JP2003113209A - Catalyst for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst capable of rapidly increasing particle diameter in a reactor and reducing fine particle trouble such as aggregation or sticking due to a high olefin polymerization activity possessed thereby and further realizing industrial long-term stable operation due to no occurrence of particle crushing and economically excellent due to the high olefin polymerization activity possessed thereby. SOLUTION: This catalyst for polymerizing an olefin is obtained by bringing components [A], [B], [C] and, as necessary, [D] into contact with each other. Component [A] is a compound of groups 4 to 6 transition metals of the periodic table having a conjugated 5-membered ring ligand; component [B] is a phyllosilicate; component [C] is an organic compound in which a group 15 atom of the periodic table having at least one active hydrogen is directly bound to one carbon atom in the 5- to 14-membered ring structure and at least one 1-30C hydrocarbon group is bounded to other carbon atoms forming the ring structure; and component [D] is an organoaluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the catalyst. More specifically, by using an organic compound having a specific structure containing a group 15 atom of the periodic table, an olefin polymer can be obtained with higher activity than ever before.
The present invention provides a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, there has been proposed a method using a catalyst composed of (1) a metallocene compound, (2) an ion-exchange layered compound, an inorganic silicate, etc. Kaihei 5-301
No. 917 and No. 8-127613). In the polymerization method using these catalysts, a conventional so-called methylalumoxane is used by supporting it on a carrier such as an inorganic oxide such as silica or alumina, or an organic substance (JP-A-60-350).
No. 07, No. 61-31404, No. 61-108610.
No. 61-276805, No. 61-296008, etc.), the polymerization activity per transition metal and Al as well as per solid component is high, but it cannot be said to be sufficient and further improvement. Was needed.

[0003]

The present invention solves the above problems and provides an olefin polymerization catalyst capable of obtaining an olefin polymer with higher activity, and an olefin polymerization method using the same.

[0004]

Means for Solving the Problems The present invention has been made as a result of extensive studies aimed at achieving such an object. Specifically, the invention according to claim 1 is as follows. An olefin polymerization catalyst obtained by contacting the following component [A], component [B], component [C] and, if necessary, component [D]. Component [A]: Periodic Table No. 4 to 5 having a conjugated five-membered ring ligand
Group 6 transition metal compound component [B]: Layered silicate component [C]: Group 15 atom of the periodic table having at least one active hydrogen is directly attached to one carbon atom in a 5- to 14-membered ring structure. Organic compound component [D] in which at least one hydrocarbon group having 1 to 30 carbon atoms is bonded to another carbon atom which is bonded and forms the ring structure: an organoaluminum compound

The present invention also resides in a method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst. The atomic periodicity in the present invention is based on the Group 18 system recommended by IUPAC in 1989.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Component [A] <Transition metal compound of Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand> Component [A] used in the present invention is represented by the following general formula [1]. ], [2], [3] or [4]. [Wherein A and A ′ are ligands having the same or different conjugated five-membered ring structures, Q is a bonding group bridging two conjugated five-membered ring ligands at any position, and M is A transition metal atom of Group 4 to 6 of the periodic table, Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to M, a hydrogen atom, a halogen atom or a hydrocarbon. Base,
Q'is a bonding group bridging Z with any position of the conjugated five-membered ring ligand, and X and Y are hydrogen atoms bonded to M,
Halogen atom, hydrocarbon group, alkoxy group, amino group,
A phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group are shown, respectively. ]

A and A'are conjugated five-membered ring ligands,
As described above, these may be the same or different in the same compound. A typical example of this conjugated five-membered ring ligand is a conjugated carbon five-membered ring ligand, that is, a cyclopentadienyl group. The cyclopentadienyl group may have 5 hydrogen atoms, or may be a derivative thereof, that is, some of the hydrogen atoms may be substituted with a substituent.

One specific example of this substituent has 1 to 1 carbon atoms.
Although it is a hydrocarbon group of 20, preferably 1 to 12, this hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are Each of them may be bonded at the other end (ω-end) to form a ring together with a part of the cyclopentadienyl group. As a typical example of the latter, those in which two substituents are bonded at their ω-ends to share two adjacent carbon atoms in the cyclopentadienyl group to form a condensed six-membered ring That is, an indenyl group can be mentioned. Further, a fluorenyl group in which two condensed 6-membered rings are bonded to the conjugated position of a cyclopentadienyl group and an azulenyl group forming a condensed 7-membered ring can be mentioned.

Therefore, a typical example of the conjugated five-membered ring ligand can be a substituted or unsubstituted cyclopentadienyl group, indenyl group or fluorenyl group, and azulenyl group. As the substituent of the cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups (for example, a silicon atom containing —Si (R ¹ ))
(A group having about 1 to 24 carbon atoms in the form of (R ² ) (R ³ )),
Phosphorus-containing hydrocarbon group (e.g., a phosphorus atom -P (R ¹⁾
(A group having about 1 to 18 carbon atoms in the form of (R ² )), a nitrogen-containing hydrocarbon group (for example, a nitrogen atom is —N (R ¹ ) (R ² ).
In the form of a group having about 1 to 18 carbon atoms) or a boron-containing hydrocarbon group (for example, a boron atom containing -B (R ¹ )).
(A group having about 1 to 18 carbon atoms in the form of (R ² )).
When there are a plurality of these substituents, the respective substituents may be the same or different.

Q is a bonding group which bridges between two conjugated five-membered ring ligands at any position, and Q'is a bonding group which bridges between any position of the conjugated five-membered ring ligand and a Z group. Represents a group. Specifically, Q and Q ′ are (a) a methylene group, an ethylene group,
1 to 2 carbon atoms such as isopropylene group, phenylmethylmethylene group, diphenylmethylene group and cyclohexylene group
An alkylene group of 0, (b) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisilirene group, or other silylene group, (ha) germanium, phosphorus, nitrogen, boron or aluminum A hydrocarbon group containing, specifically (CH
₃ ) ₂ Ge group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C
₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH
₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C
₆ H ₅ ) Al group, (CH ₃ O) Al group and the like. Preferred are alkylene groups and silylene groups.

Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to M, a hydrogen atom, a halogen atom or a hydrocarbon group.
Specific examples of preferable Z include oxygen (—O).
-), Sulfur (-S-), 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 4 carbon atoms
0, preferably 1-18 nitrogen-containing hydrocarbon groups, 1-40 carbon atoms, preferably 1-18 phosphorus-containing hydrocarbon groups,
It is a hydrogen atom, chlorine, bromine, or a hydrocarbon group having 1 to 20 carbon atoms.

X and Y are each hydrogen, a halogen atom,
1 to 20 carbon atoms, preferably 1 to 10 hydrocarbon groups, 1 to 20 carbon atoms, preferably 1 to 10 alkoxy groups, amino groups, 1 to 20 carbon atoms, preferably 1 to 12 phosphorus-containing hydrocarbons A group (specifically, for example, a diphenylphosphine group) or a carbon number of 1 to 20, preferably 1 to 12
Is a silicon-containing hydrocarbon group (specifically, for example, a trimethylsilyl group or a bis (trimethylsilyl) methyl group). X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group (especially one having 1 to 8 carbon atoms) and an amino group are preferable.

Therefore, in the olefin polymerization catalyst according to the present invention, the general formula [1] preferred as the component [A],
Among the compounds represented by [2], [3] or [4], particularly preferable compounds are those having respective substituents having the following contents. A, A ′ = cyclopentadienyl, n-butyl-cyclopentadienyl, dimethyl-cyclopentadienyl, diethyl-cyclopentadienyl, ethyl-
n-butyl-cyclopentadienyl, ethyl-methyl-
Cyclopentadienyl, n-butyl-methyl-cyclopentadienyl, indenyl, 2-methyl-indenyl,
2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-
Methyl-benzoindenyl, 4-hydroazulenyl,
2,4-dimethylhexahydroazurenyl, 2-methyl-4-phenyl-4H-azurenyl, 2-methyl-4-
Phenyl-hexahydroazulenyl (in the above, the position of the substituent is preferably the 1-position and / or the 3-position).
Q, Q ′ = ethylene, dimethylsilylene, isopropylidene, Z = t-butylamide, phenylamide, cyclohexylamide, X, Y = chlorine atom, methyl, diethylamino.

