ R
²⁸ may be the same or different from each other, 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, an oxygen-containing group,
It represents a sulfur-containing group or a silicon-containing group, and two or more of these may be linked to each other to form a ring. (b-7) Compound represented by the following formula (Ih) and Periodic Table Nos. 8 to 1
Compounds with Group 0 transition metal atoms

[0203]

[Chemical 50]

In the formula, R ^{31 to} R ^{34, which} may be the same or different from each other, are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 20 carbon atoms. It is a group, and two or more of these may be linked to each other to form a ring. (b-8) transition metal compound represented by the following formula (Ii)

[0205]

[Chemical 51]

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m is an integer of 0 to 3, n is an integer of 0 or 1, and p is 1 to 1. Is an integer of 3 and q
Is a number that satisfies the valence of M.

R ^{41 to} R ^{48, which} may be the same or different, are each a hydrogen atom, a halogen atom, or a carbon atom having 1 to 2 carbon atoms.
A hydrocarbon group of 0, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, two or more of which are linked to each other to form a ring. May be formed.

X is 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, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Represents a group, and when q is 2 or more, X
The plurality of groups represented by may be the same or different from each other, or the plurality of groups represented by X may be bonded to each other to form a ring.

Y is a group for bridging the boratabenzene ring and represents carbon, silicon or germanium. A is
The elements of Group 14, 15 or 16 of the periodic table are shown.

(C-1) Organometallic Compound As the (C-1) organometallic compound used in the present invention, specifically, the following periodic table groups 1, 2 and 12, 1
Group 3 organometallic compounds are used.

[0211] (C-1a) of 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 is a halogen atom, and m is 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q
<3, and m + n + p + q = 3. ) An organoaluminum compound represented by.

(C-1b) General formula M ² AlR ^a ₄ (In the formula, M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a metal of Group 1 of the periodic table and aluminum.

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

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

Specific examples of the organoaluminum compound belonging to (C-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Such as tri-n-alkyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-methylbutyl aluminum, tri 2-methylpentyl aluminum, tri 3-methylpentyl aluminum, tri 4-methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl Aluminum, tri-branched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; (i-C ₄ H ₉ ) _x
Trialkenylaluminum such as triisoprenylaluminum represented by Al _y (C ₅ H ₁₀ ) _z (wherein x, y, and z are positive numbers and z ≧ 2x); isobutylaluminum methoxy Alkyl aluminum alkoxides such as isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyls such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide Aluminum sesquialkoxide; ^Ra
_2.5 Partially alkoxylated alkyl aluminum having an average composition represented by Al (OR ^b ) _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl Aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-
Dialkyl aluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; Partial alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Halogenated alkyl aluminum; diethyl aluminum hydride Dialkyl aluminum hydrides such as dibutyl aluminum hydride; other aluminum aluminum hydrides such as ethyl aluminum dihydride and propyl aluminum dihydride, and other partially hydrogenated alkyl aluminums; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum Mention may be made of partially alkoxylated and halogenated alkylaluminums such as ethoxy bromide.

A compound similar to (C-1a) can also be used, and examples thereof include an organoaluminum 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) can be exemplified ₂ and the like.

Examples of the compound belonging to (C-1b) above include Li
_{Al (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like. In addition, (C-1) organometallic compounds include 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. It is also possible to use chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like.

It is also possible to use a compound capable of forming the above organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium.

Of the organometallic compounds (C-1), organoaluminum compounds are preferred. The above (C-1) organometallic compounds may be used alone or in combination of two or more.

(C-2) Organoaluminum Oxy Compound The (C-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. Such a benzene-insoluble organoaluminum oxy compound may be used.

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

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

Specific examples of the organoaluminum compound used when preparing the aluminoxane include the above-mentioned (C-1a)
The same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds may be used alone or in combination of two or more.

The solvent used for the preparation of the aluminoxane includes aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Some are preferred, that is, those that are insoluble or sparingly soluble in benzene.

Examples of the organoaluminum oxy compound used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (IV).

[0228]

[Chemical 52]

In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁸ may be the same as or different from each other, and each has a hydrogen atom, a halogen atom, and a carbon atom number of 1 to 10.
Shows a hydrocarbon group of.

