JPH11140111A - Catalyst for olefin polymerization and manufacture of olefin polymer therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst for an olefin polymer having a high molecular weight by employing a group IV-VI transition metal compound having at least one conjugated five-member ligand, an ion-exchangeable layer compound other than a silicate or an inorganic silicate, and a compound containing a nitrogen or a phosphorus atom as essential components. SOLUTION: As a catalyst component, an organoaluminum compound can be also employed. A transition metal compound having a conjugated five-member ligand is preferably a compound represented by formula I, II, III or IV. In formulas I-IV, A and A' are each conjugated five-member ligand; Q is a linkage bond crosslinking two conjugated five-member ligands at a desired position; Z is a ligand containing a nitrogen atom, an oxygen atom or the like; Q' is a linkage bond crosslinking a desired position of a conjugated five-member ligand and a Z; M is a group IV-VI metal atom in the periodic table; and X and Y are each H, a halogen atom, a hydrocarbon group or the like. A compound containing a nitrogen or a phosphorus atom is preferably nitrils, pyridine, a trialkyl phosphine or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More specifically, the present invention provides a catalyst for olefin polymerization, in which a high molecular weight olefin polymer can be obtained by using a nitrogen- or phosphorus-containing compound, and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art As a method for producing an olefin polymer by polymerizing an olefin in the presence of a polymerization catalyst, a catalyst system comprising (1) a metallocene and (2) an aluminoxane has conventionally been used as a catalyst system. Have already been proposed (JP-A-60-35007, JP-B-4-12283, etc.). The polymerization method using these catalyst systems has a very high polymerization activity per transition metal as compared with a method using a so-called Ziegler-Natta catalyst comprising a titanium compound or a vanadium compound and an organoaluminum compound, and
An olefin polymer having a narrow molecular weight distribution or composition distribution can be obtained.

However, a large amount of aluminoxane is required in order to industrially obtain sufficient polymerization activity using these catalysts, so that the polymerization activity per aluminum is low and not only economically disadvantageous, There were problems such as the necessity of removing the catalyst residue from the produced polymer.

On the other hand, a method has been proposed in which olefin polymerization is carried out using a catalyst system in which one or both of a metallocene compound and an aluminoxane are supported on an inorganic oxide such as silica or alumina (JP-A-61-108610). JP, JP-A-60-135408, JP-A-61-29600
No. 8, JP-A-3-74412, JP-A-3-744.
No. 15). Further, a method of polymerizing an olefin using a catalyst system in which one or both of a metallocene compound and an organic aluminum are supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-1-101303). No. 1-207303,
JP-A-3-234709 and JP-A-3-501869). However, even in these methods, the polymerization activity per aluminum was still not sufficient, and the amount of catalyst residue in the produced olefin polymer was not negligible.

As a method for solving these problems,
A catalyst comprising an ion-exchange layered compound or an inorganic silicate, an organoaluminum and a metallocene compound has been proposed (JP-A-5-295022, etc.). In these catalysts, the polymerization activity per transition metal or aluminum is sufficiently high, but hydrogen is by-produced during the polymerization, and the generated hydrogen may make it difficult to increase the molecular weight of the olefin polymer. In order to obtain a molecular weight product, control the hydrogen concentration in the reaction system,
Alternatively, a problem such as a need to take special measures such as removal of by-produced hydrogen may occur, and improvement of the catalyst system has been desired. The present invention solves the above problems, and provides an olefin polymerization catalyst capable of obtaining an olefin polymer having a large molecular weight, and a method for polymerizing an olefin using the catalyst.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of such a situation, and as a result, have reached the present invention. That is, the gist of the present invention is [A] a transition metal compound belonging to Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand,
[B] An olefin polymerization catalyst comprising an ion-exchange layered compound or inorganic silicate other than silicate, and [C] a nitrogen or phosphorus-containing compound as essential components, and a method for polymerizing olefins using this catalyst. Exist. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component [A] constituting the catalyst of the present invention is a transition metal compound belonging to Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. Preferred as such transition metal compounds are those represented by the following general formula [1]:
It is a compound represented by [2], [3] or [4].

[0008]

Embedded image

Wherein A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, and Q ′ represents an optional conjugated five-membered ring ligand. Position and Z
And M represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, and a phosphorus-containing hydrocarbon. Or a silicon-containing hydrocarbon group. )

A and A 'are conjugated five-membered ring ligands, which may be the same or different in the same compound, as described above. Specific examples of the conjugated five-membered ring ligand include a conjugated five-membered ring ligand, that is, a cyclopentadienyl group. The cyclopentadienyl group may be one having 5 hydrogen atoms [C ₅ H _5- ], and a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with a substituent, Is also good. Examples of the substituent include a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when a plurality of these are present, two or more of them are bonded at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the enyl group. As an example of the latter, two substituents are bonded at each ω-terminal to form a fused ring by sharing two adjacent carbon atoms in the cyclopentadienyl group. In particular,
Those forming a fused 6-membered ring, that is, an indenyl group, a tetrahydroindenyl group or a fluorenyl group,
Examples thereof include an azulenyl group and a dihydroazulenyl group forming a condensed 7-membered ring, and derivatives obtained by substituting hydrogen atoms on these rings.

Further, these may have a substituent on a sub-membered ring or on a cyclopentadienyl ring, and specific substituents include 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
Hydrocarbon groups, fluorine, chlorine, halogen atoms such as bromine,
A halogenated hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
2 alkoxy _{group, -Si (R 1) (R} 2) a silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by (R _3), -P
(R ₁ ) a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms represented by (R ₂ ); a carbon atom having 1 carbon atom represented by —N (R ₁ ) (R ₂ )
To 18 nitrogen-containing hydrocarbon groups, or -B (R ₁ )
Include boron-containing hydrocarbon group having 1 to 18 carbon atoms represented by (R _2). When there are a plurality of these substituents, each substituent may be the same or different. R _{1 to} R ₃ described above may be the same or different, and include a hydrogen atom,
And represents an alkyl group having 1 to 20 carbon atoms.

Q is a bonding group bridging any two positions between the two conjugated five-membered ligands, and Q 'is a bonding group bridging any position of the conjugated five-membered ligand and the group represented by Z. Represents a group. Specific examples of Q and Q ′ include (a) a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group and the like;
To 20 alkylene groups, (b) silylene groups such as silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group, and tetramethyldisilylene group, (c) germanium, phosphorus, nitrogen, and boron Alternatively, a hydrocarbon group containing aluminum, specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (C
_{H 3) P, (C 6} H 5) P, (C 4 H 9) N, (C 6 H
_{5) N, (CH 3)} B, (C 4 H 9) B, (C 6 H 5)
B is a hydrocarbon group represented by (C ₆ H ₅ ) Al and (CH ₃ O) Al. Preferred among these are alkylene groups and silylene groups.

M is a metal atom selected from Groups 4 to 6 of the periodic table, preferably a metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium and the like. Among them, zirconium and hafnium are preferred. Z is a nitrogen atom,
A ligand containing an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, a hydrogen atom, a halogen atom or a hydrocarbon group. Specific examples of preferred examples include an oxygen atom, a sulfur atom, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and 1 to 40 carbon atoms. Preferably 1 to 18 silicon-containing hydrocarbon groups, 1 to 40 carbon atoms, preferably 1 to 1
A nitrogen-containing hydrocarbon group of 8; a phosphorus-containing hydrocarbon group having 1 to 40, preferably 1 to 18 carbon atoms; a hydrogen atom; chlorine, bromine; and a hydrocarbon group having 1 to 20 carbon atoms.

X and Y each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and diphenyl. 1 to 1 carbon atoms such as phosphine group
20, a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as a trimethylsilyl group and a bis (trimethylsilyl) methyl group. X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group, particularly those having 1 to 8 carbon atoms, and an amino group are preferred.

In the catalyst for olefin polymerization according to the present invention, A, A ', Q,
Among Q ', Z, M, X, and Y, particularly preferred are compounds constituted by bonds such as the following ligands and derivatives thereof. A, A ′ = cyclopentadienyl,
Methylenecyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2,3-trimethylcyclopentadienyl,
1,2,4-trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, indenyl, 2-methyl-
Indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methylbenzoindenyl, fluorenyl,
1-methylfluorenyl, 2-ethylfluorenyl,
2,4-dimethyl-4-hydroazulenyl, 2-methyl-4-phenyl-4-hydroazulenyl, Q ₂ = ethylene, dimethylsilylene, isopropylidene Z = t-butylamide, phenylamide, cyclohexylamide, M = germanium, zirconium, Hafnium X, Y = chlorine, methyl, diethylamino.

The components [A] represented by the general formulas (1) to (4) may be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas. it can. The following are specific examples of the transition metal compound represented by A or A '.

