JP2000281708A - Olefin polymerization catalyst, and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly active catalyst by using as the constituents a transition metal compound having a specified structure, an organoaluminum compound, a boron compound and a phenol. SOLUTION: The polymerization catalyst contains (A) a transition metal compound represented by any one of formula I to formula III, (B) an organoaluminum compound represented by the formula: EaAlZ3-a (C) a boron compound represented by the formula: BQ1Q2Q3, G+(BQ1Q2Q3Q4)- or (L-H)+(BQ1 Q2Q3Q4)-, and (D) a phenol, wherein the molar rations of component B, component C and component D respectively to the transition metal atoms of component A are (0.1 to 10,000):1, (0.01 to 100):1, and (0.1 to 10,000):1. In the formula, M is a group 4 transition metal atom; A is a group 16 atom; (j) is a group 14 atom; Cp is a cyclopentadiene type anion; X1 and R1 to R6 are each H, halogeno or the like; X2 is a group 16 atom; E is a hydrocarbon group; Z is H or halogeno; 0<a<=3; Q1 to Q4 are each halogeno, a hydrocarbon group or the like; G+ is an inorganic or organic cation; and (L-H)+ is Bronsted acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization using a metallocene transition metal compound and a method for producing a highly active olefin polymer using the catalyst for olefin polymerization.

[0002]

2. Description of the Related Art Many reports have already been made on processes for producing olefin polymers using metallocene complexes. For example, in JP-A-58-19306,
A method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported. This screw (η
^In a method for producing an olefin polymer using ⁵ -cyclopentadienyl) zirconium dichloride and methylaluminoxane, the activity is insufficient from an industrial viewpoint, and the molecular weight of the obtained olefin polymer is low. Was something.

JP-A-1-101303 reports a method for producing an olefin polymer using a reaction product of glucose and trimethylaluminum and bis (η ⁵ -cyclopentadienyl) titanium dichloride. However, its activity was insufficient from an industrial point of view.

JP-A-4-359002 discloses a reaction product of β-cyclodextrin, which is an organic compound having one or more hydroxyl groups, with trimethylaluminum, and bis (η ⁵ -cyclopentadienyl)
A method for producing an olefin polymer using a (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex and trimethylaluminum which has been pre-contacted has been reported, but its activity is insufficient from an industrial viewpoint. Met. Tetrahydrofuran is an inhibitor of polymerization activity, and the metallocene complex coordinated by the compound has essentially low polymerization activity.

JP-A-6-329713 reports a method for producing an olefin polymer using an aluminum compound having an electron-withdrawing group as a catalyst component for olefin polymerization. Reaction of pentafluorophenol and trimethylaluminum is a compound having an electron-withdrawing group, and bis - using (eta ^{5-methyl-cyclopentadienyl)} titanium dichloride, it is reported a method of producing an olefin polymer However, its activity was insufficient from an industrial point of view.

[0006] In JP-A-8-311120,
A method for producing an olefin polymer using a phenolic compound as a component of an olefin polymerization catalyst has been reported. Non-bridged half metallocene complexes pentamethylcyclopentadienyltitanium dichloro (diphenyl phosphide), methylalumoxane and 2,6-
A method for producing an olefin polymer using di-tert-butylphenol has been reported, and although its activity is somewhat high, the molecular weight of the obtained polymer, particularly, the molecular weight of the polymer obtained in high-temperature polymerization, is as follows: It was inadequate.

In Japanese Patent Application Laid-Open No. 9-87313, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, triisobutylaluminum and N A method for producing a copolymer of ethylene and hexene-1 using N, N-dimethylanilinium tetrakispentafluorophenylborate has been reported, and a copolymer of high molecular weight ethylene and hexene-1 has high activity. However, from an industrial point of view, further improvement in activity has been desired.

In Japanese Patent Application Laid-Open No. 9-278817,
The reaction product of bisphenol -A and trimethylaluminum is an aromatic compound having two or more hydroxy groups attached to the aromatic ring, dimethylsilylene (tert- butylamino) (eta ⁵ - cyclopentadienyl) titanium dichloride, and tri Although a method for producing an olefin polymer using isobutylaluminum has been reported, its activity was insufficient from an industrial viewpoint.