The organoaluminum oxy compound containing boron represented by the general formula (IV) has the following general formula (V):
An alkylboronic acid represented by R ¹⁷ -B- (OH) ₂ (V) (wherein R ¹⁷ represents the same group as described above) and an organoaluminum compound, and they are inert under an inert gas atmosphere. In a solvent,
It can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

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

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the above-mentioned (C-1a)
The same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to can be mentioned.

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

The above-mentioned (C-2) organoaluminum oxy compound may be used alone or in combination of two or more kinds. (C-3) Reaction to form an ion pair by reacting with a transition metal compound
Transition metal compounds used in the compound (A) of the invention or the transition metal compound (B) reacts with to form an ion pair compound (C
-3) (hereinafter, referred to as "ionized ionic compound") are described in JP-A-1-501950 and JP-A-1-5.
No. 02036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, and Japanese Patent Application Laid-Open No. 3-207703.
Japanese Patent Laid-Open No. 3-207704, USP-53
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in No. 21106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

Examples of the ionic compound include compounds represented by the following general formula (VI).

[0237]

[Chemical 53]

In the formula, examples of R ¹⁹ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{20 to} R ^{23, which} may be the same or different from each other, are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations.

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-dimethylaniline. Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Can be mentioned.

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

R ¹⁹ is preferably a carbonium cation, an ammonium cation or the like, particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

As the ionic compound, trialkyl-substituted ammonium salt, N, N-dialkylanilinium salt,
A dialkyl ammonium salt, a triaryl phosphonium salt, etc. can also be mentioned.

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

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron.

Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
Other examples include N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (VII) or (VIII), and the like.

[0248]

[Chemical 54]

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

[0250]

[Chemical 55]

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium]. ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Butyl) ammonium] dodecachlorododecaborate and other anion salts; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecarate) Examples thereof include salts of metal borane anions such as borate) nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodeca hydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,
7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarbaundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodeca hydride-8-
Methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarbaundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undeca hydride-7-
Examples thereof include salts of metal carborane anions such as carbaundecaborate) nickelate (IV).

The heteropoly compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin,
It is composed of one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorous Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdo Tungstic acid, phosphomolybdo niobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium. ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.

The above (C-3) ionized ionic compound may be used alone or in combination of two or more. When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (C-2) such as methylaluminoxane as a co-catalyst component, it exhibits a very high polymerization activity for olefin compounds. When an ionizable ionic compound (C-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a co-catalyst component, an olefin polymer having excellent activity and a very high molecular weight can be obtained.

Further, the olefin polymerization catalyst according to the present invention comprises the above-mentioned transition metal compound (A), transition metal compound (B), (C-1) organometallic compound, (C-2) organoaluminum oxy compound, and (C-3) together with at least one compound (C) selected from ionized ionic compounds,
If necessary, the carrier (D) as described below can be used.

(D) Carrier The carrier (D) used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid.

Of these, the inorganic compound is preferably a porous oxide, an inorganic chloride, clay, a clay mineral or an ion-exchange layered compound. Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , and B.
₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or a mixture or mixture containing these is used, for example natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -C
r ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. can be used. Of these, SiO ₂ and / or Al ₂ O
Those containing ₃ as a main component are preferable.

The above inorganic oxide is 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 ,
Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxides may be contained.

The properties of such a porous oxide differ depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20.
˜200 μm and specific surface area of 50˜1000 m ²
/ G, preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 3.0 cm ³ / g. Such a carrier may be used as needed.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

As the inorganic chloride, MgCl ₂ , MgB
r ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is, or may be used after being crushed by a ball mill or a vibration mill. Further, it is also possible to use the one obtained by dissolving the inorganic chloride in a solvent such as alcohol and then depositing it in the form of fine particles with a depositing agent.

The clay used in the present invention is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. . Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally occurring compounds, and artificial synthetic products can also be used.

As the clay, clay mineral or ion-exchange layered compound, clay, clay mineral, or ionic crystallinity having a layered crystal structure of hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. A compound etc. can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrrome clay, allophane, hisingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, Nacrite, dickite, halloysite, etc. may be mentioned, and the ion-exchange layered compound is α-Zr (HAsO ₄ ) ₂ · H.
_{2 O, α-Zr (HPO} 4) 2, α-Zr (KPO 4) 2 · 3H 2
O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂
O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂
Examples thereof include crystalline acid salts of polyvalent metals such as H ₂ O.