(A) As the compound represented by the general formula [1], that is, the transition metal compound having no binding group Q and having two conjugated five-membered ring ligands, the following compounds can be mentioned. (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadichloride) (Enyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) bis (n-butylcyclopentadienyl) zirconium dichloride, (8) bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, (9)
Bis (indenyl) zirconium dichloride, (10)
Bis (4,5,6,7-telorahydroindenyl) zirconium dichloride, (11) bis (2-methyl-4,
5,6,7-terolahydroindenyl) zirconium dichloride, (12) bis (2-methyl-4H-azulenyl) zirconium dichloride, (13) bis (2-methyl-4-phenylazulenyl) zirconium dichloride, (14 ) Bis (fluorenyl) zirconium dichloride, (15) bis (cyclopentadienyl) zirconium monochloride monohydride, (16) bis (cyclopentadienyl) methylzirconium monochloride, (17) bis (cyclopentadienyl) ethyl Zirconium monochloride, (18) bis (cyclopentadienyl) phenyl zirconium monochloride, (19)
Bis (cyclopentadienyl) zirconium dimethyl,
(20) bis (cyclopentadienyl) zirconium diphenyl, (21) bis (cyclopentadienyl) zirconium dineopentyl, (22) bis (cyclopentadienyl) zirconium dihydride, (23) (cyclopentadienyl ) (Indenyl) zirconium dichloride, (24) (cyclopentadienyl) (fluorenyl) zirconium dichloride,

(B) (b-1) The compounds represented by the general formula [2], that is, those having a binding group Q = alkylene group, include the following. (1) methylene bis (indenyl) zirconium dichloride, (2) ethylene bis (indenyl) zirconium dichloride, (3) ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride,
(5) ethylene bis (indenyl) zirconium monomethoxide monochloride, (6) ethylene bis (indenyl) zirconium diethoxide, (7) ethylene bis (indenyl) zirconium dimethyl, (8) ethylene bis (4,5,6) , 7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride, (11) ethylenebis (2,4- Dimethylindenyl) zirconium dichloride, (12) ethylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (13) ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3'-tert-butyl -5'-methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride,
(15) ethylene-1,2-bis (4-indenyl) zirconium dichloride, (16) ethylene-1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride, (17) ethylene-1 , 2-bis (4-
Phenylindenyl) zirconium dichloride,

(18) isopropylidenebis (indenyl) zirconium dichloride, (19) isopropylidenebis (fluorenyl) zirconium dichloride, (2)
0) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (21) isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) ) (3'-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (2
3) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride hydride, (24) methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dimethyl, (25) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (26) methylene (cyclopentadienyl) (trimethyl (Cyclopentadienyl) zirconium dichloride, (27) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride,

(28) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (29) isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride,
(30) isopropylidene (cyclopentadienyl)
(3-methylindenyl) zirconium dichloride,
(31) isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, (32) isopropylidene (2-methylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (33) isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(34) isopropylidene (2,5-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (35) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) ) Zirconium dichloride,

(36) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (37) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(38) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
9) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (4
0) ethylene bis [4- (2-methylindenyl)] zirconium dichloride, (41) ethylene bis [4-
(2,7-dimethyl-indenyl)] zirconium dichloride, (42) ethylene bis [4- (2-phenylindenyl)] zirconium dichloride, (43) ethylene bis [4- (1-phenyl-3-methyl-indenyl) )] Zirconium dichloride, (44) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (4
5) diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, (46) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (47) cyclohexylidene (2,5-dimethylcyclopentadienyl) ( 3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride. In addition, the following compounds may be mentioned as an azulene complex and a complex having a sub-membered ring having a larger number of carbon atoms.

(1) Methylene bis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (2) Methylene bis {1,1 ′-(2-methyl-4-hydroazulenyl)} zirconium Dichloride (3) Methylenebis {1,1 '-(2,4-dimethyl-
4-hydroazulenyl)｝ zirconium dichloride (4) methylenebis ｛1,1 '-(4-hydroazulenyl)｝ zirconium dichloride (5) methylenebis ｛1,1'-(2-ethyl-4-hydroazulenyl)｝ zirconium dichloride (6) Methylene bis {1,1 ′-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride (7) Methylene bis {1,1 ′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride ( 8) Methylene bis {1,1 ′-(2,4,4-trimethyl-4-hydroazulenyl)} zirconium dichloride (9) Methylene bis {1,1 ′-(2-methyl-4-phenyl-6-isopropyl-4-) Hydroazulenyl)｝
Zirconium dichloride (10) Methylene bis {1,1 '-(2-methyl-4-
Phenyl-7-isopropyl-4-hydroazulenyl) zirconium dichloride (11) methylenebis {1,1 ′-(2-methyl-4,
(5,6,7,8-pentahydroazulenyl)} zirconium dichloride (12) methylenebis {1,1 ′-(2-methyl-4-)
Phenyl-4,5,6,7,8-pentahydroazulenyl) {zirconium dichloride (13) methylenebis {1,1 ′-(4-methyl-4-
(Hydroazulenyl)} zirconium dichloride (14) methylenebis {1,1 ′-(4-phenyl-4)
-Hydroazulenyl) ニ ル zirconium dichloride (15) methylenebis {1,1 ′-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride (16) methylenebis {1,1 ′-(4-naphthyl-4)
-Hydroazulenyl) zirconium dichloride (17) methylenebis {1,1 '-(2-phenyl-4)
-Hydroazulenyl) zirconium dichloride (18) methylenebis {1,1 ′-(2-benzyl-4)
-Hydroazulenyl) zirconium dichloride (19) methylenebis {1,1 '-(2-styryl-4)
-Hydroazulenyl) zirconium dichloride (20) methylenebis {1,1 '-(2-t-butyl-
4-hydroazulenyl) zirconium dichloride (21) methylenebis {1,1 '-(2-methyl-6-
(Isopropyl-4-hydroazulenyl)} zirconium dichloride (22) methylenebis {1,1 ′-(2-ethyl-4,
7-diisopropyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride (23) methylenebis (1,1′-cyclopentacyclooctenyl) zirconium dichloride

(24) Methylene bis {1,1 '-(4-
Methylcyclopentacyclooctenyl)｝ zirconium dichloride (25) methylenebis ｛1,1 ′-(4-ethylcyclopentacyclooctenyl)｝ zirconium dichloride (26) methylenebis ｛1,1 ′-(4,6-dimethylcyclo) (Pentacyclooctenyl)} zirconium dichloride (27) methylenebis {1,1 ′-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride (28) methylenebis {1,1 ′-(2-methyl- 5-
(Phenylcyclopentacyclooctenyl) テ zirconium dichloride (29) methylenebis メ チ レ ン 1,1 ′-(4-phenylcyclopentacyclooctenyl)｝ zirconium dichloride (30) methylenebis メ チ レ ン 1,1 ′-(2-ethyl-4-
Phenylcyclopentacyclooctenyl)｝ zirconium dichloride (31) methylenebis ｛1,1 '-(4-methyl-4,5,
6,7,8,9-hexahydrocyclopentacyclooctenyl) zirconium dichloride (32) methylenebis (9-bicyclo [8.3.0] trideca-2-methylpentaenyl) zirconium dichloride (33) methylenebis (9 -Bicyclo [8.3.0] trideca-2,12-dimethylpentaenyl) zirconium dichloride (34) methylenebis (9-bicyclo [8.3.0] trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride (35) methylenebis (9-bicyclo [8.3.0] trideca-2-phenyl, 12-ethylpentaenyl) zirconium dichloride (36) ethylenebis {1,1 ′-(4-hydroazulenyl)} zirconium dichloride

(37) Ethylene bis {1,1 '-(2-
Methyl-4-hydroazulenyl) zirconium dichloride (38) ethylenebis {1,1 ′-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride (39) ethylenebis {1,1 ′-(2-methyl- 4-
Phenyl-4-hydroazulenyl) zirconium dichloride (40) ethylenebis {1,1 '-(2-ethyl-4-
(Hydroazulenyl)} zirconium dichloride (41) ethylenebis {1,1 ′-(2-ethyl-4-)
Methyl-4-hydroazulenyl) zirconium dichloride (42) ethylenebis {1,1 ′-(2-ethyl-4-
Phenyl-4-hydroazulenyl) zirconium dichloride (43) ethylenebis {1,1 ′-(2,4,4-trimethyl-4-hydroazulenyl)} zirconium dichloride (44) ethylenebis {1,1 ′-(2- Methyl-4-
Phenyl-6-isopropyl-4-hydroazulenyl) zirconium dichloride (45) ethylenebis {1,1 ′-(2-methyl-4-
Phenyl-7-isopropyl-4-hydroazulenyl) zirconium dichloride (46) ethylenebis {1,1 ′-(2-methyl-4,
(5,6,7,8-pentahydroazulenyl)} zirconium dichloride (47) ethylenebis {1,1 ′-(2-methyl-4-)
Phenyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride

(48) Ethylene bis {1,1 '-(4-methyl-4-hydroazulenyl)} zirconium dichloride (49) Ethylene bis {1,1'-(4-phenyl-4)
-Hydroazulenyl) zirconium dichloride (50) ethylenebis {1,1 '-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride (51) ethylenebis {1,1'-(4-naphthyl-4)
-Hydroazulenyl) zirconium dichloride (52) ethylenebis {1,1 '-(2-phenyl-4)
-Hydroazulenyl) zirconium dichloride (53) ethylenebis {1,1 '-(2-benzyl-4)
-Hydroazulenyl) zirconium dichloride (54) ethylenebis {1,1 '-(2-styryl-4)
-Hydroazulenyl) zirconium dichloride (55) ethylenebis {1,1 '-(2-t-butyl-
4-hydroazulenyl) zirconium dichloride (56) ethylenebis {1,1 '-(2-methyl-6-
(Isopropyl-4-hydroazulenyl)} zirconium dichloride (57) ethylenebis {1,1 ′-(2-ethyl-4,
7-diisopropyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride (58) ethylenebis (1,1'-cyclopentacyclooctenyl) zirconium dichloride (59) ethylenebis {1,1 '-(4-methylcyclopentacyclooctenyl)｝ zirconium dichloride (60) ethylenebis {1,1'-(4-ethylcyclopentacyclooctenyl)｝ zirconium dichloride (61) ethylenebis {1,1'- (4,6-dimethylcyclopentacyclooctenyl) zirconium dichloride (62) ethylene bis {1,1 '-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride (63) ethylene bis} 1 , 1 '-(2-methyl-5-
(Phenylcyclopentacyclooctenyl)｝ zirconium dichloride (64) ethylenebis ｛1,1 '-(4-phenylcyclopentacyclooctenyl)｝ zirconium dichloride (65) ethylenebis ｛1,1'-(2-ethyl- 4-
Phenylcyclopentacyclooctenyl) zirconium dichloride (66) ethylenebis {1,1 ′-(4-methyl-4,
5,6,7,8,9-Hexahydrocyclopentacyclooctenyl) zirconium dichloride (67) Ethylenebis (9-bicyclo [8.3.0] trideca-2-methylpentaenyl) zirconium dichloride (68) Ethylene bis (9-bicyclo [8.3.0] trideca-2,12-dimethylpentaenyl) zirconium dichloride (69) Ethylene bis (9-bicyclo [8.3.0] trideca-2,12-dimethyloctahydro Pentaenyl) zirconium dichloride