In the present invention, the component [A] is within the group of compounds represented by the same general formula, and / or
It can be used as a mixture of two or more kinds of compounds represented by different general formulas. Below, M is H
In the case of f (hafnium) atom, the compound will be specifically exemplified.

(A) A compound represented by the general formula [1], that is, a hafnium compound having no conjugated group Q and two conjugated five-membered ring ligands: (1) Bis (cyclopentadienyl) Hafnium dichloride, (2) bis (methylcyclopentadienyl) hafnium dichloride, (3) bis (dimethylcyclopentadienyl) hafnium dichloride, (4) bis (trimethylcyclopentadienyl) hafnium dichloride,
(5) Bis (tetramethylcyclopentadienyl) hafnium dichloride, (6) bis (pentamethylcyclopentadienyl) hafnium dichloride, (7) bis (i
-Propylcyclopentadienyl) hafnium dichloride, (8) bis (n-butylcyclopentadienyl) hafnium dichloride, (9) bis (t-butylcyclopentadienyl) hafnium dichloride, (10) bis (ethyl-n) -Butyl-cyclopentadienyl) hafnium dichloride,

(11) Bis (ethyl-methyl-cyclopentadienyl) hafnium dichloride, (12) bis (n-butyl-methyl-cyclopentadienyl) hafnium dichloride, (13) (cyclopentadienyl)
(N-Butyl-cyclopentadienyl) hafnium dichloride, (14) (cyclopentadienyl) (ethyl-
Methyl-cyclopentadienyl) hafnium dichloride, (15) (n-butylcyclopentadienyl) (dimethylcyclopentadienyl) hafnium dichloride,
(16) Bis (indenyl) hafnium dichloride,
(17) Bis (tetrahydroindenyl) hafnium dichloride, (18) bis (2-methylindenyl) hafnium dichloride, (19) bis (2-methyltetrahydroindenyl) hafnium dichloride, (20) bis (fluorenyl) hafnium dichloride ,

(21) Bis (cyclopentadienyl) hafnium monochloride monohydride, (22) bis (cyclopentadienyl) methylhafnium monochloride, (23) bis (cyclopentadienyl) ethylhafnium monochloride, ( 24) bis (cyclopentadienyl) phenyl hafnium monochloride, (25) bis (cyclopentadienyl) hafnium dimethyl, (2)
6) bis (cyclopentadienyl) hafnium diphenyl, (27) bis (cyclopentadienyl) hafnium dinopentyl, (28) bis (cyclopentadienyl) hafnium dihydride, (29) (cyclopentadienyl) (Indenyl) hafnium dichloride,
(30) (cyclopentadienyl) (fluorenyl) hafnium dichloride, (31) (cyclopentadienyl) (azurenyl) hafnium dichloride, etc.,

(B) A compound represented by the general formula [2], that is, a hafnium compound having a binding group Q, for example, (b-1) Q = alkylene group: (1) methylenebis (indenyl) hafnium dichloride, (2) Ethylenebis (indenyl) hafnium dichloride, (3) ethylenebis (indenyl) hafnium monochloride monohydride, (4) ethylenebis (indenyl) methylhafnium monochloride, (5)
Ethylene bis (indenyl) hafnium monomethoxide monochloride, (6) ethylene bis (indenyl) hafnium diethoxide, (7) ethylene bis (indenyl) hafnium dimethyl, (8) ethylene bis (4,
5,6,7-Tetrahydroindenyl) hafnium dichloride, (9) ethylenebis (2-methylindenyl)
Hafnium dichloride, (10) ethylenebis (2-ethylindenyl) hafnium dichloride,

(11) ethylenebis (2,4-dimethylindenyl) hafnium dichloride, (12) ethylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) hafnium dichloride, (13) ethylene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-
Methylcyclopentadienyl) hafnium dichloride,
(14) Ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, (15) Ethylene-1,2-bis (4-indenyl) ) Hafnium dichloride, (16) ethylene 1,2-bis [4- (2,7-
Dimethylindenyl)] hafnium dichloride, (1
7) Ethylene 1,2-bis (4-phenylindenyl)
Hafnium dichloride, (18) isopropylidene bis (indenyl) hafnium dichloride, (19) isopropylidene (2,4-dimethylcyclopentadienyl)
(3 ′, 5′-dimethylpentadienyl) hafnium dichloride, (20) ethylenebis (indenyl) hafnium monochloride monohydride,

(21) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium mono Chloride monohydride, (23) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dimethyl, (24) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium Diphenyl, (25) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, (26) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, (27) isopropylidene (cyclopene) Dienyl) (3,4-dimethyl cyclopentadienyl) hafnium dichloride, (28)
Isopropylidene (cyclopentadienyl) (2,3,
4,5-Tetramethylcyclopentadienyl) hafnium dichloride, (29) isopropylidene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, (30) isopropylidene (cyclopentadienyl) (fluorenyl) hafnium Dichloride,

(31) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, (32) isopropylidene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, (33) isopropylidene (2,5-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) hafnium dichloride, (34) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ( 35)
Ethylene (cyclopentadienyl) (3,5-dimethylpentadienyl) hafnium dichloride, (36) ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, (37) ethylene (2,5-dimethylcyclopentadienyl) ) (Fluorenyl) hafnium dichloride, (38) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (39) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) Hafnium dichloride, (40) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, (41) cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, 42) cyclohexylidene (2,5
-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) hafnium dichloride,
(43) Dichloro {1,1'-dimethylmethylenebis [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} hafnium, (44) dichloro {1,1'-
Trimethylenebis [2-methyl-4- (4-biphenylyl) -4H-azulenyl]} hafnium,

(B-2) Compound having Q = silylene group: (1) dimethylsilylenebis (indenyl) hafnium dichloride, (2) dimethylsilylenebis (4,5,5)
6,7-Tetrahydroindenyl) hafnium dichloride, (3) Dimethylsilylenebis (2-methylindenyl) hafnium dichloride, (4) Dimethylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, (5) Dimethylsilylene Bis (2-methyl-4,
5,6,7-Tetrahydroindenyl) hafnium dichloride, (6) dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, (7) dimethyl Silylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, (8) Dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, (9) Dimethylsilylenebis (2-methyl-4) , 4-Dimethyl-4,5,6,7-tetrahydro-4-cyraindenyl) hafnium dichloride, (1
0) dimethylsilylenebis [4- (2-phenylindenyl)] hafnium dichloride,

(11) Dimethylsilylenebis [4- (2
-T-butylindenyl) hafnium dichloride, (1
2) Dimethylsilylene bis [4- (2-phenyl-3-
Methylindenyl)] hafnium dichloride, (13)
Dimethylsilylene bis [4- (2-methyl-4,5,5
6,7-Tetrahydroindenyl)] hafnium dichloride, (14) phenylmethylsilylenebis (indenyl) hafnium dichloride, (15) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, (16) ) Phenylmethylsilylene (2,4-dimethylcyclopentadienyl)
(3 ′, 5′-Dimethylcyclopentadienyl) hafnium dichloride, (17) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ′, 4 ′, 5′-trimethylcyclopentadienyl) hafnium dichloride, (18) phenylmethylsilylenebis (tetramethylcyclopentadienyl) hafnium dichloride, (19) diphenylsilylenebis (indenyl) hafnium dichloride, ( 20) tetramethyldisilylenebis (indenyl) hafnium dichloride,

(21) Tetramethyldisilylenebis (cyclopentadienyl) hafnium dichloride, (22)
Tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) hafnium dichloride, (23)
Dimethylsilylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) hafnium dichloride, (24) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, (25) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium Dichloride, (26) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, (27) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) hafnium dichloride, (28) ) Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) hafnium dichloride, (29) dimethylsilylene (cyclopentadienyl) (fluorenyl)
Hafnium dichloride, (30) dimethyl silylene (3
-T-butyl-cyclopentadienyl) (fluorenyl) hafnium dichloride,