Such clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by mercury porosimetry.
Those of 0.3 to 5 cc / g are particularly preferable. Here, the pore volume is measured in a pore radius range of 20 to ³ × 10 ⁴ Å by a mercury porosimetry method using a mercury porosimeter.

[0265] The pore volume with a radius of 20 Å or more is 0.1 cc /
When a carrier having a particle size smaller than g is used as the carrier, it tends to be difficult to obtain high polymerization activity. It is also preferable to chemically treat the clay and clay mineral used in the present invention.
As chemical treatment, surface treatment to remove impurities adhering to the surface, treatment that affects the crystal structure of clay, etc.
Either can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment not only removes impurities on the surface but also increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. Alkali treatment destroys the crystal structure of clay, resulting in a change in clay structure.
Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

The ion-exchangeable layered compound used in the present invention is a layered compound in which the interlayer is enlarged by utilizing the ion-exchange property and exchanging the interlayer exchangeable ion with another large bulky ion. May be. Such bulky ions play a pillar-like role for supporting the layered structure, and are usually called pillars. Further, such introduction of another substance between the layers of the layered compound is called intercalation. As the guest compound to be intercalated, a cationic inorganic compound such as TiCl ₄ , ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
Metal alkoxides such as B (OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ ,
Examples thereof include metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. Moreover, when intercalating these compounds, Si (OR) ₄ , Al (O
Polymers obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group etc.) such as R) ₃ and Ge (OR) _4, etc., SiO ₂
It is also possible to coexist with a colloidal inorganic compound such as. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after treatment such as ball milling and sieving. Further, it may be used after newly adsorbing water or adsorbing water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

Of these, preferred are clays and clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
A granular or fine particle solid in the range of μm can be mentioned. Specifically, ethylene, propylene, 1-
Number of carbon atoms such as butene and 4-methyl-1-pentene is 2
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers or vinylcyclohexane, (co) polymers produced by using styrene as a main component, and modified products thereof.

The olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A), transition metal compound (B), (C-
1) at least one compound (C) selected from an organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3) an ionized ionic compound, if necessary, together with a carrier (D). Accordingly, a specific organic compound component (E) as described later can be included.

(E) Organic Compound Component In the present invention, the (E) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such an organic compound include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

As the alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used,
Here, R ³¹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As alcohols, those in which R ³¹ is a halogenated hydrocarbon are preferable. Further, the phenolic compound is preferably one in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms.

The carboxylic acid is usually R³²-COO
What is represented by H is used. R ³²Is 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A hydrocarbon group, especially halo having 1 to 50 carbon atoms.
A genated hydrocarbon group is preferred.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, phosphate having a P═O bond, and phosphine oxide compounds are preferably used.
As the sulfonate, those represented by the following general formula (IX) are used.

[0276]

[Chemical 56]

In the formula, M is an element of Groups 1 to 14 of the periodic table. R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n
Is 1 ≦ n ≦ 7.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. At the time of polymerization, the usage of each component,
The order of addition is arbitrarily selected, but the following method is exemplified. (1) A method of adding the component (A), the component (B) and the component (C) to the polymerization vessel in any order. (2) A method of adding the catalyst component in which the component (A) is supported on the carrier (D), the component (B) and the component (C) to the polymerization vessel in any order. (3) A method of adding the catalyst component in which the component (B) is carried on the carrier (D), the component (A) and the component (C) to the polymerization vessel in any order. (4) A method of adding the catalyst component in which the component (C) is carried on the carrier (D), the component (A) and the component (B) to the polymerization vessel in any order. (5) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (D) and the component (C) are added to the polymerization vessel in any order. (6) A method of adding a catalyst component in which the component (A) is supported on the carrier (D), a catalyst component in which the component (B) is supported on the carrier (D), and the component (C) to the polymerization vessel in any order. (7) A method in which the catalyst component in which the component (A) and the component (C) are supported on the carrier (D) and the component (B) are added to the polymerization vessel in any order. (8) A method of adding a catalyst component in which components (B) and (C) are supported on a carrier (D), and component (A) to a polymerization vessel in any order. (9) A method of adding a catalyst component in which a component (A), a component (B) and a component (C) are supported on a carrier (D) to a polymerization vessel.

In each of the above methods (1) to (8), at least two or more catalyst components may be contacted in advance. In each of the above methods (4), (7), (8) and (9) in which the component (C) is supported, the unsupported component (C) may be added in any order if necessary. Good. In this case, the component (C) may be the same or different.