In Japanese Patent Application Laid-Open No. 9-291107, a reaction product of 2,6-di-tert-butyl-4-methylphenol, which is an organic Lewis base having steric hindrance, with triisobutylaluminum, bis (n-octadecylcycloalkyl) is disclosed. A method for producing an olefin polymer using (pentadienyl) zirconium dichloride and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate has been reported. It was inadequate. In addition, propylene polymerization has been reported using the above catalyst components,
A liquid oligomer was obtained, and a substantial polymer was not obtained.

[0010]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a highly active catalyst for olefin polymerization using a metallocene transition metal compound and a method for producing an olefin polymer using the catalyst for olefin polymerization. The purpose is to provide.

[0011]

That is, the present invention provides an olefin polymerization catalyst using the following (A), (B), (C) and (D), and an olefin polymerization using the olefin polymerization catalyst. The present invention relates to a method for producing a united product. (A): a transition metal compound represented by the following general formula [I], [II] or [III] (In the general formulas [I], [II] and [III], M represents a transition metal atom of Group 4 of the periodic table of the element, and A represents an atom of Group 16 of the periodic table of the element.) Show, J
Represents an atom belonging to Group 14 of the periodic table of the elements. Cp represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group. An aryloxy group, a disubstituted amino group,
Alkylthio group, aralkylthio group, arylthio group,
It represents an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² represents an atom of Group 16 of the periodic table of the element. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. Multiple M, A, J, C
p, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. ) (B) the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E may or may not be the same.
Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a is a number satisfying 0 <a ≦ 3. (C): a boron compound represented by any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a general formula G ⁺ (BQ ^{1 Q 2 Q 3 Q 4)} - boron compound represented by (C3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent atom And Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid.) (D): Phenols

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. (A) Transition metal compound The transition metal compound used in the present invention has the following general formula [I],
It is a transition metal compound represented by [II] or [III]. (In the general formulas [I], [II] and [III], M represents a transition metal atom of Group 4 of the periodic table of the element, and A represents an atom of Group 16 of the periodic table of the element.) Show, J
Represents an atom belonging to Group 14 of the periodic table of the elements. Cp represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group. An aryloxy group, a disubstituted amino group,
Alkylthio group, aralkylthio group, arylthio group,
It represents an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² represents an atom of Group 16 of the periodic table of the element. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. Multiple M, A, J, C
p, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. )

The above general formula [I], [II] or [III]
In the above, the transition metal atom represented by M represents a transition metal atom belonging to Group 4 of the Periodic Table of the Elements (IUPAC Revised Edition of Inorganic Chemical Nomenclature, 1989), for example, a titanium atom, a zirconium atom, a hafnium atom and the like. It is. Preferably, it is a titanium atom or a zirconium atom.

In the general formulas [I], [II] and [III], the atom of Group 16 of the periodic table of the element represented by A includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like. Preferably, it is an oxygen atom.

In the general formulas [I], [II] and [III], examples of atoms belonging to group 14 of the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Preferably, it is a carbon atom or a silicon atom.

Cyclopentadi represented by the substituent Cp
Examples of the group having an ene-type anion skeleton include η^Five−
(Substituted) cyclopentadienyl group, η^Five-(Replace) in
Denenyl group, η^Five-(Substituted) fluorenyl group and the like.
To give a concrete example, for example, η^Five−cyclopentadiene
Group, η^Five-Methylcyclopentadienyl group, η^Five−Jimme
Tylcyclopentadienyl group, η^Five-Trimethylcyclo
Pentadienyl group, η^Five-Tetramethylcyclopentadi
Enyl group, η^Five-Pentamethylcyclopentadienyl
Group, η^Five-Ethylcyclopentadienyl group, η^Five-N-pu
Ropylcyclopentadienyl group, η^Five-Isopropyl
Clopentadienyl group, η^Five-N-butylcyclopenta
Dienyl group, η^Five-Sec-butylcyclopentadienyl
Group, η^Five-Tert-butylcyclopentadienyl
Group, η^Five-Phenylcyclopentadienyl group, η^Five-Bird
Methylsilylcyclopentadienyl group, η^Five-Tert
-Butyldimethylsilylcyclopentadienyl group, η^Five
-Indenyl group, η^Five-Methylindenyl group, η^Five−Jimme
Tilindenyl group, η^Five-N-propylindenyl group,
η^Five-Isopropylindenyl group, η^Five-N-butylin
Denenyl group, η^Five-Tert-butylindenyl group, η^Five−
Phenylindenyl group, η^Five-Methylphenylindeni
Group, η^Five-Naphthylindenyl group, η^Five-Trimethylsi
Rilindenyl group, η^FiveA tetrahydroindenyl group,
η^FiveA fluorenyl group, η^Five-Methylfluorenyl group, η
^Five-Dimethylfluorenyl group, η^Five-Tert-butyl ether
Fluorenyl group, η^Five-Di-tert-butylfluorenyl
Group, η^FiveA phenylfluorenyl group, η^Five-Diphenyl
Fluorenyl group, η^Five-Trimethylsilylfluorenyl
Group, η^Five-Bistrimethylsilylfluorenyl group or the like
And preferably η^FiveA cyclopentadienyl group,
η^Five-Methylcyclopentadienyl group, η^Five-N-butyl
Cyclopentadienyl group, η^Five-Tert-butylsic
Lopentadienyl group, η^Five-Tetramethylcyclopenta
Dienyl group, η^Five-Pentamethylcyclopentadienyl
Group, η^Five-Indenyl group, η^Five-Tetrahydroindenyl
Group, or η^Five-A fluorenyl group.