(31) Dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, (32) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) hafnium Dichloride, (33) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, (34) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (35) dimethylsilylene ( 2-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (36) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (37) diethylsilylene (2-methylcyclopentadiene) Le) (2 ', 7'-di -t- butyl-fluorenyl) hafnium dichloride, (38) dimethylsilylene (2,5-dimethyl-cyclopentadienyl)
(2 ′, 7′-di-t-butylfluorenyl) hafnium dichloride, (39) dimethylsilylene (2-ethylcyclopentadienyl) (2 ′, 7′-di-t-butylfluorenyl) hafnium Dichloride, (40) dimethylsilylene (diethylcyclopentadienyl) (2 ',
7'-di-t-butylfluorenyl) hafnium dichloride,

(41) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (42) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (43) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (44) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, (45) dimethylsilylene bis [1- (2-methyl-4-phenyl-4
H-azurenyl)] hafnium dichloride, (46) dichloro {1,1′-dimethylsilylenebis [2-i-propyl-4- (4-biphenylyl) -4H-azurenyl]} hafnium, (47) dichloro {1, 1'-Dimethylsilylenebis [2-methyl-4- (2-fluoro-
4-biphenylyl) -4H-azulenyl]} hafnium, (48) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl]} hafnium, ( 49) Dichloro {1,1′-dimethylsilylenebis [2-methyl-
4- (4-chlorophenyl) -4H-azurenyl]} hafnium, (50) dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (2 ', 6'-dimethyl-
4-biphenylyl) -4H-azulenyl]} hafnium,

(51) Dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (1-naphthyl) -4H
-Azurenyl]} hafnium, (52) dichloro {1,
1'-Dimethylsilylenebis [2-i-propyl-4-
(1-naphthyl) -4H-azulenyl]} hafnium,
(53) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (2-naphthyl) -4H-azurenyl]} hafnium, (54) Dichloro {1,1'-dimethylsilylenebis [2-i -Propyl-4- (4-t-
Butylphenyl) -4H-azulenyl]} hafnium,
(55) Dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (9-anthryl) -4H-azurenyl]} hafnium, (56) Dichloro {dimethylsilylene-1- [2-methyl-4-] (4-biphenylyl)-
4H-azurenyl] -1- [2-methyl-4- (4-biphenylyl) indenyl]} hafnium, (57) dichloro {1,1′-dimethylsilylenebis [2-methyl-
4- (4-biphenylyl) -4H-5,6,7,8-tetrahydroazulenyl]} hafnium, etc.

(B-3) Q = Compound of hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum: (1) dimethylgermylene bis (indenyl) hafnium dichloride, (2) dimethylgermylene (cyclopentadiene) (Enyl) (fluorenyl) hafnium dichloride,
(3) Methylaluminum bis (indenyl) hafnium dichloride, (4) Phenylaluminum bis (indenyl) hafnium dichloride, (5) Phenylphosphinobis (indenyl) hafnium dichloride, (6)
Ethylholanobis (indenyl) hafnium dichloride, (7) phenylaminobis (indenyl) hafnium dichloride, (8) phenylamino (cyclopentadienyl) (fluorenyl) hafnium dichloride,
(9) dichloro {1,1′-dimethylgermylenebis [2-methyl-4- (4-biphenylyl) -4H-azulenyl]} hafnium,

(C) A compound represented by the general formula [3], that is, a hafnium compound having no conjugated group Q'and one conjugated five-membered ring ligand: (1) pentamethylcyclopentadienyl -Bis (phenyl) aminohafnium dichloride, (2) indenyl-bis (phenyl) amido hafnium dichloride,
(3) Pentamethylcyclopentadienyl-bis (trimethylsilyl) aminohafnium dichloride, (4) Pentamethylcyclopentadienylphenoxyhafnium dichloride, (5) Cyclopentadienylhafnium trichloride, (6) Pentamethylcyclopentadichloride Enyl hafnium trichloride, (7) cyclopentadienyl hafnium benzyl dichloride, (8) cyclopentadienyl hafnium dichlorohydride, (9) cyclopentadienyl hafnium triethoxide, and the like.

(D) A compound represented by the general formula [4], that is, a hafnium compound having one conjugated five-membered ring ligand bridged with a bonding group Q ': (1) dimethylsilylene (tetramethylcyclopentadiene) (Enyl) phenylamido hafnium dichloride, (2)
Dimethylsilylene (tetramethylcyclopentadienyl) -t-butylamido hafnium dichloride, (3)
Dimethylsilylene (indenyl) cyclohexylamide hafnium dichloride, (4) dimethylsilylene (tetrahydroindenyl) decylamide hafnium dichloride, (5) dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) hafnium dichloride, (6) dimethylgermylene (Tetramethylcyclopentadienyl) (phenyl) aminohafnium dichloride and the like are exemplified.

Further, it is also possible to use the compounds of the above (a) to (d) in which chlorine is replaced with bromine, iodine, hydride, methyl, phenyl, diethylamide group or the like. In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. Of these, preferred are the compounds exemplified in (a) and (b). In addition, when asymmetric carbon is generated in these metallocene-based transition metal compounds, one of stereoisomers or a mixture thereof (including a racemate) is shown unless otherwise specified.

As the component [A], the general formula [1],
A large number of hafnium compounds (when M is Hf atom) represented by [2], [3] or [4] are exemplified. Although illustration is omitted below, it can be similarly used when M is a transition metal of Groups 4 to 6 of the periodic table such as zirconium, titanium, and chromium. Two or more types of component [A] may be used. Among the above hafnium compounds, (a),
Two or more compounds such as (b) and (c) may be combined, and a hafnium compound and a zirconium compound may be combined.

Component [B] <Layered silicate> The component [B] used in the present invention accounts for the majority of the clay mineral, and is preferably an ion-exchangeable layered silicate. A layered silicate is a silicate 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. Most of the layered silicates are naturally produced mainly as the main components of clay minerals, but these layered silicates are not limited to those of natural origin, and may be synthetic products.

Specific examples of the layered silicate include known layered silicates described in Haruo Shiramizu, "Clay Mineralogy," Asakura Shoten (1995), such as dickite,
Kaolins such as nakrite, kaolinite, anoxite, metahalloysite, halloysite, serpentine family such as chrysotile, risaldite, antigorite, montmorillonite, sauconite, beidellite, nontronite, saponite, teniolite, hectorite, stevensite. Smectite group such as, vermiculite group such as vermiculite, mica, illite, sericite, mica group such as glaucolite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group. These may form a mixed layer.

Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Preferred are smectites such as teniolite, vermiculites, and mica. Typical examples of the smectites are montmorillonite, beidellite,
They are saponite, nontonite, hectorite, sauconite and the like. "Ben clay SL" (Mizawa Chemical Co., Ltd.), "Kunipia", "Smecton" (Kunimine Industries Co., Ltd.), "Montmorillonite K10" (Aldrich, Jute Chemie), "K-Catalysts series" (Jute Chemie) It is also possible to use a commercial product such as a product manufactured by the company. Typical examples of the mica group include muscovite, paragonite, phlogopite, biotite, and lepidrite. Commercially available "Synthetic mica somasif" (made by Corp Chemical), "Fluorine phlogopite", "Fluorotetrasilicon mica",
Commercially available products such as "Teniolite" (all manufactured by Topy Industries, Ltd.) can also be used. More preferred are smectites such as "Ben clay SL".

In general, natural products are often non-ion-exchangeable (non-swellable), and in that case, they have ion-exchangeable (or swellable) properties so as to have preferable ion-exchangeable (or swellable) properties. It is preferable to carry out a treatment for imparting the property. Among such treatments, the following chemical treatments are particularly preferable. That is, it is preferable that these silicates are chemically treated. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment, (b) alkali treatment, (c) salt treatment, (d) organic substance treatment and the like can be mentioned.

These treatments remove impurities on the surface, exchange cations between layers, Al and F in the crystal structure.
It acts to elute cations such as e and Mg, and as a result, forms an ionic complex, a molecular complex, an organic derivative, etc., and can change the surface area, interlayer distance, solid acidity, and the like. These treatments may be performed alone or two or more treatments may be combined. As the (a) acid used in the chemical treatment, a purposeful inorganic acid or organic acid,
Preferred examples include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like, and (b) alkalis include NaOH and K.
OH, NH _{3 and the} like can be mentioned. (C) As salt, 2
At least one selected from the group consisting of group 14 to group 14 atoms
A compound composed of a cation containing one kind of atom and at least one kind of anion selected from the group consisting of a halogen atom or an anion derived from an inorganic acid or an organic acid is preferable.