Further, the solid catalyst component in which the component (A) and the component (C) are supported on the above component (D), and the solid catalyst component in which the component (B) and the component (C) are supported on the component (D). The solid catalyst component in which the component (A), the component (B) and the component (C) are supported on the component (D) may have an olefin prepolymerized, and the solid catalyst component further preliminarily polymerized on the prepolymerized solid catalyst component The catalyst component may be supported.

In the olefin polymerization method according to the present invention,
An olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the above olefin polymerization catalyst.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane. Alicyclic hydrocarbons such as; benzene, toluene, xylene, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, and other halogenated hydrocarbons, or mixtures thereof. The olefin itself is used as a solvent. You can also

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is
It is usually used in an amount of 10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to 10 ^-4 mol per liter of reaction volume, and the component (B) is usually 10 ^-12 to 10 ^-2 mol, It is preferably used in an amount so as to be 10 ⁻¹⁰ to 10 ⁻³ mol.
The component (B) has a molar ratio [(B) / (A)] of the component (B) and the component (A) of usually 0.0001 to 200,
It is preferably used in an amount of 0.001 to 100.

The component (C-1) is the same as the component (C-1) and the component (A).
And a molar ratio [(C-1) / M] of all transition metal atoms (M) in the component (B) is usually 0.01 to 100,000, preferably 0.05 to 50,000. To be The component (C-2) is composed of the aluminum atom in the component (C-2) and the transition metal atom (M) in the components (A) and (B).
And the molar ratio [(C-2) / M] is usually 10 to 50000
It is used in an amount of 0, preferably 20 to 100,000. The component (C-3) is a molar ratio of the component (C-3) to the transition metal atom (M) in the components (A) and (B) [(C-
3) / M] is usually used in an amount of 1-10, preferably 1-5.

The component (E) is the same as the component (C) in the component (c-1).
In the case of, the molar ratio [(E) / (c-1)] is usually 0.0
When the component (C) is the component (c-2) in an amount of 1 to 10, preferably 0.1 to 5, the molar ratio [(E) /
(C-2)] is usually 0.001 to 2, preferably 0.00
When the component (C) is the component (c-3), the molar ratio [(E) / (c-3)] is usually 0.01.
It is used in an amount such that it is -10, preferably 0.1-5.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually from -50 to +200.
C., preferably in the range of 0 to 170.degree. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to
It is under the condition of 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Further, it can be adjusted depending on the difference in the component (C) used.

As the olefin which can be polymerized by such an olefin polymerization catalyst, a linear or branched α-olefin having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-
Hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,
8a-Octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1)-
Α-β-unsaturated carboxylic acid such as 5-heptene-2,3-dicarboxylic acid anhydride, and metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; acrylic acid Methyl, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,
N-Butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc. Α, β-unsaturated carboxylic acid ester of; vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconic acid ester, etc. .

It is also possible to use vinylcyclohexane, dienes or polyenes. The diene or polyene has 4 to 30 carbon atoms, preferably 4 carbon atoms.
A cyclic or chain compound having 20 to 20 and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,
7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene,
5,9-dimethyl-1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, Mono- or polyalkyl styrenes such as m-ethyl styrene and p-ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, vinyl benzoate methyl, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-chloro styrene, divinyl Functional group-containing styrene derivatives such as benzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. These olefins may be used alone or in combination of two or more.

[0291]

The olefin polymerization catalyst according to the present invention is
It is possible to obtain a polymer having a high polymerization activity and a wide molecular weight distribution. Olefin (co) obtained by the method of the present invention
Since the polymer has a wide molecular weight distribution, it has excellent moldability.

[0292]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

In this example, the intrinsic viscosity ([η]) was measured in decalin at 135 ° C. The molecular weight distribution (Mw / Mn) was obtained by measuring with gel permeation chromatography (GPC) at 140 ° C. using o-dichlorobenzene as a solvent.

[0294]

Example 1 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen.
The liquid and gas phases were saturated with ethylene. After that, methylaluminoxane is converted into aluminum atom by 1.25 m
mol, followed by addition of 0.00025 mmol of 1,3-dimethylcyclopentadienyl zirconium dichloride and 0.00025 mmol of the following zirconium compound (1) to start polymerization. 25 under normal pressure ethylene gas atmosphere
After reacting at 5 ° C for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. 8 polymer
After drying under reduced pressure at 0 ° C for 10 hours, polyethylene (P
4.52 g of E) was obtained. The intrinsic viscosity [η] of the obtained polyethylene was 2.6 dl / g and the molecular weight distribution measured by GPC was 42.7.