(70) Ethylene bis (9-bicyclo [8.3.0] trideca-2-phenyl, 12-ethylpentaenyl) zirconium dichloride (71) Ethylene (1-indenyl) ｛1- (4-hydroazulenyl) {Zirconium dichloride (72) ethylene {1- (2-methylindenyl)}}
{1- (2-methyl-4-hydroazulenyl)} zirconium dichloride (73) ethylene {1- (2-methyl-4,5-benzoindenyl)} 1- (2,4-dimethyl-4-hydroazulenyl) {Zirconium dichloride (74) ethylene} 1- (2-methyl-4-phenylindenyl) {1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (75) ethylene} 1- (2- Ethyl-4-phenylindenyl) {1- (2-ethyl-4-hydroazulenyl)} zirconium dichloride (76) ethylene {1- (2,4-dimethylcyclopentadienyl)} 1- (2-ethyl -4-methyl-4-
(Hydroazulenyl) {zirconium dichloride (77) ethylene} 1- (2-methyl-4,5-benzoindenyl)} 1- (2-ethyl-4-phenyl-4)
-Hydroazulenyl) ニ ル zirconium dichloride (78) ethylene ｛1- (2-methyl-4-phenylindenyl)｝ ｛1- (2,4,4-trimethyl-4-hydroazulenyl)｝ zirconium dichloride (79) ethylene ｛1 -(2,4,7-trimethylindenyl) {1- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride (80) ethylene {1- (2-ethyl-4, 5-benzoindenyl) {1- (2-methyl-4-phenyl-7)
-Isopropyl-4-hydroazulenyl) {zirconium dichloride (81) ethylene {1- (2-methyltetrahydroindenyl)} 1- (2-methyl-4,5,6,7,8-
(Pentahydroazulenyl) {zirconium dichloride (82) ethylene} 1- (2-t-butyl-4-methylcyclopentadienyl)} 1- (2-methyl-4-phenyl-4,5,6,7 , 8-pentahydroazulenyl) {zirconium dichloride (83) ethylene} 1- (2-ethyl-4-phenylindenyl) {1- (4-methyl-4-hydroazulenyl)} zirconium dichloride (84) ethylene} 1- (2-phenylindenyl)}
{1- (4-phenyl-4-hydroazulenyl)} zirconium dichloride (85) ethylene {1- (2-propyl-4-phenylindenyl)} 1- (4-isopropyl-4-hydroazulenyl)} zirconium dichloride ( 86) Ethylene {1- (2-t-butylindenyl)} 1- (4-naphthyl-4-hydroazulenyl)} zirconium dichloride

(87) Dimethylmethylenebis {1,1 ′
-(4-hydroazulenyl) zirconium dichloride (88) dimethylmethylenebis {1,1 '-(2-methyl-4-hydroazulenyl)} zirconium dichloride (89) dimethylmethylenebis {1,1'-(2,4-
Dimethyl-4-hydroazulenyl) zirconium dichloride (90) dimethylmethylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (91) dimethylmethylenebis {1,1 ′-( 2-ethyl-4-hydroazulenyl) zirconium dichloride (92) dimethylmethylenebis {1,1 '-(2-ethyl-4-methyl-4-hydroazulenyl) zirconium dichloride (93) dimethylmethylenebis {1,1' -(2-ethyl-4-phenyl-4-hydroazulenyl) {zirconium dichloride (94) dimethylmethylenebis} 1,1 '-(2,4
4-trimethyl-4-hydroazulenyl) {zirconium dichloride (95) dimethylmethylenebis {1,1 ′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride (96) dimethylmethylenebis} 1,1 ′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) zirconium dichloride (97) dimethylmethylenebis {1,1 ′-(2-methyl-4,5,6,7, 8-pentahydroazulenyl)｝
Zirconium dichloride (98) dimethylmethylenebis {1,1 ′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride (99) dimethylmethylenebis {1, 1 ′-(4-methyl-4-hydroazulenyl)｝ zirconium dichloride (100) dimethylmethylenebis {1,1 ′-(4-phenyl-4-hydroazulenyl)｝ zirconium dichloride (101) dimethylmethylenebis ｛1,1 ′ -(4-isopropyl-4-hydroazulenyl) zirconium dichloride (102) dimethylmethylenebis {1,1 '-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride

(103) dimethylmethylenebis {1,
1 ′-(2-phenyl-4-hydroazulenyl) ニ ル zirconium dichloride (104) dimethylmethylenebis ｛1,1 ′-(2-benzyl-4-hydroazulenyl) ニ ル zirconium dichloride (105) dimethylmethylenebis メ チ レ ン 1,1 ′ -(2-styryl-4-hydroazulenyl) zirconium dichloride (106) dimethylmethylenebis {1,1 '-(2-t
-Butyl-4-hydroazulenyl)｝ zirconium dichloride (107) dimethylmethylenebis {1,1 ′-(2-methyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride (108) dimethylmethylenebis {1,1′- (2-ethyl 4,7-diisopropylhexahydroazulenyl) zirconium dichloride (109) dimethylmethylenebis (1,1'-cyclopentacyclooctenyl) zirconium dichloride (110) dimethylmethylenebis {1,1 '-( 4-methylcyclopentacyclooctenyl) {zirconium dichloride (111) dimethylmethylenebis {1,1 ′-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride (112) dimethylmethylenebis {1,1 ′-( 4,6
-Dimethylcyclopentacyclooctenyl)｝ zirconium dichloride (113) dimethylmethylenebis ｛1,1 '-(4-methyl-6-isopropylcyclopentacyclooctenyl)｝ zirconium dichloride (114) dimethylmethylenebis ｛1,1 '-(2-methyl-5-phenylcyclopentacyclooctenyl)}
Zirconium dichloride (115) dimethylmethylenebis {1,1 ′-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride (116) dimethylmethylenebis {1,1 ′-(2-ethyl-4-phenylcyclopentacyclo) Octenyl)｝
Zirconium dichloride (117) Dimethylmethylenebis {1,1 '-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)} zirconium dichloride (118) Dimethylmethylenebis (9 -Bicyclo [8.
3.0] Trideca-2-methylpentaenyl) zirconium dichloride (119) dimethylmethylenebis (9-bicyclo [8.
3.0] Trideca-2,12-dimethylpentaenyl)
Zirconium dichloride (120) dimethylmethylenebis (9-bicyclo [8.
3.0] Trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride (121) dimethylmethylenebis (9-bicyclo [8.
3.0] Trideca-2-phenyl, 12-ethylpentaenyl) zirconium dichloride

(122) Dimethylmethylene (1-indenyl) {1- (4-hydroazulenyl)} zirconium dichloride (123) Dimethylmethylene {1- (2-methylindenyl)} 1- (2-methyl-4-) (Hydroazulenyl) {zirconium dichloride (124) dimethylmethylene} 1- (2-methyl-4,
5-benzoindenyl) {1- (2,4-dimethyl-
4-hydroazulenyl) {zirconium dichloride (125) dimethylmethylene} 1- (2-methyl-4-)
Phenylindenyl) {1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (126) dimethylmethylene} 1- (2-ethyl-4-
Phenylindenyl) {1- (2-ethyl-4-hydroazulenyl)} zirconium dichloride (127) dimethylmethylene {1- (2,4-dimethylcyclopentadienyl)} 1- (2-ethyl-4- Methyl-4-hydroazulenyl) {zirconium dichloride (128) dimethylmethylene} 1- (2-methyl-4,
5-benzoindenyl) {1- (2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (129) dimethylmethylene} 1- (2-methyl-4-
Phenylindenyl) {1- (2,4,4-trimethyl-4-hydroazulenyl)} zirconium dichloride (130) dimethylmethylene {1- (2,4,7-trimethylindenyl)} 1- (2- Methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) {zirconium dichloride (131) dimethylmethylene} 1- (2-ethyl-4,
5-benzoindenyl) {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}
Zirconium dichloride (132) dimethyl methylene {1- (2-methyltetrahydroindenyl)} 1- (2-methyl-4,5,
6,7,8-pentahydroazulenyl) zirconium dichloride

(133) Dimethylmethylene {1- (2-)
t-butyl-4-methylcyclopentadienyl) {1
-(2-methyl-4-phenyl-4,5,6,7,8-
(Pentahydroazulenyl) {zirconium dichloride (134) dimethylmethylene} 1- (2-ethyl-4-)
Phenylindenyl) {1- (4-methyl-4-hydroazulenyl)} zirconium dichloride (135) dimethylmethylene {1- (2-phenylindenyl)} 1- (4-phenyl-4-hydroazulenyl)} zirconium Dichloride (136) dimethylmethylene {1- (2-propyl-4)
-Phenylindenyl) {1- (4-isopropylazulenyl)} zirconium dichloride (137) dimethylmethylene {1- (2-t-butylindenyl)} 1- (4-naphthyl-4-hydroazulenyl)} Zirconium dichloride (138) Dimethylmethylenebis [1,1 '-{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (139) Dimethylmethylenebis [1,1'-{2- Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (140) dimethylmethylenebis [1,1 '-{2-methyl-4- (4-trifluoromethylphenyl) -4-
Hydroazulenyl}] zirconium dichloride (141) ethylenebis [1,1 ′-{2-methyl-4
-(4-Fluorophenyl) -4-hydroazulenyl} zirconium dichloride (142) ethylenebis [1,1 '-{2-methyl-4
-(4-chlorophenyl) -4-hydroazulenyl}]
Zirconium dichloride (143) Ethylene bis [1,1 '-{2-methyl-4
-(4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (144) trimethylenebis [1,1 '-{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (145) trimethylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (146) trimethylenebis [1,1'-{2-methyl-4 -(4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride

(B-2) Examples of Q = silylene group include the following. (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5
6,7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (5) dimethylsilylene Bis (2-methyl-
4,5,6,7-tetrahydroindenyl) zirconium dichloride, (6) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (7)
Dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, (8) dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, (9) dimethylsilylenebis (2-methyl- 4,4-dimethyl-4,5,6,7-tetrahydro-4-silinedenyl) zirconium dichloride, (10) dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride, (11)
Dimethylsilylenebis [4- (2-tert-butylindenyl)] zirconium dichloride, (12) dimethylsilylenebis [4- (2-tert-butylindenyl)] zirconium dichloride, (13) dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, (14) dimethylsilylenebis [4- (2-phenyl-3-methylindenyl)] zirconium dichloride,