More preferred are Li, Mg, Ca,
Al, Ti, Zr, Hf, V, Nb, Ta, Cr, M
n, W, Mn, Fe, Co, Ni, Cu, Zn, B, A
1, an ion derived from 1, Ge or Sn is used as a cation, and an ion derived from Cl, SO ₄ , NO ₃ , OH, C ₂ H ₄ and PO ₄ is used as an anion. (D) As the organic substance, alcohol (aliphatic alcohol having 1 to 4 carbon atoms, preferably, for example, methanol, ethanol, propanol, ethylene glycol, glycerin, carbon number 6)
~ 8 aromatic alcohol, preferably for example phenol, higher hydrocarbons (C5-10, preferably 5)
8), preferably hexane, heptane, etc.)
Can be given. Further, formamide, hydrazine, dimethylsulfoxide, N-methylformamide, N, N
-Preferably dimethylaniline and the like. Two or more kinds of salts and acids may be used.

When the salt treatment and the acid treatment are combined, a method of performing the salt treatment and then the acid treatment, a method of performing the acid treatment and then the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment There is. The treatment conditions with salts and acids are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting the layered silicate is eluted. Further, salts and acids are toluene,
In an organic solvent such as n-heptane or ethanol, or if the salt or acid is liquid at the treatment temperature, it can be used without a solvent, but is preferably used as an aqueous solution.

The component [B] of the present invention is used before all the steps,
During any of the following time points, crushing, granulating, sizing,
The particle properties can be controlled by fractionation or the like. The method can be any purposeful. In particular, if the granulation method is shown, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method, Examples thereof include an emulsion granulation method and a submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method among the above.

Component [C] <Specific active hydrogen compound> The component [C] used in the catalyst of the present invention is at least 1
5-14 atoms of Group 15 of the Periodic Table having 1 active hydrogen
1 to 30 carbon atoms directly bonded to one carbon atom in the membered ring structure and bonded to another carbon atom forming the ring structure
Is an organic compound having at least one hydrocarbon group.

Here, active hydrogen means Iwanami Shoten 1982.
"Risk and Chemistry Dictionary 3rd Edition Supplement" 24
As described in the section of active hydrogen on page 8, the hydrogen atom in an organic compound is divided into one that is directly bonded to carbon and one that is bonded to oxygen, nitrogen, etc., and the latter is reacted. It is called because it has strong nature. In the present invention, a compound in which active hydrogen is bonded to an atom of Group 15 of the periodic table, specifically, any atom of nitrogen, phosphorus, arsenic, antimony and bismuth is used. The compound bonded to the nitrogen atom is a primary or secondary amine, the compound bonded to the phosphorus atom is a primary or secondary phosphine, and the compound bonded to an arsenic atom is arsine. Examples of the compound bound to the antimony atom include stibines, and examples of the compound bonded to the bismuth atom include bismuthines.

Here, the 5- to 14-membered ring structure is mainly a structure having carbon atoms as ring members, and can be specifically classified into the following seven types. (C-1) Monocyclic saturated hydrocarbon structure (C-2) Monocyclic unsaturated hydrocarbon structure (C-3) Condensed polycyclic hydrocarbon structure (C-4) Part of condensed polycyclic hydrocarbon A structure corresponding to the hydrogenated compound structure (C-5) bridged cyclic hydrocarbon structure (C-6) spiro hydrocarbon structure (C-7) (C-1) to (C-6). Heterocyclic compound structure in which at least one of the carbon atoms has been replaced by a heteroatom in IUPAC Nomenclature of Organic Chemistry Committee, published in 1979 by Kenzo Hirayama, translated by Namedo 1988, "Nomenclature of Organic Chemistry and Biochemistry Revised 2nd Edition" From page 18 to page 64,
The above categories are described in detail. The details of the 5- to 14-membered ring structure are as follows. Hereinafter, the ring structure is represented by the name of a hydrocarbon group.

(C-1) Monocyclic saturated hydrocarbon structure cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group,
Cyclotridecanyl group, cyclotetradecanyl group,

(C-2) Monocyclic unsaturated hydrocarbon structure 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1-yl group, cyclopentylidene group, cyclohexenyl group, 1,3- Cyclohexadienyl group, 2,
4-cyclohexadiene-1-ylidene group, 1-cyclodecene-4-ynyl group, 1-cyclotetradecene-4-
Inyl group, phenyl group

(C-3) Condensed polycyclic hydrocarbon structure pentalenyl group, indenyl group, naphthalenyl group, azulenyl group, heptanenyl group, biphenylenyl group, as-
Indacenyl group, s-indacenyl group, acenaphthylenyl group, fluorenyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, 1H-cyclopentacyclooctenyl group, benzocyclooctenyl group,

(C-4) Structure of partially hydrogenated compound of condensed polycyclic hydrocarbon group 1,4-dihydronaphthalenyl group, tetradecahydroanthracenyl group, 6,7-dihydro-5H-benzocyclohep Tenyl group, 4,5,6,7,8,9-hexahydro-1H-cyclopentacyclooctenyl group, indanyl group

(C-5) Bridged cyclic hydrocarbon structure Bicyclo [3.2.1] octanyl group, bicyclo [5.
2.0] nonanyl group, bicyclo [2.2.2] octa-
2-enyl group, tricyclo [2.2.1.0] heptanyl group, tricyclo [5.3.1.1] dodecanyl group, tricyclo [5.4.0.0] undecanyl group, tricyclo [7.3. 2.0] Tetradecanyl group, 1,4-dihydro-1,4-methanopentalenyl group,

(C-6) Spirohydrocarbon Structure Spiro [3.4] octanyl group, spiro [4.5] deca-1,6-dienyl group, spiro [cyclopentane-1,
1'-indenyl] group,

(C-7) A structure corresponding to (C-1) to (C-6) in which at least one of carbon atoms in the structure is substituted with a hetero atom, a thianthrenyl group, pyranyl Group, chromenyl group, phenoxathinyl group, carbazolyl group, acridinyl group, morpholinyl group, 1-oxaspiro [4.5] decanyl group, 1,2,3,4-tetrahydroquinoline-4-spiro-4'-piperidinyl Group, 7-azabicyclo [2.
2.1] heptanyl group, 2,6-dioxabicyclo [3.2.1] oct-7-yl group

Examples of the 5- to 14-membered ring structure include the structures described above. (C-2) monocyclic unsaturated hydrocarbon structure, (C-3) condensed polycyclic hydrocarbon structure and ( C-4) partially hydrogenated compound structure of condensed polycyclic hydrocarbon, (C-5) bridged cyclic hydrocarbon structure and (C-6) spiro hydrocarbon structure are preferable, and among these, (C-2)
Further preferred are compounds having an aromatic ring structure belonging to

The hydrocarbon group having 1 to 30 carbon atoms which is bonded to another carbon atom other than the carbon atom to which the group 15 atom of the periodic table is bonded is a hydrocarbon group which may be linear, branched or cyclic. And may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the term "hydrocarbon group having 1 to 30 carbon atoms" as used herein means that the hydrogen atom of the hydrocarbon group is a halogen atom,
It also includes a hydrocarbon derivative group substituted with a trialkylsilyl group such as a trimethylsilyl group or a triethylsilyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. Of the substituted hydrocarbon groups, those having a structure containing a Lewis base moiety formed of an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom or the like in the linear or branched portion of the hydrocarbon group are not preferred.

Component 5 [C], to which at least one active hydrogen-containing Group 15 atom of the periodic table is directly bound 5
Α position on the ring, based on the carbon atom in the 14-membered ring structure,
1 carbon atom at the α'position, γ position, or γ'position
It is preferable that at least one hydrocarbon group of -30 is bonded. Further, the hydrocarbon group having 1 to 30 carbon atoms is 2
There may be two or more, but in this case, it is preferable not to have two at the α position and α ′ position on the ring at the same time.