Examples of the halogen atom for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ^{5 and} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. It is an atom or a bromine atom, more preferably a chlorine atom.

The alkyl group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 1 to 2 carbon atoms.
An alkyl group of 0 is preferable, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n-
Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group, isobutyl Or an amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 7 to 7 carbon atoms.
20 aralkyl groups are preferred, for example a benzyl group,
(2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (3,5
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like,
More preferably, it is a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aryl group represented by the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has ^{6 to 2} carbon atoms.
And an aryl group of 0 is preferable, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group,
6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5
-Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4
5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like, and more preferably a phenyl group. All of these aryl groups are a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom,
It may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituted silyl group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is a silyl group substituted by a hydrocarbon group, wherein the hydrocarbon group is Is a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group.
Disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-
Butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 20 alkoxy groups, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-
A pentadeoxy group, an n-icosoxy group, and the like,
More preferably, they are a methoxy group, an ethoxy group, an isopropoxy group, or a tert-butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkyloxy group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group. A (2-methylphenyl) methoxy group,
(3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group,
(2,5-dimethylphenyl) methoxy group, (2,6-
(Dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an octylphenyl) methoxy group, an (n-decylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aryloxy group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy group, 2 -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,
3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group Group,
2-tert-butyl-6-methylphenoxy group, 2,
3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6
-Trimethylphenoxy group, 2-tert-butyl-
3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-te
rt-butyl-3-methylphenoxy group, 2-tert
-Butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,
4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,
4,6-trimethylphenoxy group, 2,6-di-ter
t-butyl-3,4-dimethylphenoxy group, 2,3
5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-
Di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl Examples include a phenoxy group, a naphthoxy group, and an anthracenoxy group. All of these aryloxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The disubstituted amino group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups or silyl groups, Here, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. An alkyl group having 1 to 10 carbon atoms such as a cyclohexyl group, an aryl group having 6 to 10 carbon atoms such as a phenyl group, an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, and a silyl group. Include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of such a disubstituted amino group include a dimethylamino group, a diethylamino group,
Di-n-propylamino group, diisopropylamino group,
Di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group, diisobutylamino group, tert-butylisopropylamino group, di-n
-Hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, and the like, preferably dimethylamino group, diethylamino group, diisopropylamino group, -Tert-butylamino group and bistrimethylsilylamino group. Each of these disubstituted amino groups is a fluorine atom, a chlorine atom,
A halogen atom such as a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The alkylthio group in the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 1 carbon atom.
To 20 alkylthio groups, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, t
tert-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n
-Eicosylthio group and the like, and more preferably a methylthio group, an ethylthio group, an isopropylthio group or a tert-butylthio group. All of these alkylthio groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkylthio group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkylthio group having 7 to 20 carbon atoms, for example, a benzylthio group, ( 2-methylphenyl) methylthio group, (3
-Methylphenyl) methylthio group, (4-methylphenyl) methylthio group, (2,3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group,
(2,6-dimethylphenyl) methylthio group, (3,4
-Dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, (2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6 -Trimethylphenyl) methylthio group, (2,4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3 , 4,5-tetramethylphenyl) methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group Group, (ethylphenyl) methylthio group,
(N-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n
-Hexylphenyl) methylthio group, (n-octylphenyl) methylthio group, (n-decylphenyl) methylthio group, naphthylmethylthio group, anthracenylmethylthio group, and the like, and more preferably a benzylthio group. All of these aralkylthio groups include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, alkoxy groups such as a methoxy group and an ethoxy group, aryloxy groups such as a phenoxy group, and aralkyloxy groups such as a benzyloxy group. It may be partially substituted with a group or the like.