(15) Phenylmethylsilylenebis (indenyl) zirconium dichloride, (16) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (17) phenylmethylsilylene (2,4- Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (18) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (19) phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (20) diphenylsilylenebis (indenyl) zirconium dichloride, ( 21) tetramethyldisilylenebis (indenyl) zirconium dichloride, (22) tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, (2)
3) tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride,
(24) Dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (25) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (26) dimethylsilylene (cyclopentadienyl) (tetramethylcyclo (Pentadienyl) zirconium dichloride, (27) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (28) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) Zirconium dichloride, (2
9) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (30) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3)
1) dimethylsilylene (3-tert-butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, (32) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (33) dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,

(34) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (35) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (36) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (37) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (38) diethylsilylene (2-methylcyclopentadienyl) ) (2 ', 7'-di-tert-butylfluorenyl) zirconium dichloride, (39) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2', 7'-di-tert-butylfluorenyl) Nyl) zirconium dichlori , (40) dimethylsilylene (2-
Ethylcyclopentadienyl) (2 ', 7'-di-t-
Butylfluorenyl) zirconium dichloride, (4
1) Dimethylsilylene (diethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) zirconium dichloride, (42) Dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium Dichloride, (43) dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (44) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (45)
Dimethylsilylene (diethylcyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (46) dimethylsilylenebis [1- (2-methyl-4-vitro-4-phenylazulenyl)] zirconium dichloride. In addition, the following compounds may be mentioned as an azulene complex and a complex having a sub-membered ring having a larger number of carbon atoms.

(1) Dimethylsilylene bis {1,1'-
(4-hydroazulenyl) zirconium dichloride (2) dimethylsilylenebis {1,1 '-(2-methyl-4-hydroazulenyl)} zirconium dichloride (3) dimethylsilylenebis {1,1'-(2,4-dimethyl -4-hydroazulenyl)｝ zirconium dichloride (4) dimethylsilylenebis ｛1,1 '-(2-methyl-4-phenyl-4-hydroazulenyl)｝ zirconium dichloride (5) dimethylsilylenebis ｛1,1'-(2 -Ethyl-4-hydroazulenyl) ニ ル zirconium dichloride (6) dimethylsilylenebis ｛1,1 '-(2-ethyl-4-methyl-4-hydroazulenyl)｝ zirconium dichloride (7) dimethylsilylenebis ｛1,1'- (2-ethyl-4-phenyl-4-hydroazulenyl) zirconium Dichloride (8) dimethylsilylene bis {1,1 '- (2,4,4
-Trimethyl-4-hydroazulenyl) zirconium dichloride (9) dimethylsilylenebis {1,1 '-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) zirconium dichloride (10) dimethylsilylenebis} 1 , 1 ′-(2-Methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) {zirconium dichloride (11) dimethylsilylenebis} 1,1 ′-(2-methyl-4,5,6,7,8 -Pentahydroazulenyl)｝
Zirconium dichloride (12) Dimethylsilylenebis {1,1 '-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride (13) Dimethylsilylenebis {1, 1 ′-(4-methyl-4-hydroazulenyl)｝ zirconium dichloride (14) dimethylsilylene bis ｛1,1 ′-(4-phenyl-4-hydroazulenyl)｝ zirconium dichloride (15) dimethylsilylene bis ｛1,1 ′ -(4-isopropyl-4-hydroazulenyl) zirconium dichloride (16) dimethylsilylenebis {1,1 '-(4-naphthyl-4-hydroazulenyl) zirconium dichloride (17) dimethylsilylenebis {1,1'-( 2-phenyl-4-hydroazulenyl) zirconium dichloride (18) Dimethylsilylenebis {1,1 ′-(2-benzyl-4-hydroazulenyl)} zirconium dichloride (19) Dimethylsilylenebis {1,1 ′-(2-styryl-4-hydroazulenyl)} zirconium dichloride (20 ) Dimethylsilylenebis {1,1 '-(2-t-
(Butyl-4-hydroazulenyl) zirconium dichloride (21) dimethylsilylene bis {1,1 '-(2-methyl-6-isopropyl-4-hydroazulenyl) zirconium dichloride (22) dimethylsilylenebis {1,1'-( 2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydro-4-hydroazulenyl) zirconium dichloride (23) dimethylsilylenebis (1,1′-cyclopentacyclooctenyl) zirconium dichloride ( 24) Dimethylsilylenebis {1,1 ′-(4-methylcyclopentacyclooctenyl)} zirconium dichloride (25) Dimethylsilylenebis {1,1 ′-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride ( 26) Dimethylsilylene bis ｛1, '- (4,6
(Dimethylcyclopentacyclooctenyl) zirconium dichloride (27) Dimethylsilylene bis 1,1 '-(4-methyl-6-isopropylcyclopentacyclooctenyl) zirconium dichloride (28) Dimethylsilylene bis 1,1' -(2-methyl-5-phenylcyclopentacyclooctenyl) {zirconium dichloride (29) dimethylsilylenebis {1,1 '-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride (30) dimethylsilylenebis} 1,1 '-(2-ethyl-4-phenylcyclopentacyclooctenyl) {zirconium dichloride (31) dimethylsilylenebis} 1,1'-(4-methyl-4,5,6,7,8,9 -Hexahydrocyclopentacyclooctenyl) zirconium Chloride (32) dimethylsilylene-bis (9-bicyclo [8.
3.0] Trideca-2-methylpentaenyl) zirconium dichloride (33) dimethylsilylenebis (9-bicyclo [8.
3.0] Trideca-2,12-dimethylpentaenyl)
Zirconium dichloride (34) dimethylsilylenebis (9-bicyclo [8.
3.0] Trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride (35) dimethylsilylenebis (9-bicyclo [8.
3.0] Trideca-2-phenyl, 12-ethylpentaenyl) zirconium dichloride

(36) dimethylsilylene {1- (indenyl)} 1-(-4-hydroazulenyl) zirconium dichloride (37) dimethylsilylene {1- (2-methylindenyl)} 1- (2-methyl-4) -Hydroazulenyl)｝
Zirconium dichloride (38) dimethylsilylene {1- (2-methyl-4,5)
-Benzoindenyl) {1- (2,4-dimethyl-4)
-Hydroazulenyl) ニ ル zirconium dichloride (39) dimethylsilylene ｛1- (2-methyl-4phenylindenyl)｝ ｛1- (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (40) dimethylsilylene ｛1 -(2ethyl-4-phenylindenyl) {1- (2ethyl-4-hydroazulenyl)} zirconium dichloride (41) dimethylsilylene {1- (2,4-dimethylcyclopentadienyl)} 1- (2- Ethyl-4-methyl-4-hydroazulenyl) {zirconium dichloride (42) dimethylsilylene} 1- (2-methyl-4,5
-Benzoindenyl) {1- (2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (43) dimethylsilylene {1- (2-methyl-4-phenylindenyl)} 1- (2 , 4,4-trimethyl-4-hydroazulenyl) zirconium dichloride (44) dimethylsilylene {1- (2,4,7-trimethylindenyl)} 1- (2-methyl-4-phenyl-
6-isopropyl-4-hydroazulenyl) {zirconium dichloride (45) dimethylsilylene} 1- (2-ethyl-4,5
-Benzoindenyl) {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride (46) dimethylsilylene {1- (2-methyltetrahydroindenyl)} 1- ( 2-methyl-4,5,6
7,8-pentahydroazulenyl) {zirconium dichloride (47) dimethylsilylene} 1- (2-t-butyl-4)
-Methylcyclopentadienyl) {1- (2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride (48) dimethylsilylene} 1- (2-ethyl -4-phenylindenyl) {1- (4-methyl-4-hydroazulenyl)} zirconium dichloride (49) dimethylsilylene {1- (2-phenylindenyl)} 1- (4-phenyl-4-hydroazulenyl)}
Zirconium dichloride (50) dimethylsilylene {1- (2-propyl-4-)
Phenylindenyl) {1- (4-isopropyl-4)
-Hydroazulenyl) ニ ル zirconium dichloride (51) dimethylsilylene ｛1- (2-t-butylindenyl)｝ ｛1- (4-naphthylazulenyl)｝ zirconium dichloride

(52) (Methyl) (phenyl) silylenebis {1,1 ′-(4-hydroazulenyl)} zirconium dichloride (53) (methyl) (phenyl) silylenebis {1,1 ′
-(2-methyl-4-hydroazulenyl) {zirconium dichloride (54) (methyl) (phenyl) silylenebis} 1,1 '
-(2,4-dimethyl-4-hydroazulenyl) {zirconium dichloride (55) (methyl) (phenyl) silylenebis} 1,1 '
-(2-methyl-4-phenyl-4-hydroazulenyl) {zirconium dichloride (56) (methyl) (phenyl) silylenebis} 1,1 '
-(2-ethyl-4-hydroazulenyl) {zirconium dichloride (57) (methyl) (phenyl) silylenebis} 1,1 '
-(2-ethyl-4-methyl-4-hydroazulenyl) {zirconium dichloride (58) (methyl) (phenyl) silylenebis} 1,1 '
-(2-ethyl-4-phenyl-4-hydroazulenyl) {zirconium dichloride (59) (methyl) (phenyl) silylenebis} 1,1 '
-(2,4,4-trimethyl-4-hydroazulenyl) {zirconium dichloride (60) (methyl) (phenyl) silylenebis} 1,1 '
-(2-methyl-4-phenyl-6-isopropyl-4
-Hydroazulenyl) ニ ル zirconium dichloride (61) (methyl) (phenyl) silylenebis ｛1,1 '
-(2-methyl-4-phenyl-7-isopropyl-4
-Hydroazulenyl) ニ ル zirconium dichloride (62) (methyl) (phenyl) silylenebis ｛1,1 '
-(2-methyl-4,5,6,7,8-pentahydroazulenyl) {zirconium dichloride (63) (methyl) (phenyl) silylenebis} 1,1 '
-(2-methyl-4-phenyl-4,5,6,7,8-
Pentahydroazulenyl) zirconium dichloride