With respect to the above-mentioned component [C], a specific example will be given by taking as an example the case where the atom of Group 15 of the periodic table is a nitrogen compound. As a compound belonging to (C-1), (2-methylcyclopentyl) amine , (2-ethylcyclopentyl) amine, (2-propylcyclopentyl) amine,
(3-methylcyclopentyl) amine, (4-methylcyclopentyl) amine, (2-methylcyclohexyl)
Amine, (2,3-dimethylcyclohexyl) amine,
(2,4-dimethylcyclohexyl) amine, (2,5
-Dimethylcyclohexyl) amine, (2,6-dimethylcyclohexyl) amine, (3,4-dimethylcyclohexyl) amine, (3,5-dimethylcyclohexyl) amine, (2-ethyl-3-methylcyclohexyl) amine, (2 , 3,4-Trimethylcyclohexyl) amine, (2,3,5-trimethylcyclohexyl) amine, (2,4-dimethylcyclooctyl) amine, (2,3,4-trimethylcyclooctyl) amine, di (2- Methylcyclopentyl) amine, 1,3-
Diamino-2,5-dimethylhexane, etc.

As the compound belonging to (C-2), (2-
Methyl-2-cyclopenten-1-yl) amine, (3
-Methyl-2-cyclopenten-1-yl) amine,
(4-Methyl-2-cyclopenten-1-yl) amine, (5-methyl-2-cyclopenten-1-yl) amine, (2-n-butyl-2-cyclopenten-1-yl) amine, (2, 3-dimethyl-2-cyclopenten-1-yl) amine, (2,4-dimethyl-2-cyclopenten-1-yl) amine, (2,5-dimethyl-2
-Cyclopenten-1-yl) amine, (3,4-dimethyl-2-cyclopenten-1-yl) amine, (3,4-dimethyl-2-cyclopenten-1-yl) amine
5-dimethyl-2-cyclopenten-1-yl) amine, (4,5-dimethyl-2-cyclopenten-1-yl) amine, (2-methyl-2,4-cyclopentadiene-1-yl) amine, 2 -Methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 2-propylaniline, 2-n-butylaniline,
2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,6-diisopropylaniline, 3 -Ethyl-4-methylaniline, N, N-di (2-methylphenyl) amine, N, N-di (2,5-dimethylphenyl)
Amine, N-methyl-N-di (2,5-dimethylphenyl) amine, 2,3,4-trimethylaniline, 1,3
-Diamino-2,5-dimethylbenzene, 4,4'-diamino-3,3 ', 6,6'-tetramethylbiphenyl, etc.

As compounds belonging to (C-3), 1- (pentalenyl) amine, 1- (2-methylpentalenyl)
Amine, 1- (3-methylpentalenyl) amine, 1-
(Indenyl) amine, 1- (2-methylindenyl)
Amine, 1- (3-methylindenyl) amine, 2-
(Indenyl) amine, (1-methylnaphthyl) amine, (3-methylnaphthyl) amine, (1,4-dimethylnaphthyl) amine, 1- (2-methylazulenyl) amine, 2- (1-methylazulenyl) amine, 7 -(8
-Methylazurenyl) amine, (1-methylanthryl) amine, etc.

As compounds belonging to (C-4), (2-methyl-1,4-dihydronaphthalen-1-yl) amine, (2,3-dimethyl-1,4-dihydronaphthalen-1-yl) amine, (2,4-Dimethyl-1,4-dihydronaphthalen-1-yl) amine, (1-methyl-
5,6,7,8-tetrahydronaphthyl) amine, (2
-Methyl-6,7-dihydro-5H-benzocyclohepten-1-yl) amine, (3-Methyl-6,7-dihydro-5H-benzocyclohepten-1-yl) amine, (3-methyl -6,7-Dihydro-5H-benzocyclohepten-2-yl) amine, (3-methyl-6,6
7-dihydro-5H-benzocyclohepten-4-yl) amine, (8-methyl-6,7-dihydro-5H-
Benzocyclohepten-9-yl) amine, etc.

Compounds belonging to (C-5) include (1-methyl-bicyclo [3.2.1] oct-2-yl) amine and (3-methyl-bicyclo [3.2.1] octa-2.
-Yl) amine, (4-methyl-bicyclo [3.2.
1] oct-2-yl) amine, (1-methyl-tricyclo [2.2.1.0] heptan-2-yl) amine,
(1-Methyl-tricyclo [2.2.1.0] heptan-7-yl) amine, (1,3-Dimethyl-tricyclo [2.2.1.0] heptan-2-yl) amine, etc.

(1-Methyl-spiro [3.4] octane-2-yl) amine as a compound belonging to (C-6),
(1,3-Dimethyl-spiro [3.4] octane-2-
Yl) amine, (1,1,3-trimethyl-spiro [3.4] octane-2-yl) amine, (1,1,
3,3-Tetramethyl-spiro [3.4] octane-2
-Yl) amines, etc.

As the compound belonging to (C-7), (1-methylthianthrenyl) amine, (2-methylpyranyl)
Amine, (2-methylchromenyl) amine, (1-methylphenoxathinyl) amine, (1-methylcarbazolyl) amine, (3,4,5-trimethylacridinyl) amine, (2,4 , 5,6-Tetramethylmorpholinyl) amine, (2,6-dimethyl-1-oxaspiro [4.5] decan-3-yl) amine, (1,2 ′,
6'-trimethyl-1,2,3,4-tetrahydroquinolin-4-spiro-4'-piperidin-2-yl) amine, (2,4-dimethyl-7-azabicyclo [2.2.
1] heptan-1-yl) amine, (1,5,7-trimethyl-2,6-dioxabicyclo [3.2.1] oct-7-yl) amine and the like.

Specific compound names have been mentioned above, but these are merely examples, and the present invention is not limited to these compounds. The above is an example of amines, but the same applies to arsines, stibines, bismuthines and the like. Further, the component [C] may be used in combination of two or more kinds.

Component [D] <Organoaluminum Compound> The component [D] is used as necessary. Examples of the organoaluminum compound used as the component [D] are compounds represented by the following general formula. AlR ⁸ _j X _3-j (In the formula, R ⁸ represents a C _{1 to} C ₂₀ hydrocarbon group, X represents hydrogen, halogen, an alkoxy group, and j represents a number of 0 <j ≦ 3.)
Specifically, it is a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trioctylaluminum, or a halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum methoxide.
In addition, aluminoxane such as methylaluminoxane can be used. Of these, trialkylaluminum is particularly preferable.

Further, as a catalyst component, a boron compound such as Lewis acid represented by tris (pentafluorophenyl) boron, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl). An anionic compound represented by borate can also be used.

The contact of the component [A], the component [B], and the component [C] is not particularly limited, but they can be contacted in the following contacting order. a1. After bringing the component [A] and the component [B] into contact with each other, the component [C] is added. a2. The component [A] and the component [C] are brought into contact with each other and then added to the component [B]. b1. After contacting the component [B] and the component [C], the component [A] is added. In addition, the three components may be contacted at the same time.

Further, the component [C] can be directly added to the component [A], the component [B], the component [D] which is used if necessary, and the polymerization system in which the olefin is present. In this case, the component [C] is the component [A], the component [B], the contact product of the component [A] and the component [B], the contact product of the component [A] and the component [D], and the component [B]. ] And the contact product of the component [D], or the contact product of the component [A], the component [B] and the component [D], and then contact with the olefin, the component [C] Can be mentioned as a preferable olefin polymerization method. Furthermore, when the component [D] is used, the contact of the component [A], the component [B], and the component [C] is not particularly limited as long as it is purposeful. ], Component [B], contact product of component [A] and component [B], contact product of component [A] and component [D], contact product of component [B] and component [D], component A method for adding component [C], which comprises contacting either [A], component [B], or a contact product of component [D] and then newly contacting component [D] in the presence of an olefin. Can be mentioned as a preferable olefin polymerization method when the component [D] is used.

The amount of the component [A] used is 0.001 to 10000 mmol, preferably 0.01 to 100 mmol, per 1 g of the component [B]. The amount of the component [C] used is 0.001 to 100 mm per 1 g of the component [B].
ol, preferably 0.01 to 9.0 mmol. The atomic ratio of the transition metal in the component [A] to the component [C] is 1: 0.001 to 1000, preferably 0.1 to 100.
Is. When the component [C] is added to the polymerization system, the preferable range of the amount of the component [C] used is 0.01 to 9 in the case of slurry polymerization or solution polymerization in the presence of a solvent per 1 g of the component [B]. 0 mmol, more preferably 0.0
5 to 5.0 mmol, and 0.00 in the case of gas phase polymerization
1-2.0 mmol, more preferably 0.005-1.
It is 0 mmol. The amount of component [D] used is the same as component [B]
It is 0.01 to 10000 mmol, preferably 0.1 to 100 mmol per 1 g. Further, the atomic ratio of the transition metal in the component [A] to the aluminum in the component [D] is 1: 0.01 to 10,000, preferably 0.1 to 100.
It is 0. Further, the atomic ratio of aluminum in the component [C] and the component [D] is 1: 0.1 to 1000, preferably 1 :.
1 to 500, more preferably 1: 6 to 200. These usage ratios are examples of normal ratios,
Of course, if the catalyst is purposeful, the present invention is not limited by the above range of the use ratio.