The arylthio group represented by the substituent X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ has 6 carbon atoms.
To 20 arylthio groups are preferred, for example, phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2,3-dimethylphenylthio, 2,4-dimethylphenylthio ,
2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,
5-dimethylphenylthio group, 2-tert-butyl-
3-methylphenylthio group, 2-tert-butyl-4
-Methylphenylthio group, 2-tert-butyl-5-
Methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,
3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethylphenylthio group, 2-tert- Butyl-3,5-dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-
4,5-dimethylphenylthio group, 2,6-di-ter
t-butyl-4-methylphenylthio group, 3,4,5-
Trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl-3,4,
5-trimethylphenylthio group, 2,3,4,6-tetramethylphenylthio group, 2-tert-butyl-3,
4,6-trimethylphenylthio group, 2,6-di-te
rt-butyl-3,4-dimethylphenylthio group, 2,
3,5,6-tetramethylphenylthio group, 2-ter
t-butyl-3,5,6-trimethylphenylthio group,
2,6-di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec
-Butylphenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n-tetradecylphenylthio group, naphthylthio group, anthracenylthio group, etc. Is mentioned. All of these arylthio groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

As the alkylseleno group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ , an alkylseleno group having 1 to 20 carbon atoms is preferable, for example, a methylseleno group, ethylseleno Group, n-propylseleno group, isopropylseleno group, n-butylseleno group, sec-butylseleno group, tert-butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, an n-dodecylseleno group,
Examples thereof include an n-pentadecylseleno group and an n-eicosylseleno group, and more preferred are a methylseleno group, an ethylseleno group, an isopropylseleno group, and a tert-butylseleno group. All of these alkylseleno groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aralkylseleno group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkylseleno group having 7 to 20 carbon atoms, for example, a benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group, (2,3-dimethylphenyl) methylseleno group, (2,4-dimethylphenyl) methylseleno group, 2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group,
(2,3,4-trimethylphenyl) methylseleno group,
(2,3,5-trimethylphenyl) methylseleno group,
(2,3,6-trimethylphenyl) methylseleno group,
(2,4,5-trimethylphenyl) methylseleno group,
(2,4,6-trimethylphenyl) methylseleno group,
(3,4,5-trimethylphenyl) methylseleno group,
(2,3,4,5-tetramethylphenyl) methylseleno group, (2,3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (penta (Methylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-
(Propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group,
(N-hexylphenyl) methylseleno, (n-octylphenyl) methylseleno, (n-decylphenyl) methylseleno, naphthylmethylseleno, anthracenylmethylseleno, and the like, more preferably benzylseleno is there. All of these aralkyl seleno groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

As the arylseleno group for the substituents X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an arylseleno group having 6 to 20 carbon atoms is preferable. 2-methylphenylseleno group, 3-methylphenylseleno group, 4-methylphenylseleno group, 2,
3-dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 2,5-dimethylphenylseleno group,
2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4-methylphenyl Seleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2,3,4-trimethylphenylseleno group, 2,
3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2-tert-butyl-3, 4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di-tert-butyl-3-methyl Phenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-
tert-butyl-4-methylphenylseleno group, 3,
4,5-trimethylphenylseleno group, 2,3,4,5
-Tetramethylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group, 2,
3,4,6-tetramethylphenylseleno group, 2-te
rt-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group, 2,3,5,6-tetramethylphenylseleno group, 2- tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno Group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n
-Hexylphenylseleno group, n-octylphenylseleno group, n-decylphenylseleno group, n-tetradecylphenylseleno group, naphthylseleno group, anthracenylseleno group and the like. All of these arylseleno groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

Preferably, X ¹ is independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, more preferably a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. is there.

R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group,
An aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group, wherein R ¹ is an alkyl group, an aralkyl group,
An aryl group or a substituted silyl group is particularly preferred.

R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

The above general formula [I], [II] or [III]
X ² represents an atom of Group 16 of the Periodic Table of the Elements in the Specific examples, oxygen atom, sulfur atom, selenium atom, preferably an oxygen atom or a sulfur atom, more preferably oxygen Is an atom.