[0295]

[Chemical 57]

[0296]

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the zirconium compound (1) was not used. As a result, 0.40 g of polyethylene was obtained. The intrinsic viscosity [η] of the obtained polyethylene is 14 dl / g, GPC
The measured molecular weight distribution was 2.05.

[0297]

Example 2 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and the liquid phase and the gas phase were saturated with a mixed gas of ethylene 50 liter / hr and propylene 150 liter / hr. It was After that, methylaluminoxane was converted into aluminum atoms in an amount of 1.25 mmol and 1,3-dimethylcyclopentadienylzirconium dichloride 0.0005 mmol.
And a zirconium compound (1) (0.0005 mmol) were mixed in a toluene solution to initiate polymerization. 25 ° C
After 10 minutes of polymerization, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After filtering with a glass filter to remove the solvent, it was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours. The ethylene / propylene copolymer obtained was 2.
57 g, propylene content measured by IR is 33 m
ol%, [η] was 1.71 dl / g, and the molecular weight distribution measured by GPC was 50.0.

[0299]

Comparative Example 2 Polymerization was carried out in the same manner as in Example 2 except that 1,3-dimethylcyclopentadienyl zirconium dichloride was not used, and 0.8 g of a polymer was obtained. The propylene content of the obtained ethylene / propylene copolymer was 31 mol%, the intrinsic viscosity [η] was 0.03 dl / g, and the molecular weight distribution measured by GPC was 2.
It was 02.

[0300]

Example 3 A glass autoclave having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, was charged with 250 ml of toluene, and ethylene 100 liter / hr and propylene 100 were charged.
The liquid phase and the gas phase were saturated with a mixed gas of liter / hr. After that, triisobutylaluminum 0.25mm
After adding ol, triisobutylaluminum 0.02
mmol, 1,3-dimethylcyclopentadienyl zirconium dichloride 0.0005 mmol, 0.0005 mmol of the following zirconium compound (2), and a premixed solution of 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added, Polymerization started. After carrying out the polymerization at 50 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer was 0.78 g, the propylene content measured by IR was 6.5 mol%, [η] was 10.6 dl / g, and GPC
The measured molecular weight distribution was 9.16.

[0301]

[Chemical 58]

[0302]

Comparative Example 3 Polymerization was carried out in the same manner as in Example 3, except that 1,3-dimethylcyclopentadienyl zirconium dichloride was not used, and as a result, 0.38 g of a polymer was obtained. The ethylene / propylene copolymer obtained had a propylene content of 6.1 mol%, an intrinsic viscosity [η] of 14.7 dl / g, and a molecular weight distribution measured by GPC of 2.15.

[0303]

Example 4 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml that had been sufficiently replaced with nitrogen, and the liquid phase and the gas phase were saturated with a mixed gas of 100 liter / hr of ethylene and 10 liter / hr of hydrogen. . Then, after adding triisobutylaluminum 0.5 mmol, triisobutylaluminum 0.05 mmol,
(tert-Butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride 0.00
25 mmol, 0.002 of zirconium compound (1)
A premixed solution of 5 mmol and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. 25
After polymerization was carried out at 5 ° C for 5 minutes, a small amount of isobutanol was added to terminate the polymerization.

The polymer solution thus obtained was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. The polyethylene obtained was 2.5 g, [η] was 12.5 dl / g, and the molecular weight distribution by GPC measurement was 7.37.

[0305]

Comparative Example 4 Preparation and polymerization were carried out in the same manner as in Example 4, except that (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride was not used. The polyethylene obtained was 1.2 g, [η] = 19.4 dl / g, GPC
The measured molecular weight distribution was 2.10.

[0306]

[Example 5] [Preparation of solid catalyst component] 10 kg of silica dried at 250 ° C for 10 hours was suspended in 154 liters of toluene and then cooled to 0 ° C. Then methyl aluminoxane solution (Al = 1.33 mol / liter) 5
7.5 liters were added dropwise in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Then, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and at that temperature, 2
The reaction was allowed for 0 hours. After that, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The obtained solid catalyst component was washed twice with toluene and then resuspended in toluene to obtain a solid catalyst component (A) (total volume 200 liters).