Before using the catalyst comprising the components [A] and [B] as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4- Olefin such as methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene can be preliminarily polymerized in a small amount (preliminary polymerization). Since the prepolymerized catalyst is stable during the main polymerization, it is possible to prevent the generation of fine powdered polymer due to particle crushing and to produce polymer particles having excellent fluidity. It is preferable because the polymerization reaction can be stably operated. The prepolymerization step also has the advantage of promoting the formation of active sites. That is, by carrying out preliminary polymerization, the component [B]
Is finely dispersed in the prepolymerized catalyst particles to increase the surface area and form new polymerization active precursor points, or the prepolymerized polymer contains the polymerization active points, thereby The industrial handling advantages such as the fact that contact between the spots and the poisonous substance is restricted and deactivation can be prevented can be mentioned.

This preliminary polymerization with ethylene or the like can be carried out before, during, or after all steps in the catalyst production as long as the effect is not lost, in an inert solvent or without a solvent. Medium (or when the liquid α-olefin is used for prepolymerization, it may be the α-olefin), under the contact of the above-mentioned components, an organoaluminum such as the above-mentioned component [D] is newly added if necessary. , Ethylene, propylene, etc. are provided, and 0.01 to 1000 g, preferably 0.1 to 100 g per 1 g of catalyst component
It is desirable to carry out so that the polymer of The prepolymerization temperature is -100 to 100 ° C, preferably -60 to 10
The prepolymerization time is 0.1 to 100 hours, preferably 0.1 to 20 hours.

The olefins which can be polymerized by the olefin polymerization catalyst of the present invention include ethylene, propylene, butene-1,3-methylbutene-1,3-methylpentene-1,4-methylpentene-1, vinylcycloalkane and butadiene. And the like, non-conjugated dienes such as 1,5-hexadiene, styrene, and derivatives thereof. Further, the polymerization can be suitably applied to generally known random copolymerization and block copolymerization as well as homopolymerization.
The polymerization reaction is butane, pentane, hexane, heptane,
Inert hydrocarbons such as toluene and cyclohexane and liquefied α
-It is preferable to carry out the gas phase polymerization in the presence of a solvent such as an olefin, or in a state in which substantially no liquid phase of the solvent or the monomer exists. The gas phase polymerization can be carried out using a reactor such as a fluidized bed, a stirred bed, or a stirred fluidized bed equipped with a stirrer / mixer. The conditions such as polymerization temperature and polymerization pressure are not particularly limited, but the polymerization temperature is generally -50 to 250 ° C, preferably 0 to 100 ° C, and the polymerization pressure is usually
Normal pressure to about 2000 kgf / cm ² , preferably normal pressure to 2
00 kgf / cm ² , more preferably normal pressure to 50 kgf
The range is / cm ² . Further, hydrogen may be present as a molecular weight modifier in the polymerization system.

[0070]

EXAMPLES The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

Example 1 (1) Acid Treatment of Clay Mineral 37 kg of a commercially available granulated and classified product of swelling montmorillonite was dispersed in 148 kg of 25% sulfuric acid and stirred at 90 ° C. for 2 hours. This was filtered and washed with demineralized water. (2) Salt treatment of clay mineral Commercially available titanyl sulfate (manufactured by Sakai Chemical Industry Co., Ltd., containing 7.5% of TiO _{2 and} 25.6% of SO 4) 23
The total amount of the sulfuric acid-treated montmorillonite cake obtained in (1) above was dispersed in 6 kg, and the mixture was stirred at 30 ° C. for 3 hours. After filtering and washing this with demineralized water to pH 3.5, the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours to obtain a titanium salt-treated montmorillonite. Of this pre-dried montmorillonite, the aperture is 15
The particles that passed through the 0 mesh sieve were further subjected to a speed of 3 kg / hr (retention time: 1 at a temperature of 200 ° C. under a countercurrent nitrogen stream (nitrogen flow rate: 49 Nm ³ / h) using a rotary kiln.
It was continuously dried at 0 min) and collected under dry nitrogen.

(3) Preparation of catalyst and prepolymerization In a nitrogen atmosphere, a reactor equipped with an induction stirrer having a capacity of 0.92 m ³ was prepared. The salt-treated montmorillonite particles prepared in (2) above were dried at 200 ° C. and 5.0 kg and n. -Heptane 392
L was introduced and the temperature was 13 ° C. Here, while maintaining the temperature under stirring, bis (n-butylcyclopentadienyl) hafnium dichloride 1.20 mol (590
g) was added and stirred for 15 minutes. Subsequently, while maintaining the temperature, triethylaluminum 4.90 mol (56
0 g) was added and stirring was continued for another 20 minutes. Next, the temperature of the system was raised to 80 ° C. over about 1 hour, and ethylene gas was supplied for 2 hours to carry out prepolymerization. The ethylene gas supply rate at this time was 36 kg / hr for 15 minutes from the start, and was 17 kg / hr thereafter. The supply of ethylene was stopped and the ethylene gas in the reactor was replaced with nitrogen.
This prepolymerization catalyst slurry was washed with n-heptane containing triethylaluminum (TEA) at a concentration of 1 mmol / L to a washing rate of 1/127, and then, in a nitrogen atmosphere, a tank type equipped with a steam jacket for conductive heat reception. The solvent was removed by extracting into a vibration type vacuum dryer and drying under reduced pressure while heating at 70 ° C. As a result, 43.1 kg of the prepolymerized catalyst powder was recovered.

(4) Copolymerization of ethylene / 1-hexene Slurry using the prepolymerized catalyst powder obtained in (3) above
Polymerization was carried out. That is, 3L Oh with an induction stirrer
180 ml of 1-hexene and n-heptane were added to the tclave.
1.5 L, 2,5-dimethylaniline 0.25 mmol
(As a 0.1 mmol / ml n-heptane solution 2.
5 ml), the catalyst of the above (3) was added to the component [B] 100 mg phase
After adding the equivalents in order with stirring at room temperature, 8 minutes after 15 minutes
The temperature was raised to 0 ° C. Then, while maintaining the temperature, triiso
Butyl aluminum 2.5 mmol with ethylene
Introduce ethylene and continue to introduce ethylene to a total pressure of 22 kg / c
m ²The temperature was maintained at -G, and polymerization was carried out at 80 ° C for 0.40 hours.
After 0.40 hours, ethanol was added to terminate the polymerization.
The obtained ethylene-1-hexene copolymer was 101 g.
Yes, per 1 g of component [B], copolymer per hour
The produced amount was 2523 g / g / hr. Table of catalyst composition
Table 1 shows the polymerization results and product properties.

[Examples 2 to 8] In the same manner as in Example 1 (4), slurry polymerization was carried out using the prepolymerized catalyst powder obtained in Example 1 (3). However, the organic compounds added as the component [C] and the amounts used are as shown in Table 1. The catalyst composition is shown in Table 1, and the polymerization results and product properties are shown in Table 2.

[Examples 9-10] Ethylene / 1-hexene gas phase copolymerization was carried out using the prepolymerized catalyst powder obtained in Example 1 (3). That is, a continuous gas phase polymerization reactor in which a mixed gas of ethylene, hexene and hydrogen (hexene / ethylene = 1.8% by weight, hydrogen / ethylene = 0.041% by weight) was circulated was obtained in Example 1 (3). Slurry solution of prepolymerization catalyst (8.0 g of prepolymerization catalyst of Example 1 (3) and 2,5
-Dimethylaniline 0.39 mmol in Example 9
In Example 10, 0.46 mmol was slurried with 2.0 L of n-heptane) as the component [B].
5 mg / hr (52 mg / hr in Example 10), triisobutylaluminum and diethylaluminum ethoxide were intermittently supplied at 100 mg / hr and 68 mg / hr, respectively. The polymerization reaction conditions were a polymerization temperature of 90 ° C. and an ethylene partial pressure of 18 kg / cm ² . The catalyst composition is shown in Table 3,
The results of polymerization and the physical properties of the products are shown in Table 4.