(64) diphenylsilylene bis ｛1,
1 '-(4-hydroazulenyl) ニ ル zirconium dichloride (65) diphenylsilylenebis ｛1,1'-(2-methyl-4-hydroazulenyl)｝ zirconium dichloride (66) diphenylsilylenebis ｛1,1 '-(2, 4
-Dimethyl-4-hydroazulenyl)｝ zirconium dichloride (67) diphenylsilylenebis ｛1,1 '-(2-methyl-4-phenyl-4-hydroazulenyl)｝ zirconium dichloride (68) diphenylsilylenebis ｛1,1'- (2-ethyl-4-hydroazulenyl) ニ ル zirconium dichloride (69) diphenylsilylenebis ｛1,1 '-(2-ethyl-4-methyl-4-hydroazulenyl)｝ zirconium dichloride (70) diphenylsilylenebis ｛1,1 '-(2-ethyl-4-phenyl-4-hydroazulenyl) {zirconium dichloride (71) diphenylsilylenebis} 1,1'-(2
4,4-trimethyl-4-hydroazulenyl) ニ ル zirconium dichloride (72) diphenylsilylenebis レ ン 1,1 '-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)｝ zirconium dichloride (73) diphenylsilylene Bis {1,1 ′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride (74) diphenylsilylene bis {1,1 ′-(2-methyl-4,5,6, 7,8-pentahydroazulenyl) zirconium dichloride (75) diphenylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium Dichloride

(76) Tetramethyldisilylenebis {1,1 ′-(4-hydroazulenyl)} zirconium dichloride (77) Tetramethyldisilylenebis {1,1 ′-(2
-Methyl-4-hydroazulenyl) {zirconium dichloride (78) tetramethyldisilylenebis} 1,1′-
(2,4-dimethyl-4-hydroazulenyl) {zirconium dichloride (79) tetramethyldisilylenebis} 1,1 ′-(2
-Methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (80) tetramethyldisilylenebis {1,1 '-(2
-Ethyl-4-hydroazulenyl) {zirconium dichloride (81) tetramethyldisilylenebis} 1,1 ′-(2
-Ethyl-4-methyl-4-hydroazulenyl) {zirconium dichloride (82) tetramethyldisilylenebis} 1,1 ′-(2
-Ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (83) tetramethyldisilylenebis {1,1'-
(2,4,4-trimethyl-4-hydroazulenyl)}
Zirconium dichloride (84) tetramethyldisilylenebis {1,1 '-(2
-Methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) {zirconium dichloride (85) tetramethyldisilylenebis} 1,1 ′-(2
-Methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) {zirconium dichloride (86) tetramethyldisilylenebis} 1,1 ′-(2
-Methyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride (87) tetramethyldisilylenebis {1,1 '-(2
-Methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride

(88) Dimethylsilylenebis {1,1 ′
-(2-trifluoromethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (89) dimethylsilylenebis {1,1 '-(2-ethyl-4-indolyl-4-hydroazulenyl)} zirconium dichloride (90) Dimethylsilylenebis {1,1 ′-(2-ethyl-4-phenoxy-4-hydroazulenyl)} zirconium dichloride (91) Dimethylsilylenebis {1,1 ′-(2-fluoro-4-pyrazolyl-4-hydroazulenyl) {Zirconium dichloride (92) silacyclohexylidenebis} 1,1 ′-(2
-Methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (93) silacyclohexylidenebis {1,1 '-(2
-Methyl-4-furyl-4-hydroazulenyl) zirconium dichloride

(94) Dimethylsilylene bis {1,1 '
-(2-methyl-4-trifluoromethyl-4-hydroazulenyl} zirconium dichloride (95) dimethylsilylenebis [1,1 '-{2-methyl-4- (2-fluorophenyl) -4-hydroazulenyl}] zirconium Dichloride (96) dimethylsilylenebis [1,1 ′-{2-methyl-4- (3-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (97) dimethylsilylenebis [1,1 ′-{2-methyl -4- (4-Fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (98) dimethylsilylenebis [1,1 '-{2-ethyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (99) dimethylsilylenebis [1,1 ′-{2-methyl-4- (2-k (Lorophenyl) -4-hydroazulenyl}] zirconium dichloride (100) dimethylsilylenebis [1,1 '-{2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (101) dimethylsilylenebis [1 , 1 '-{2-Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (102) dimethylsilylenebis [1,1'-{2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] zirconium dichloride (103) dimethylsilylenebis [1,1 '-{2-methyl-4- (2-trifluoromethylphenyl) -4-]
Hydroazulenyl}] zirconium dichloride (104) dimethylsilylenebis [1,1 ′-{2-methyl-4- (3-trifluoromethylphenyl) -4-
Hydroazulenyl}] zirconium dichloride (105) dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-trifluoromethylphenyl) -4-
Hydroazulenyl}] zirconium dichloride (106) dimethylsilylenebis [1,1 ′-{2-ethyl-4- (4-trifluoromethylphenyl) -4-
Hydroazulenyl}] zirconium dichloride (107) dimethylsilylenebis [1,1 ′-{2-methyl-4- (2,4-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (108) dimethylsilylenebis [1,1 '-{2-methyl-4- (2,5-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (109) dimethylsilylenebis [1,1'-{2-methyl-4- (2,6-difluoro) (Phenyl) -4-hydroazulenyl}] zirconium dichloride (110) dimethylsilylenebis [1,1 ′-{2-methyl-4- (3,5-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (111) dimethylsilylene Bis [1,1 ′-{2-methyl-4- (2,4,6-to Trifluorophenyl) -4
-Hydroazulenyl}] zirconium dichloride (112) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
[1- {2-methyl-4- (4-chlorophenyl) -4]
-Hydroazulenyl}] zirconium dichloride (113) dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-fluorophenyl) -6-isopropyl-4-hydroazulenyl}] zirconium dichloride (114) dimethylsilylenebis [ 1,1 '-$ 2,8
-Dimethyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (115) dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -6-ylpropyl-4- Hydroazulenyl}] zirconium dichloride (116) dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -7-iropropyl-4-hydroazulenyl}] zirconium dichloride (117) dimethylsilylenebis [1, 1 '-$ 2,8
-Dimethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (118) dimethylsilylenebis [1,1 '-{2-methyl-4- (4-trifluoromethylphenyl) -6-
Isopropyl-4-hydroazulenyl}] zirconium dichloride (119) dimethylsilylenebis [1,1 '-{2-methyl-4- (4-trifluoromethylphenyl) -7-
Isopropyl-4-hydroazulenyl}] zirconium dichloride (120) dimethylsilylenebis [1,1 '-{2,8
-Dimethyl-4- (4-trifluoromethylphenyl)
-4-Hydroazulenyl}] zirconium dichloride (121) dimethylsilylenebis [1,1 '-{2-methyl-4- (4-fluoro-α-naphthyl) -4-hydroazulenyl}] zirconium dichloride (122) dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-fluoro-β-naphthyl) -4-hydroazulenyl}] zirconium dichloride

(123) (Methyl) (phenyl) silylenebis [1,1 ′-{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (124) (methyl) (phenyl) silylenebis [1,
1 '-{2-methyl-4- (4-chlorophenyl) -4
-Hydroazulenyl}] zirconium dichloride (125) (methyl) (phenyl) silylenebis [1,
1 ′-{2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (126) diphenylsilylenebis [1,1 ′-{2-
Methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (127) diphenylsilylenebis [1,1 '-{2-
Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (128) diphenylsilylenebis [1,1 '-{2-
Methyl-4- (4-trifluoromethylphenyl) -4
-Hydroazulenyl}] zirconium dichloride (129) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (130) dimethylsilylene [1- {2-ethyl-4-
(4-fluorophenyl) dihydroazulenyl}] {1
-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (131) dimethylsilylene [1- {2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (132) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (133) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenyl-4,5,6,7,
8-pentahydroazulenyl) zirconium dichloride (134) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4- (4-fluorophenyl)-
4,5,6,7,8-pentahydroazulenyl) zirconium dichloride (135) dimethylsilylene [1- {2-ethyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-ethyl-4-phenyl-4,5,6,7,
8-pentahydroazulenyl) zirconium dichloride (136) dimethylsilylene [1- {2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenyl-4,5,6,7,
8-pentahydroazulenyl) zirconium dichloride (137) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4-phenyl-4,
5,6,7,8-pentahydroazulenyl) zirconium dichloride (138) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenylindenyl)} zirconium dichloride (139) dimethylsilylene [1- {2-ethyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-ethyl-4-phenylindenyl)} zirconium dichloride (140) dimethylsilylene [1- {2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4-phenylindenyl)} zirconium dichloride (141) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (142) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride (143) dimethylsilylene [1- {2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride (144) dimethylsilylene [1- {2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl}]
{1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride

(145) Dimethylsilylene [1- ｛2-
Methyl-4- (4-chlorophenyl) -4,5,6
7,8-pentahydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (146) dimethylsilylene [1- {2-methyl-4-
(4-fluorophenyl) indenyl}] {1- (2-
Methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (147) dimethylsilylene [1- {2-ethyl-4-
(4-fluorophenyl) indenyl}] {1- (2-
Ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (148) dimethylsilylene [1- {2-methyl-4-
(4-chlorophenyl) indenyl}] {1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (149) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) indenyl}]
{1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (150) dimethylsilylene [1- {2-methyl-4-
(4-trifluoromethylphenyl) indenyl}]
{1- (2-methyl-4- (4-chlorophenyl-4-)
(Hydroazulenyl)} zirconium dichloride (151) dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-fluorophenyl) cyclopentacyclooctenyl)} zirconium dichloride (152) dimethylsilylenebis [1,1 ′ -{2-Ethyl-4- (4-chlorophenyl) cyclopentacyclooctenyl)} zirconium dichloride (153) dimethylsilylenebis [1,1 '-} 2-methyl-5- (4-trifluoromethylphenyl) cyclo Pentacyclooctenyl) zirconium dichloride

Q = As a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum,
The following are mentioned. (1) dimethylgermanium bis (indenyl) zirconium dichloride, (2) dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl)
Zirconium dichloride, (4) phenylaluminum bis (indenyl) zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride, (6) ethylboranobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like. In addition, the following compounds may be mentioned as an azulene complex and a complex having a sub-membered ring having a larger number of carbon atoms.