22.4 ml of the suspension of the solid catalyst component (A) thus obtained was transferred to a 200 ml glass flask, and 148 ml of toluene and a toluene solution of dicyclopentadienylzirconium dichloride (Z
r = 0.005 mmol / liter) 8.6 ml and a toluene solution of zirconium compound (1) (Zr = 0.0
(01 mmol / l) 43 ml and added at room temperature for 2
Stir for hours. This suspension was washed 3 times with 200 ml of hexane, and hexane was added to obtain 200 ml of a suspension to obtain a solid catalyst component (B).

[Polymerization] 1 liter of heptane was charged into a 2 liter autoclave made of SUS that had been sufficiently replaced with nitrogen, and the mixture was heated to 70 ° C. to saturate the gas phase and the liquid phase with ethylene.
Then, triisobutylaluminum 1.0 mmol,
Add 0.005 mmol of the solid catalyst component (B) in terms of contained Zr atom, and add 75 ° C and ethylene pressure of 8 kg.
/ Cm ² G for 90 minutes.

The obtained polymer suspension was filtered through a glass filter, washed twice with 500 ml of hexane, and then at 80 ° C.
It was dried under reduced pressure for 10 hours. The polyethylene obtained is 7
It was 6 g, [η] was 8.11 dl / g, and the molecular weight distribution by GPC measurement was 5.72.

[0310]

Comparative Example 5 Preparation and polymerization were carried out in the same manner except that dicyclopentadienyl zirconium dichloride was not used in the preparation of the solid catalyst component of Example 5. The obtained polyethylene was 31 g, and [η] = 14.0 dl /
g, the molecular weight distribution measured by GPC was 2.25.

[Brief description of drawings]

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

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Makoto Mitani             6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture             Mitsui Chemicals, Inc. (72) Inventor Terusuke Fujita             6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture             Mitsui Chemicals, Inc. F-term (reference) 4J028 AA02A AB00A AB01A AB02A                       AC00A AC01A AC08A AC09A                       AC10A AC18A AC19A AC20A                       AC26A AC27A AC28A AC29A                       AC31A AC45A AC47A AC48A                       BA01B BA02B BB01B BB02B                       BC01B BC05B BC06B BC08B                       BC09B BC12B BC15B BC16B                       BC17B BC18B BC19B BC24B                       BC25B BC27B BC29B CA15C                       CA16C CA25C CA26C CA27C                       CA28C CA29C CA30C CB09C                       EB01 EB02 EB03 EB04 EB05                       EB07 EB08 EB09 EB10 EB11                       EB13 EB14 EB16 EB17 EB18                       EB21 EB24 EB25 EB26 GA04                       GA06 GB01                 4J100 AA02P AA04P AA05P AA07P                       AA09P AA15P AA16P AA17P                       AA18P AA19P AA20P AA21P                       AB01P AB02P AB03P AB04P                       AB07P AB08P AB16P AG02P                       AG04P AG05P AG08P AJ02P                       AJ08P AJ09P AK08P AK13P                       AK20P AK21P AK31P AK32P                       AL03P AL04P AL10P AL46P                       AR03P AR04P AR09P AR11P                       AR16P AR22P AS01P AS02P                       AS03P AS11P AS15P AU21P                       BA03P BA05P BA06P BA16P                       BA20P BB18P BC54P BC55P                       CA01 CA04 DA04 FA10

Claims (3)

[Claims] 1. A transition metal compound of Group 4 of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, and (B)
A transition metal compound represented by the following general formula (I), and (C)
(C-1) an organometallic compound, (C-2) an organoaluminumoxy compound, and (C-3) a compound which reacts with a transition metal compound (A) or a transition metal compound (B) to form an ion pair A catalyst for olefin polymerization, which comprises at least one compound represented by the formula: (In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , and R ^{1 to} R ⁶ may be the same or different from each other, a hydrogen atom, Indicates a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Two or more of them may be linked to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ are linked. Also, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, phosphorus Containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, A group containing rumanium or a group containing tin, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring; May be formed.) 2. The transition metal compound (A) according to claim 1.
A transition metal compound (B), an organic metal compound (C-1),
(C-2) An organoaluminum oxy compound and (C-3) an olefin polymerization characterized by containing a carrier (D) in addition to at least one compound (C) selected from ionized ionic compounds catalyst. 3. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.