[Comparative Examples 1 to 5] Vapor phase copolymerization of ethylene / 1-hexene was carried out using the prepolymerized catalyst powder obtained in Example 1 (3). However, the component [C] was not added, or an organic compound not included in claim 1 was used in place of the component [C]. The catalyst composition is shown in Table 5, and the polymerization results and product properties are shown in Table 6.

[Example 11] (1) Chromium salt treatment of clay mineral The acid-treated montmorillonite cake obtained in the same manner as in Example 1 (1) was pre-dried at 110 ° C for 10 hours to obtain particulate acid-treated montmorillonite. Got Next, 200g of pure water
After dissolving the commercially available _{Cr (NO 3) 3 · 9H} 2 O 48g to, dispersing the particulate acid treated montmorillonite 20g, and stirred for 3 hours at 90 ° C.. PH 6 with demineralized water
After filtering and washing to 11
Preliminary drying was performed at 0 ° C. for 10 hours to obtain a chromium salt-treated montmorillonite in the form of particles having a good flowability. The preliminary dried montmorillonite particles were further dried under reduced pressure at 200 ° C. for 2 hours to obtain dried montmorillonite particles. (2) Chromium salt-treated montmorillonite organic Al treatment In a nitrogen atmosphere, in a 300 mL flask, 10.1 g of the chromium salt-treated montmorillonite particles obtained in (1) was n-
It was dispersed in 202 ml of heptane to obtain a slurry. Then, with stirring at room temperature, n-
Heptane solution (concentration 0.622 mol / L) 48.2 m
1 was added. After contacting at room temperature for 1 hour, the supernatant was extracted and the solid portion was washed with n-heptane. (3) Preparation of catalyst and prepolymerization In a nitrogen atmosphere, a reactor with an induction stirring device having a volume of 1 L was charged with n.
-550 ml of heptane and the total amount of the organic Al-treated montmorillonite obtained in (2) were introduced into the reactor. Then, at 30 ° C., 9.60 mmol (1.10.
g) was added and stirring was continued for another 10 minutes. 2.40 mmol (0.702 g) of bis (cyclopentadienyl) zirconium dichloride was added to 234 m of toluene.
l as a solution and stirred at 30 ° C. for 10 minutes,
The temperature was raised to 60 ° C., and stirring was continued for another 10 minutes. While maintaining the temperature of the system, ethylene gas was introduced at a rate of 1.0 NL / min for 18 minutes to carry out prepolymerization. The supply of ethylene was stopped, the reactor contents were washed with n-heptane under a nitrogen atmosphere, and then dried under reduced pressure while heating at 70 ° C to remove the solvent. As a result, the prepolymerization catalyst powder 2
7.5 g was recovered. (4) Ethylene homopolymerization Slurry polymerization was performed using the prepolymerized catalyst powder obtained in (3) above. That is, in a 3 L autoclave equipped with an induction stirrer, 1.5 L of n-heptane, 0.75 mmol of 2,5-dimethylaniline (7.5 ml as a 0.1 mmol / ml n-heptane solution), the catalyst of the above (3) 300 mg of component [B] was sequentially added to the mixture while stirring at room temperature, and the temperature was raised to 93 ° C. in 15 minutes. Then, while maintaining the temperature, triisobutylaluminum 2.5
mmol was introduced together with ethylene, the introduction of ethylene was continued and the total pressure was maintained at 7 kg / cm ² -G, and 2 at 93 ° C.
Polymerization was carried out for a time. After 2 hours, ethanol was added to terminate the polymerization. The amount of the obtained ethylene homopolymer was 165 g, and the amount of the copolymer produced per 1 g of the component [B] was 275 g / g / hr per hour. Table 7 shows the catalyst composition.
Table 8 shows the polymerization results and product properties.

Comparative Example 6 Ethylene homopolymerization was carried out in the same manner as in Example 11 (4) using the prepolymerized catalyst powder obtained in Example 11 (3). However, the component [C] 2,5-dimethylaniline was not used. The catalyst composition is shown in Table 7, and the polymerization results and product properties are shown in Table 8.

Example 12 (1) Synthesis of component [A] [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] Zirconium] is synthesized in JP-A-11-24.
According to the method described in the example of JP-A No. 090. Bromochlorobenzene (1.84 g, 9.59 mmol) was dissolved in a mixed solvent of diethyl ether (10 mL) and hexane (10 mL), and a solution of t-butyllithium in pentane (1
1.7 mL, 19.18 mmol, 1.64 N) -7
It was added dropwise at 8 ° C. The mixture was stirred at -70 ° C for 20 minutes and at -5 ° C for 1.5 hours. 2-Methylazulene (1.22
(g, 8.63 mmol) was added, and the mixture was stirred at -5 ° C for 10 minutes and at room temperature for 1.5 hours, almost purple was disappeared and a white precipitate was formed. Cooled to 0 ° C and tetrahydrofuran (10 mL)
Was added, and N-methylimidazole (15 μL) and dimethyldichlorosilane (0.52 mL, 4.31 mmol) were added.
Was added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1.5 hours.
After that, dilute hydrochloric acid was added, and after liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane and hexane-dichloromethane 1: 1) to obtain dimethylbis-1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -1,4. -Dihydroazulene) (2.06 g, 85%) was obtained. The azulene (1.27 g) obtained above was dissolved in diethyl ether (15 mL), and a hexane solution of n-butyllithium (2.8 mL, 1.6 mol / L) was obtained at -78 ° C.
Was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. The solvent was distilled off, and toluene (5 mL) and diethyl ether (0.
12 mL) was added. After cooling to −78 ° C., sublimation-purified zirconium tetrachloride (530 mg) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 4 hours. The obtained solution was subjected to frit filtration using Celite, and washed on the frit with toluene (3 mL). What was separated by filtration was extracted with dichloromethane and concentrated under reduced pressure to dichloro [1,1'-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4H].
-Azulenyl)] zirconium racemic / meso mixture (906 mg, including toluene) was obtained. The racemic / meso ratio was 6: 4. Complex Purification The racemic / meso mixture (906 mg, containing toluene) obtained above was suspended in dichloromethane (25 mL), and irradiated with 40 spectra using a high pressure mercury lamp (100 W). This solution was filtered using a frit, and the solvent was distilled off under reduced pressure. Toluene (7 mL) was added to the obtained solid, and the mixture was left standing and the supernatant was removed. The same operation is performed with toluene (5 mL,
6 mL) and finally hexane (8 mL, 5 m
It was washed with L). When dried under reduced pressure, a racemate (275 mg) was obtained as a yellow powder. ¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.95
(S, 6H, SiMe ₂ ), 2.13 (s, 6H, 2-
Me), 4.83 (brs, 2H, 4-H), 5.7.
0-5.90 (m, 8H), 6.05-6.11 (m,
2H), 6.73 (d, 2H), 7.25-7.30.
(M, 8H, arom.). ^{negative CI-MS722 (M + C} 36 H 32 35 Cl 4 Si
⁹⁰ Zr).