Specific examples of the transition metal compound represented by the general formula [I] include methylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclo Pentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( η ⁵ -cyclopentadienyl) (3-
Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, methylene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3-phenyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetra Methylcyclopentadienyl) (3
- trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-
Methoxy-2-phenoxy) titanium dichloride,
Methylene (η ⁵ -tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropylidene (η ⁵
-Cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (eta ⁵ - cyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert Butyl-5-methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3, 5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵
-Tetramethylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-phenyl-2 - phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl Enyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η
⁵ -tetramethylcyclopentadienyl) (3-ter
t- butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-phenyl-2 phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3
- trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclo Pentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetra Methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride , diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5- Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc. And compounds in which titanium is changed to zirconium or hafnium, or dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino). , (Η ⁵
- cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl)
(Η ⁵ -n-butylcyclopentadienyl), (η ⁵ -t
ert- butylcyclopentadienyl), (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -ter
t-butyldimethylsilylcyclopentadienyl),
(Η ⁵ -indenyl), (η ⁵ -methylindenyl),
(Eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to (3,5-dimethyl-2-phenoxy) the (2-phenoxy), (3-methyl-2-phenoxy), (3 , 5-Di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-)
Phenoxy) or a transition metal compound such as a compound changed to (3-trimethylsilyl-2-phenoxy),

Dimethylsilylene (η^Five-Cyclopentadi
Enyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (η^Five-Cyclopentadienyl) (3
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilene (η^Five-Cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium
Dichloride, dimethylsilylene (η^Five-Cyclopentane
Dienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethyl silyl
(Η^Five-Cyclopentadienyl) (3,5-di-te
rt-butyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titani
Um dichloride, dimethylsilylene (η^Five-Cyclope
Antadienyl) (3-tert-butyldimethylsilyl)
-5-methyl-2-phenoxy) titanium dichlori
Dimethylsilylene (η^Five-Cyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Cyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichlorai
Dimethylsilylene (η^Five-Cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Cyclopentadienyl) (3,5-diamyl-2-f
Enoxy) titanium dichloride, dimethylsilylene
(Η^Five-Cyclopentadienyl) (1-naphthoxy-2
-Yl) titanium dichloride, dimethylsilylene
(Η^Five-Tetramethylcyclopentadienyl) (2-f
Enoxy) titanium dichloride, dimethylsilylene
(Η ^Five-Tetramethylcyclopentadienyl) (3-meth
Tyl-2-phenoxy) titanium dichloride, dime
Tylsilylene (η^Five-Tetramethylcyclopentadienyl
) (3,5-dimethyl-2-phenoxy) titanium
Dichloride, dimethylsilylene (η^Five-Tetramethyl
Cyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, dimethyl silyl
(Η^Five-Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) tita
Dichloride, dimethylsilylene (η^Five-Tetra
Methylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (η^Five-Tetramethylcyclopentadi
Enyl) (5-methyl-3-phenyl-2-phenoxy)
C) Titanium dichloride, dimethylsilylene (η^Five
-Tetramethylcyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy
C) Titanium dichloride, dimethylsilylene (η^Five
-Tetramethylcyclopentadienyl) (5-methyl-
3-trimethylsilyl-2-phenoxy) titaniumdi
Chloride, dimethylsilylene (η^Five-Tetramethylsi
Clopentadienyl) (3-tert-butyl-5-meth
Toxi-2-phenoxy) titanium dichloride, di
Methylsilylene (η^Five-Tetramethylcyclopentadie
Nyl) (3-tert-butyl-5-chloro-2-fe
Noxy) titanium dichloride, dimethylsilylene
(Η^Five-Tetramethylcyclopentadienyl) (3,5
-Diamyl-2-phenoxy) titanium dichlorai
Dimethylsilylene (η^Five-Tetramethylcyclopen
Tadienyl) (1-naphthoxy-2-yl) titanium
Dichloride, etc., and η of these compounds^Five-Cyclope
Ntadienyl to η^Five-Methylcyclopentadienyl, η^Five
-Dimethylcyclopentadienyl, η^Five-Trimethylsi
Clopentadienyl, η^Five-Ethylcyclopentadienyl
Le), η^Five-N-propylcyclopentadienyl, η^Five−
Isopropylcyclopentadienyl, η^Five-N-butyl
Cyclopentadienyl, η^Five-Sec-butylcyclope
Ntadienyl, η^Five-Isobutylcyclopentadienyl
, Η^Five-Tert-butylcyclopentadienyl, η^Five
-Trimethylsilylcyclopentadienyl, η^Five−te
rt-butyldimethylsilylcyclopentadienyl, η
^Five-Phenylcyclopentadienyl, η^Five-Indenyl,
η^Five-Methylindenyl, η^Five-Phenylindenyl or
Is η^Five-Compound changed to fluorenyl, 2-phenoki
Is 3-phenyl-2-phenoxy, 3-trimethyl
Ryl-2-phenoxy or 3-tert-butyldi
Compounds changed to methylsilyl-2-phenoxy,
Diethylsilylene and diphenylsilylene
Compounds changed to dimethoxysilylene, titanium
Conversion of zirconium or hafnium to nickel
Compound, dichloride to dimethyl, dibenzyl, dimethoxy
, Diphenoxide, bis (dimethylamino) or
Transition gold such as a compound changed to
Genus compounds and the like.