(1) Dimethylgermylene bis {1,1 '
-(4-hydroazulenyl) zirconium dichloride (2) dimethylgermylene bis {1,1 '-(2-methyl-4-hydroazulenyl)} zirconium dichloride (3) dimethylgermylene bis {1,1'-(2 , 4-
Dimethyl-4-hydroazulenyl) zirconium dichloride (4) Dimethylgermylene bis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (5) Dimethylgermylene bis {1,1 ′ -(2-Ethyl-4-hydroazulenyl) {zirconium dichloride (6) dimethylgermylene bis} 1,1 ′-(2-ethyl-4-methyl-4-hydroazulenyl) {zirconium dichloride (7) dimethylgermylene bis} 1,1 ′-(2-ethyl-4-phenyl-4-hydroazulenyl) {zirconium dichloride (8) dimethylgermylene bis} 1,1 ′-(2,4
4-trimethyl-4-hydroazulenyl) zirconium dichloride (9) dimethylgermylene bis {1,1 '-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride (10) dimethylgermylene Bis {1,1 ′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride (11) Dimethylgermylene bis {1,1 ′-(2-methyl-4,5,6) , 7,8-Pentahydroazulenyl) zirconium dichloride (12) dimethylgermylene bis {1,1 '-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) {Zirconium dichloride (13) dimethylgermylene bis [1,1 ′-{2-methyl-4- (4-fluorophenyl) ) -4-Hydroazulenyl}] zirconium dichloride (14) dimethylgermylene bis [1,1 ′-{2-methyl-4- (4-chlorophenyl-4-hydroazulenyl}] zirconium dichloride (15) dimethylgermylene bis [1 , 1 '-{2-Methyl-4- (4-trifluorophenyl) -4-hydroazulenyl}] zirconium dichloride

(C) Examples of the compound represented by the general formula [3], that is, a transition metal compound having no binding group Q 'and having one conjugated five-membered ring ligand, include (1) pentamethyl Cyclopentadienyl-bis (phenyl) aminozirconium dichloride, (2) indenyl-bis (phenyl) amidozirconium dichloride,
(3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4)
Pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) cyclopentadienyl zirconium trichloride, (6) pentamethylcyclopentadienyl zirconium trichloride, (7) cyclopentadienyl zirconium benzyl dichloride, (8) cyclopenta Dienyl zirconium dichlorohydride,
(9) Cyclopentadienyl zirconium triethoxide and the like.

(D) Examples of the compound represented by the general formula [4], that is, a transition metal compound having one conjugated five-membered ring ligand bridged by a bonding group Q ', include (1) dimethylsilylene ( Tetramethylcyclopentadienyl) phenylamidozirconium dichloride,
(2) dimethylsilylene (tetramethylcyclopentadienyl) tert-butylamido zirconium dichloride, (3) dimethylsilylene (indenyl) cyclohexylamidozirconium dichloride, (4) dimethylsilylene (tetrahydroindenyl) decylamidozirconium dichloride, (5) ) Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride and (6) dimethylgermane (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride.

(E) Further, compounds obtained by replacing chlorine in the compounds (a) to (d) with bromine, iodine, hydride, methyl, phenyl and the like can also be used. Further, in the present invention, a compound in which zirconium is replaced by titanium, hafnium, niobium, molybdenum, tungsten or the like as the central metal of the zirconium compounds exemplified in the above (a) to (e) can be used as the component [A]. Among these, preferred are a zirconium compound, a hafnium compound and a titanium compound. More preferred are zirconium compounds and hafnium compounds.

As the component [B] of the present invention, an ion-exchange layered compound other than silicate or an inorganic silicate is used. These are compounds having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force to each other, and refer to the contained ion-exchangeable compounds. Most of these (hereinafter sometimes referred to as ion-exchanged layered silicates) are naturally produced mainly as a main component of clay minerals. Not only those but also artificial synthetic products.

Specific examples of ion-exchangeable phyllosilicates include, for example, “Clay Mineralogy” written by Haruo Shimizu, Asakura Shoten (19)
95)), a known layered silicate described in
Kaolins such as dickite, nacrite, kaolinite, anoxite, metahalloysite, halloysite, serpentine such as chrysotile, lizardite, antigolite, montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite Smectite group, vermiculite group such as vermiculite, mica group such as mica, illite, sericite, marine green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite. These may form a mixed layer.

Among these, montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Smectites such as teniolite, vermiculites and mica are preferred. As the component (B), a pore volume having a radius of 20 ° or more measured by a mercury intrusion method was 0.1%.
When a compound of less than cc / g is used, high polymerization activity tends to be difficult to obtain, so that a compound of 0.1 cc / g or more, particularly 0.3 to 5 cc / g, is preferred. Although the component [B] can be used without any particular treatment, it is also preferable to subject the component [B] to a chemical treatment. Here, the chemical treatment can be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay.

Specifically, treatment with a ball mill, sieving, etc., acid treatment by contact with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc., and organic acids such as formic acid, acetic acid, benzoic acid, etc.
Examples include alkali treatment, salt treatment, and organic substance treatment.
Acid treatment removes impurities on the surface and also removes A in the crystal structure.
The surface area is increased by eluting cations such as l, Fe, Mg and the like. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is,
Bulk ions play a pillar-like role in supporting the layered structure and are called pillars. Introducing another substance between layered substance layers is called intercalation.

Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ Zr (OR) ₄ , PO (O
Metal alcoholates such as R) ₃ , B (OR) ₃ [R is alkyl, aryl, etc.], [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ ,
[Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ )
₆ ] ^{+ and the} like. These compounds may be used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge
A polymer obtained by hydrolyzing a metal alcoholate such as (OR) ₄ or the like, a colloidal inorganic compound such as SiO _2, or the like can be coexisted. Examples of pillars include oxides formed by intercalating the hydroxide ions between layers and then heating and dehydrating.
The component [B] may be used as it is, or may be used after heat dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids.