(2) Acid treatment of clay minerals 96% sulfuric acid (2500 g) was added to 3750 mL of pure water in a separable flask, and 1000 g of commercially available montmorillonite (Benclay SL, Mizusawa Chemical Co., Ltd.) was added at 60 ° C.
The mixture was slurried with stirring. After heating this slurry to 90 ° C. over 1 hour and reacting at 90 ° C. for 5 hours,
The reaction slurry was cooled to room temperature in 1.5 hours and washed with distilled water until the washing liquid (filtrate) reached pH 3. The obtained solid was pre-dried at 130 ° C. for 2 days in a nitrogen stream, and further dried under reduced pressure at 200 ° C. for 6 hours to obtain 707.2 g of chemically treated smectite. The composition of this chemically treated montmorillonite was Al: 5.21 wt%, Si: 38.
9 wt%, Mg: 0.80 wt%, Fe: 1.60 wt
%, Na: <0.2 wt%, Al / Si = 0.1
It was 39 [mol / mol]. (2) Organic Al treatment of acid-treated montmorillonite 20.0 g of acid-treated montmorillonite obtained in (1) above was weighed in a glass reactor having an internal volume of 500 ml, and heptane 73.7 ml,
Heptane solution of trinormal octyl aluminum 126.
3 ml (50.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Then, it was washed with heptane, and finally the slurry amount was adjusted to 200.0 ml. (3) Prepolymerization with Propylene (r) -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium obtained in (1) above 218 mg (0.30 8) to heptane
Add 2.9 ml and stir, add 4.26 ml (3.0 mmol) of a solution of triisobutylaluminum in heptane at room temperature, and add 6
Stir for 0 minutes. This complex solution was added to montmorillonite treated with trinormal octylaluminum in the above (2), and stirred at room temperature for 60 minutes. Next, 209 ml of heptane was added to the above mixed slurry, and the mixture was put into a stirring autoclave having an internal volume of 1 liter and stirred. When the temperature inside the autoclave was stable at 40 ℃, propylene was added at 238.1mmo.
It was fed at l / hr for 240 minutes. After completion of the propylene feed, stirring was continued for 60 minutes while maintaining the temperature at 40 ° C. Then, the residual gas was purged and replaced with nitrogen, and then the prepolymerized slurry was recovered from the autoclave. The recovered catalyst slurry was allowed to stand and the supernatant was extracted. To the remaining solid components, 17.02 ml (12.02 mm) of a solution of triisobutylaluminum in heptane.
ol) was added at room temperature and the mixture was stirred at room temperature for 10 minutes and dried under reduced pressure to recover 68.93 g of a solid catalyst component.

(4) Propylene / Ethylene Copolymerization After thoroughly replacing the inside of the stirring autoclave with an internal volume of 3 L with propylene, 2.86 mL (2.02 mmol) of a triisobutylaluminum / n-heptane solution was added, and further 2, A solution of 5-dimethylaniline / n-heptane (6.0 ml, 3.02 μmol) was added. continue,
102 mL of hydrogen, 33 g of ethylene, and subsequently, 1500 mL of liquid propylene were introduced, the temperature was raised to 60 ° C., and the temperature was maintained. Normal heptane slurry of prepolymerization catalyst,
1 mL and 12 mg of the catalyst (excluding the weight of the prepolymerized polymer) were press-fitted with argon to start the polymerization. The temperature in the bath was maintained at 60 ° C. 1 hour later, 10 ml of ethanol
Was added and the residual gas was purged, and the obtained polymer was dried. As a result, 306 g of polymer was obtained. The catalytic activity is 38100 g-PP / g-catalyst · hour, MFR =
The ethylene content was 6.7 (g / 10 minutes) and the ethylene content was 3.3 (% by weight). The catalyst composition is shown in Table 9, and the polymerization results and product properties are shown in Table 10. In addition, MFR (Melt Flow Rate)
Is the melt flow rate of JIS-K-6758 polypropylene test method (conditions: 230 ° C., load 2.16 kg).
f). The Tm is measured by DSC using a DSC measuring device manufactured by Seiko Co., Ltd. (sample: about 5 mg).
Melted at 200 ℃ for 5 minutes, then 40 ℃ up to 10 ℃ / m
After cooling down at a rate of in and crystallization, further 10 ° C /
The melting peak temperature and the melting end temperature when the temperature was raised to 200 ° C. for min and melting was evaluated.

[Examples 13 and 14] In the same manner as in Example 12 (4), propylene / ethylene copolymerization was carried out using the prepolymerized catalyst obtained in Example 12 (3). However,
Table 9 shows the organic compounds added as the component [C] and the amounts thereof used. The catalyst composition is shown in Table 9, and the polymerization results and product properties are shown in Table 10.

[Comparative Example 7] 2,5-dimethylaniline
Example 12 except that no n-heptane solution was added.
Polymerization was carried out in the same manner as in. The catalyst composition is shown in Table 9, and the polymerization results and product properties are shown in Table 10.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

[0093]

[Table 10]

[0094]

Since the catalyst of the present invention has a high olefin polymerization activity, the particle size can be rapidly increased in the reactor to reduce fine powder troubles such as aggregation and adhesion, and further, particle crushing does not occur. In addition, industrial long-term stable operation can be realized. Further, the catalyst of the present invention has high olefin polymerization activity and is therefore economically excellent.

Continued front page    F-term (reference) 4J128 AA01 AB00 AB01 AC01 AC10                       AC20 AC28 AC39 AC41 AC42                       AC44 AD01 AD02 AD05 AD06                       AD07 AD08 AD11 AD13 BA00A                       BA01B BB00A BB01B BC15B                       BC16B BC17B BC25B CA30C                       CB63 CB63C CB64 CB64C                       CB87 CB98 EA01 EB01 EB02                       EB04 EB05 EB07 EB09 EB10                       EB11 EB13 EB15 EC02 FA02                       GA05 GA07 GA09 GB01

Claims (12)

[Claims] 1. The following component [A], component [B], component [C]
And an olefin polymerization catalyst obtained by contacting the component [D], if necessary. Component [A]: Periodic Table No. 4 to 5 having a conjugated five-membered ring ligand
Group 6 transition metal compound component [B]: Layered silicate component [C]: Group 15 atom of the periodic table having at least one active hydrogen is directly attached to one carbon atom in a 5- to 14-membered ring structure. Organic compound component [D] in which at least one hydrocarbon group having 1 to 30 carbon atoms is bonded to another carbon atom which is bonded and forms the ring structure: an organoaluminum compound 2. The component [C] has a 5- to 14-membered ring structure,
The catalyst for olefin polymerization according to claim 1, which is an aromatic ring. 3. In the component [C], an atom of Group 15 of the periodic table is directly bonded to one carbon atom in a 5- to 14-membered ring structure, and the α on the ring is based on the carbon atom. Place, α '
3. A catalyst for olefin polymerization according to claim 1 or 2, wherein a hydrocarbon group is bonded to any of the positions, γ position and γ'position. 4. In the component [C], an atom of Group 15 of the periodic table is directly bonded to one carbon atom in a 5- to 14-membered ring structure, and the α atom on the ring is based on the carbon atom. Place, α '
4. A hydrocarbon group is bonded to any of the position, γ position, and γ'position, and two are not bonded simultaneously to the α position and the α'position. The catalyst for olefin polymerization described. 5. In the component [C], an atom of Group 15 of the periodic table is directly bonded to one carbon atom in a 5- to 14-membered ring structure, and the α atom on the ring is based on the carbon atom. Place, α '
5. At least two hydrocarbon groups are bonded to any of the position, γ position and γ'position, and two are not bonded to the α position and α'position at the same time. Either one
The olefin polymerization catalyst according to the item. 6. The catalyst for olefin polymerization according to claim 1, wherein the atom of Group 15 of the periodic table in the component [C] is a nitrogen atom or a phosphorus atom. 7. The component [C], wherein the hydrocarbon group directly bonded to one carbon atom in the 5- to 14-membered ring structure is an alkyl group having 1 to 4 carbon atoms. 1 to
6. The olefin polymerization catalyst according to any one of 6). 8. The component [C] is an aniline compound in which at least two positions of the 2- to 6-positions are substituted with an alkyl group having 1 to 4 carbon atoms. The olefin polymerization catalyst according to the item. 9. The component [C] is 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline and 3,5-dimethylaniline. The catalyst for olefin polymerization according to any one of claims 1 to 8, which is at least one dimethylaniline selected from dimethylaniline. 10. A method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9. 11. A component [C], a component [A], a component [B], a component [A] and a component [B] contact product, a component [A] and a component [D] contact product, a component. It is characterized in that it is brought into contact with either the contact product of [B] and component [D] or the contact product of component [A], component [B] and component [D], and then with olefin. The method for producing an olefin polymer according to claim 10. 12. A component [C], a component [A], a component [B], a component [A] and a component [B] contact product, a component [A] and a component [D] contact product, a component. After contacting with either the contact product of [B] and component [D] or the contact product of component [A], component [B] and component [D], a new component [A] is added in the presence of olefin. The method for producing an olefin polymer according to claim 11, wherein the olefin polymer is brought into contact with D].