In the present invention, before treatment with salts
Exchangeable group 1 containing ion-exchangeable phyllosilicate
More than 40%, preferably more than 60% of the metal cations,
Ion exchange with cations dissociated from the following salts
Preferably. For the purpose of such ion exchange
Salts used in salt treatment consist of group 2-14 atoms
A cation containing at least one atom selected from the group
Compound, preferably a group 2-14 atom
A group containing at least one atom selected from the group consisting of
And the group consisting of halogen atoms, inorganic acids and organic acids
At least one anion selected from the group consisting of:
And more preferably a group consisting of group 2-14 atoms
A cation containing at least one atom selected from the group consisting of:
Cl, Br, I, F, PO_Four, SO_Four, NO_Three, C
O_Three, C_TwoO_Four, ClO_Four, OCOCH _Three, CH_ThreeCO
CHCOCH_Three, OCI_Two, O (NO_Three)_Two, O (Cl
O_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, OC
l_Three, OCOH, OCOCH_TwoCH_Three, C_TwoH_FourO_FourYou
And C₆H_FiveO₇At least one selected from the group consisting of
And a species of anion. Specifically, C
aCl_Two, CaSO_Four, CaC _TwoO_Four, Ca (NO_Three)
_Two, Ca_Three(C₆H_FiveO₇)_Two, MgCl_Two, MgBr
_Two, MgSO_Four, Mg (PO_Four)_Two, Mg (ClO_Four)
_Two, MgC_TwoO_Four, Mg (NO_Three)_Two, Mg (OCOC
H_Three)_Two, MgC_FourH_FourO_Four, Sc (OCOC
H _Three)_Two, Sc_Two(CO_Three)_Three, Sc_Two(C
_TwoO_Four)_Three, Sc (NO_Three)_Three, Sc _Two(SO_Four)_Three,
ScF_Three, ScCl_Three, ScBr_Two, ScI_Three, Y (O
COCH_Three)_Three, Y (CH_ThreeCOCHCOCH_Three)_Three,
Y_Two(CO_Three)_Three, Y_Two(C_TwoO_Four)_Three, Y (NO_Three)
_Three, Y (ClO_Four)_Three, YPO_Four, Y_Two(SO_Four)_Three,
YF_Three, YCl_Three, La (OOCH_Three)_Two, La (CH
_ThreeCOCHCOCH_Three) _Three, La_Two(CO_Three)_Three, La
(NO_Three)_Three, La (ClO_Four)_Three, La_Two(C
_TwoO_Four)_Three, LaPO_Four, La_Two(SO_Four)_Three, LaF
_Three, LaCl_Three, LaBr_Three, LaI_Three, Sm (OCO
CH_Three)_Three, Sm (CH_ThreeCOCHCOCH_Three) _Three, S
m_Two(CO_Three)_Three, Sm (NO_Three)_Three, Sm (Cl
O_Four)_Three, Sm_Two(C _TwoO_Four)_Three, SmPO_Four, Sm_Two
(SO_Four)_Three, SmF_Three, SmCl_Three, SmBr_Three, S
mI_Three, Yb (OCOCH_Three)_Three, Yb (NO_Three)_Three,
Yb (ClO_Four)_Three, Yb (C_TwoO_Four)_Three, Yb_Two(S
O_Four)_Three, YbF_Three, YbCl_Three, Ti (OCOC
H_Three)_Four, Ti (CO_Three)_Two, Ti (NO_Three)_Four, Ti
(SO_Four)_Two, TiF_Four, TiCl_Four, TiBr_Four, T
iI_Four, Zr (OCOCH_Three)_Four, Zr (CO_Three)_Two,
Zr (NO_Three)_Four, Zr (SO_Four)_Two, ZrF_Four, Zr
Cl_Four, ZrBr_Four, ZrI_Four, ZrOCl_Two, ZrO
(NO_Three)_Two, ZrO (ClO _Four)_Two, ZrO (S
O_Four), Hf (OCOCH_Three)_Four, Hf (CO_Three)_Two,
Hf (NO_Three)_Four, Hf (SO_Four)_Two, HfOCl_Two,
HfF_Four, HfCl_Four, HfBr_Four, HrI_Four, V (C
H_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VOC
l _Three, VCl_Three, VCl_Four, VBr_Three, Nb (CH_ThreeC
OCHCOCH_Three)_Five, Nb_Two(CO_Three)_Five, Nb (N
O_Three)_Five, Nb_Two(SO_Four)_Five, ZrF_Five, ZrC
l_Five, NbBr_Five, NbI_Five, Ta (OCOC
H_Three)_Five, Ta_Two(CO_Three)_Five, Ta (NO_Three)_Five, T
a_Two(SO_Four)_Five, TaF_Five, TaCl_Five, TaB
r_Five, TaI_Five, Cr (OOCH_Three)_TwoOH, Cr (C
H_ThreeCOCHCOCH_Three)_Three, Cr (NO_Three)_Three, Cr
(ClO_Four)_Three, CrPO_Four, Cr_Two(SO_Four)_Three, C
rO_TwoCl_Two, CrF_Three, CrCl_Three, CrBr_Three, C
rI_Three, MoOCl_Four, MoCl_Three, MoCl_Four, Mo
Cl_Five, MoF₆, MoI_Two, WCl_Four, WCl ₆, W
F₆, WBr_Five, Mn (OOCH_Three)_Two, Mn (CH_Three
COCHCOCH _Three)_Two, MnCO_Three, Mn (NO_Three)
_Two, MnO, Mn (ClO_Four)_Two, MnF _Two, MnCl
_Two, MnBr_Two, MnI_Two, Fe (OCOCH_Three)_Two,
Fe (CH _ThreeCOCHCOCH_Three)_Three, FeCO_Three, F
e (NO_Three)_Three, Fe (ClO_Four) _Three, FePO_Four, F
eSO_Four, Fe_Two(SO_Four)_Three, FeF_Three, FeC
l_Three, FeBr_Three, FeI_Two, FeC₆H_FiveO₇, Co
(OCOCH_Three)_Two, Co (CH _ThreeCOCHCOC
H_Three)_Three, CoCO_Three, Co (NO_Three)_Two, CoC_TwoO
_Four, Co (ClO_Four)_Two, Co_Three(PO_Four)_Two, CoS
O_Four, CoF_Two, CoCl_Two, CoBr_Two, CoI_Two,
NiCO_Three, Ni (NO_Three)_Two, NiC_TwoO_Four, Ni
(ClO_Four)_Two, NiSO_Four, NiCl_Two, NiB
r_Two, Pb (OCOCH_Three)_Four, Pb (OOC
H_Three)_Two, PbCO_Three, Pb (NO_Three)_Two, PbS
O_Four, PbHPO_Four, Pb (ClO_Four)_Two, PbF_Two,
PbCl_Two, PbBr_Two, PbI_Two, CuI_Two, CuB
r_Two, Cu (NO_Three)_Two, CuC_TwoO_Four, Cu (ClO
_Four)_Two, CuSO_Four, Cu (OCOCH_Three)_Two, Zn
(OOCH_Three)_Two, Zn (CH_ThreeCOCHCOCH_Three)
_Two, ZnCO_Three, Zn (NO_Three)_Two, Zn (ClO_Four)
_Two, Zn_Three(PO_Four)_Two, ZnSO_Four, ZnF_Two, Zn
Cl_Two, ZnBr_Two, ZnI_Two, Cd (OCOCH_Three)
_Two, Cd (CH_ThreeCOCHCOCH_Three)_Two, Cd (OC
OCH_TwoCH_Three)_Two, Cd (NO_Three)_Two, Cd (ClO
_Four)_Two, CdSO_Four, CdF_Two, CdCl_Two, CdBr
_Two, CdI_Two, AlF_Three, AlCl_Three, AlBr_Three, A
lI_Three, Al_Two(SO_Four)_Three, Al_Two(C_TwoO_Four)_Three,
Al (CH_ThreeCOCHCOCH_Three)_Three, Al (NO_Three)
_Three, AlPO_Four, GeCl_Four, GeBr_Four, GeI_Four,
Sn (OCOCH_Three)_Four, Sn (SO_Four)_Two, Sn
F_Four, SnCl_Four, SnBr_Four, SnI_FourEtc.
You. The acid treatment removes impurities on the surface, and the crystal structure A
Part or all of cations such as l, Fe, Mg, etc. are eluted
Can be made.

The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid and acetic acid. The salt and the acid used for the treatment may be two or more. When the salt treatment and the acid treatment are combined, there are a method of performing the salt treatment and then performing the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The conditions for treatment with salts and acids are not particularly limited, but usually the concentration of salts and acids is 0.1 to 3
0% by weight, treatment temperature from room temperature to boiling point, treatment time from 5 minutes to
It is preferable to select a condition of 24 hours and to elute at least a part of at least one compound contained in the ion-exchange layered silicate. Further, salts and acids are generally used in an aqueous solution.

In the present invention, the above-mentioned salt treatment and / or acid treatment is preferably performed, but shape control may be performed by pulverization or granulation before, during, or after the treatment. Further, a chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the component [B].

Here, the adsorbed water is water adsorbed on the surface of the ion-exchanged layered silicate compound particles or the crystal fracture surface, and the interlayer water is water existing between the crystal layers. In the present invention, these adsorbed water and / or interlayer water can be removed by heat treatment before use. The method of heat treatment of the adsorbed water and interlayer water of the ion-exchanged layered silicate is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. Can be The temperature at the time of heating cannot be specified unconditionally because it depends on the type of ion-exchange layered silicate and interlayer ions. However, the temperature is 100 ° C. or higher, preferably 150 ° C. or higher so that interlayer water does not remain. Is not preferable (for example, 800 ° C. or higher, depending on the heating time). Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. The heating time is at least 0.5 hour, preferably at least 1 hour. At that time, [B] after removal
The moisture content of the component is preferably 3% by weight or less, more preferably 1% by weight or less, when the moisture content when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight. .

As described above, in the present invention, particularly preferred as the component (B) are those obtained by performing salt and / or acid treatment and having a water content of 1% by weight or less.
It is an ion-exchange layered silicate. As the component (B), it is preferable to use spherical particles having an average particle diameter of 5 μm or more.
More preferably, spherical particles having an average particle size of 10 μm or more are used. More preferably, the average particle size is 10 μm or more and 100
Use spherical particles of μm or less. The average particle size here is
The particle size is represented by a number average particle size calculated by image processing of an optical micrograph (magnification: 100 times) of the particles. As the component (B), a natural product or a commercially available product may be used as it is, as long as the shape of the particle is spherical, or a product obtained by controlling the shape and particle size of the particle by granulation, sizing, sorting, or the like. You may.

The granulation method used here includes, for example, stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsion granulation. And a submerged granulation method and a compression molding granulation method, but are not particularly limited as long as the method can granulate the component [B]. Preferred examples of the granulation method include a stirring granulation method, a spray granulation method, a tumbling granulation method, and a fluidized granulation method, and particularly preferably include a stirring granulation method and a spray granulation method. When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene and xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as the dispersion medium. The concentration of the component [B] of the raw slurry liquid for spray granulation to obtain spherical particles is 0.1 to 70%, preferably 1 to 70%.
It is 50%, particularly preferably 5 to 30%. The temperature at the inlet of the hot air for spray granulation to obtain spherical particles varies depending on the dispersing medium, but when water is used as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

In the granulation, an organic substance, an inorganic solvent, an inorganic salt and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethyl celluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein,
Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel,
Gum arabic, sodium alginate and the like can be mentioned. The spherical particles obtained as described above preferably have a compressive breaking strength of 0.2 MPa or more in order to suppress crushing and fine powder in the polymerization step. In the case of such a particle strength, the effect of improving the particle properties is effectively exhibited, particularly when prepolymerization is performed.

The component [C] in the present invention is a nitrogen-containing or phosphorus-containing compound, and generally known compounds can be used. For example, examples of nitrogen-containing compounds include ethylamine, butylamine, cyclohexylamine, naphthylamine, aniline, N, N-dimethylaniline, anisidine, phenetidine, toluidine, xylidine, diethylamine, triethylamine, amines such as tetramethylenediamine, piperidine, pyridazine. , Heterocycles such as pyridine, hexaneamide, acetamide, benzenesulfonamide, imidazole-2-carboxamide, succinamide, maleamide, malamide, oxamide, alaninamide, N-methylbenzamide, acetanilide, diacetamide, triacetamide, dibenzamide, Amides such as tribenzamide, 1,2-cyclohexanedicarboximide, succinimide, N-phenylphthalimide, 2, , Imides such as 6-piperidinetrione, nitriles such as acetonitrile, hexanenitrile, benzonitrile, hexanedinitrile, cyclohexanecarbonitrile, 1,3,6-hexanetricarbonitrile, 2-thiazolecarbonitrile, benzoylcyanide , N-phenylhydroxylamine,
Hydroxylamines such as N, N-dimethylhydroxylamine, nitroso compounds such as nitrosobenzene, 1-methyl-nitrosourea, nitro compounds such as nitromethane, nitroethane, nitropropane, nitrobenzene, nitronaphthalene, nitrotoluene, nitrourea,
Alternatively, silazanes such as hexamethyldisilazane and the like can be mentioned. Of these, nitriles, pyridine and piperidine are preferred.

On the other hand, examples of the phosphorus-containing compound include C_TwoH
_FivePH_Two, C₆H_FivePH_Two, P (CH_Three)_Three, P (C₆
H_Five)_Three, (CH_Three)_TwoPC_TwoH_FourP (CH_Three)_Two,
(C₆H_Five)_TwoPC_TwoH_FourP (C₆H_Five)_Two, H_TwoPC
H_TwoCOOH, CH_ThreeCOP (C_TwoH_Five)_Two, H_TwoNC
OPH_Two, C₆H_FiveSO_TwoPH_Two, OC (PH_Two)_Two,
[(C_TwoH_Five)_TwoP] Na, PH_Three, H_TwoPOH, HP
(OH)_Two, P (OH) 3, (C₆H_Five)_TwoPOCH_Three,
(C₆H_Five)_TwoPCl, C₆H_FiveP (OH)_Two, C ₆H
_FivePCl_Two, P (OCH_Three)_Three, P (OC₆H_Five)_Three,
(C₆H_Five)_ThreePO, (C₆H_Five)_ThreeP (NC
₆H_Five), (C₆H_Five)_ThreePCH_Two, (C_TwoH_Five)_TwoP
S (SH), (CH_Three)_TwoNPO (OH)_Two, (C₆H
_Five)_TwoP (NC₆H_Five) (OH), (C₆H_Five)_TwoPO
(OH), C_TwoH_FivePO (OH)_Two, C₆H_FiveP (N)
OH, (HO)_Two(O) PCH_TwoCOOH, (C
_TwoH_Five) HPO (OH), C₆H_FivePO (Cl) (O
H), PO (OCH)_Three, PO (OCH_Three) (O
H)_Two, C₆H_FivePHS (OCH_Three), HPO (OCH
_Three)_Two, (C_TwoH_Five)_TwoPS (SC_TwoH_Five), CH_ThreeP
O (OC_TwoH_Five)_Two, C₆H_FivePOCl (OC
H_Three)_Two, PO [(CH_Three)_TwoN] (OCH_Three)_Two, (C_Two
H_Five)_TwoPCl (NC₆H_Five), CH_ThreeCOOPO (O
H)_Two, CH_ThreeCOOPO (CH_Three)_Two, P (C
₆H _Five)_Five, (C₆H_Five)_ThreePCl_TwoAnd the like.
Of these, trialkylphosphine or triarylphosphine
Lulephosphine is preferred. Such a component [C] is simply
They may be used alone or in combination of two or more.

The organoaluminum compound optionally used as the component (D) in the present invention has the general formula

[0064]

Embedded image AlR _a T _3-a

(Wherein, R is a hydrocarbon group having 1 to 20 carbon atoms, T is hydrogen, a halogen, an alkoxy group, and a is 0 <a ≦
3 number). Specific examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, or halogen or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide.
Of these, trialkyl aluminum is particularly preferred.

The method of contacting the component [A], the component [B], the component [C] and the component [D] used as required is not particularly limited. All the components [A] to [D] are brought into contact simultaneously.
After contacting the components [A], [B] and [C], the component [D] is brought into contact. After the components [A], [B] and [D] are brought into contact, the component [C] is brought into contact. [A], [C],
After contacting the component [D], the component [B] is brought into contact.
After contacting the components [B], [C] and [D], the component [A] is brought into contact.

This contact not only occurs when the catalyst is adjusted, but also when the catalyst is adjusted.
It may be performed at the time of prepolymerization with olefin or at the time of polymerization of olefin. In addition, the three components may be contacted simultaneously. Upon or after the contact of each component of the catalyst, an olefin polymer, a styrene-based polymer, an acrylic polymer or the like, or a copolymer thereof, or a solid of an inorganic oxide such as silica or alumina coexists, or May be. The contact may be performed in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, and preferably between room temperature and the boiling point of the solvent.

The amount of each component of the catalyst used is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol of the [A] component per 1 g of the [B] component, and 0 to 5 mmol per 1 g of the [B] component. 0.000001 to 10000 mm
ol, preferably 0.001 to 100 mmol,
If necessary, add component [D] to component (B) in an amount of 0.0
1-10000 mmol, preferably 0.1-100 m
mol. Further, the transition metal in the component [A] and the component [C]
The molar ratio of aluminum atoms in the component and the component [D] is 1: 0.1 to 1000: 0.01 to 1,000,000, preferably 1: 1 to 100: 0.1 to 100,000. The catalyst thus obtained may be washed after preparation or may be used as it is as an olefin polymerization catalyst without washing.

As the olefin used for the polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or any of these Derivatives and the like. In addition to homopolymerization, it can be suitably used for generally known random copolymerization and block copolymerization. Further, it can be used for copolymerization of a diene compound such as butadiene, 1,5-hexadiene, 1,7-octadiene, methyl-1,4-hexadiene, methyl-1,7-octadiene and the above-mentioned olefins.

Before the polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane are prepared using the catalyst of the present invention. And olefins such as styrene may be preliminarily polymerized. This preliminary polymerization is preferably carried out in an inert solvent under mild conditions, and is preferably carried out so as to produce 0.01 to 1000 g, preferably 0.1 to 100 g, of a polymer per 1 g of the solid catalyst. .

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene or cyclohexane or a liquefied α-olefin. The temperature is from -50 ° C to 250 ° C, and the pressure is not particularly limited.
000 kg · f / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system. Furthermore,
The polymerization may be performed in multiple stages by changing the polymerization temperature, the concentration of the molecular weight regulator, and the like.

[0072]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples unless departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated with Molecular Sieves 4A, and then degassed by bubbling with purified nitrogen. In the examples, the MFR was measured at 190 ° C. under a load of 2.16 kg in accordance with ASTM D1238. In addition,
In measuring the MFR, 0.1% by weight of 2,6-di-t-butylparacresol was added to the polymer.

[0073] Example _{1 (1) ZnSO 4 · 7H} 2 O 52 chemical treatment commercially available synthetic mica 30g of clay minerals.
5 g was dissolved in 600 ml of demineralized water and 90
Stirred at C for 3 hours. After the treatment, this solid component was washed with demineralized water and dried to obtain a Zn salt-treated synthetic mica.

(2) Heat Dehydration Treatment of Clay Mineral 10.0 g of the Zn salt-treated synthetic mica obtained in (1) was placed in a 200 ml flask and subjected to heat dehydration treatment at 200 ° C. for 2 hours under reduced pressure. The weight loss of 1.16 g was recognized by this dehydration treatment. (3) Synthesis of catalyst component 1.0 g of the Zn salt-treated synthetic mica obtained in (2) was placed in a 100 ml flask, and dispersed in 7 ml of toluene to form a slurry. Then, at room temperature, with stirring, 0.43 ml of triethylaluminum was added. After contacting at room temperature for 1 hour, the supernatant was extracted and the solid portion was washed with toluene. Toluene was added to this to form a slurry, and a toluene solution of bis (cyclopentadienyl) zirconium dichloride (4.0 μmol / ml) was added for 20.0 m.
and stirred at room temperature for 1 hour to obtain a catalyst component.

(4) Copolymerization of ethylene-1-butene In a 2-liter induction-stirring autoclave sufficiently purged with purified nitrogen, 840 ml of normal hexane, 0.24 mmol of triethylaluminum, 24.0 pyridine were used.
μmol and 160 ml of 1-butene were added, and the temperature was raised to 70 ° C. Next, 30.0 mg of the catalyst component obtained in the above (3) was introduced as a solid catalyst together with ethylene, the total pressure was kept at 25 kg · f / cm ^2, and polymerization was carried out for 1 hour while stirring was continued. The polymerization was stopped by adding 10 ml of ethanol. The amount of the obtained ethylene-1-butene copolymer was 60 g, and the MFR was 0.89.

Example 2 (1) Copolymerization of ethylene-1-butene In the same manner as in Example 1, except that pyridine was changed to 4.8 μmol of benzonitrile in (4) of Example 1, ethylene-1-butene was used. Was copolymerized, the resulting ethylene-1-butene copolymer was 35 g, and had a MF
R was 0.44.

Example 3 (1) Copolymerization of ethylene-1-butene In the same manner as in Example 1 except that pyridine was changed to 4.8 μmol of acetonitrile in (4) of Example 1, ethylene-1-butene was used. When copolymerization was performed, the amount of the obtained ethylene-1-butene copolymer was 30 g, and the MF was MF.
R was 0.24.

Example 4 (1) Copolymerization of ethylene-1-butene Ethylene-1-butene was prepared in the same manner as in Example 1 except that pyridine was changed to trimethylphosphine in (4) of Example 1.
When 1-butene was copolymerized, the obtained ethylene-1-butene copolymer was 35 g, and had an MFR of 0.8.
It was 2.

Comparative Example 1 (1) Copolymerization of ethylene-1-butene Copolymerization of ethylene-1-butene was carried out in the same manner as in Example 1 except that pyridine was not added in (4) of Example 1. As a result, the amount of the obtained ethylene-1-butene copolymer was 250 g, and the MFR was 1.48.

[0080]

According to the present invention, a high molecular weight olefin polymer can be obtained, which is extremely useful industrially.

Claims (5)

[Claims] [A] a conjugated five-membered ring ligand having at least one
Characterized in that it contains a transition metal compound belonging to Groups 4 to 6 of the periodic table, [B] an ion-exchange layered compound or an inorganic silicate excluding silicate, and [C] a nitrogen- or phosphorus-containing compound. catalyst. 2. The olefin polymerization catalyst according to claim 1, further comprising an organoaluminum compound as the component [D]. Wherein component (D) is embedded image AlR _a T _3-a (wherein, R represents a hydrocarbon group having 1 to 20 carbon atoms, T is hydrogen, halogen, alkoxy group, siloxy group Indicate a.
Represents an integer of 0 <a ≦ 3. 3. The catalyst for olefin polymerization according to claim 2, which is a compound represented by the formula: 4. Component (A) is represented by the following general formula (1):
The olefin polymerization catalyst according to any one of claims 1 to 3, wherein the catalyst is a compound represented by [2], [3] or [4]. Embedded image (Where A and A ′ represent conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q represents two conjugated five-membered ring ligands. And Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group, and Q ′ is a conjugated group. A binding group bridging any position of the five-membered ring ligand with Z; M represents a metal atom selected from Groups 4 to 6 of the periodic table; X and Y represent a hydrogen atom, a halogen atom, or a hydrocarbon Group,
It represents an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. ) 5. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.