Specific examples of the transition metal compound represented by the general formula [II] include μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride} and μ-oxobis {isopropylidene (Η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛isopropylidene (η ⁵ -cyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} , .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium methoxide ｝, Μ-oxobis ｛isopropylidene (η ⁵ -methylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} isopropylidene (η ⁵ -methylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium methoxide, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene ( eta ⁵ - tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2- phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide},

Μ-oxobis ｛dimethylsilylene (η ⁵
-Cyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛dimethylsilylene (η ⁵ − Cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵ −
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium methoxide {, μ
- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis ｛dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (η ⁵
-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium Chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium methoxide and the like, compounds in which titanium is changed to zirconium or hafnium, compounds in which chloride is changed to methyl, benzyl, phenoxide, dimethylamino or diethylamino, (η ⁵ -cyclopentadienyl) To (η ⁵
- dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadienyl), (eta ⁵ - trimethylsilyl cyclopentadienyl), (eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl), (eta ⁵ - indenyl)
(Eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to
(2-phenoxy) is (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,
5-di-tert-butyl-2-phenoxy), (3-
Phenyl-5-methyl-2-phenoxy) or (3-
Trimethylsilyl-5-methyl-2-phenoxy).

The transition metal compound represented by the general formula [III]
Specific examples of di-μ-oxobis {isopropylidene
Den (η^Five-Cyclopentadienyl) (2-phenoxy
C) Titanium, di-μ-oxobis isopropyl
Den (η^Five-Cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium
Di-μ-oxobis ｛isopropylidene (η^Five-Methyl
Cyclopentadienyl) (2-phenoxy) titanium
｝, Di-μ-oxobis ｛isopropylidene (η ^Five−
Methylcyclopentadienyl) (3-tert-butyl
-5-methyl-2-phenoxy) titanium}, di-μ
Oxobis ｛isopropylidene (η^Five-Tetramethyl
Cyclopentadienyl) (2-phenoxy) titanium
｝, Di-μ-oxobis ｛isopropylidene (η^Five−
Tetramethylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium

Di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert- Butyl-5-methyl-2-phenoxy) titanium}, di-
μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium},
Di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethyl) Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium}, a compound in which titanium of these compounds is changed to zirconium or hafnium, (η ⁵ -cyclopentadienyl) is replaced by (η ⁵ -dimethylcyclopentadienyl), (η ^Five
- trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadienyl), (eta ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert - butyldimethylsilyl cyclopentadienyl), (eta ⁵ - indenyl), (eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - fluorenyl) compound was changed to (2-phenoxy ) Is (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy),
(3,5-di-tert-butyl-2-phenoxy),
Compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy) are exemplified.

The transition metal compound represented by the general formula [I] is synthesized, for example, by the method described in JP-A-9-87313. In addition, the above general formula [II] or [II
The transition metal compound represented by I] can be obtained, for example, by reacting the transition metal compound represented by the above general formula [I] with 0.5 times or 1 times the amount of water. At this time, a method of directly reacting the transition metal compound with a required amount of water, a method of charging the transition metal compound into a solvent such as a hydrocarbon containing the required amount of water, and a method of adding the transition metal to a solvent such as a dried hydrocarbon. A method in which a compound is charged and an inert gas containing a required amount of water or the like is further allowed to flow can be adopted.

[0045] (B) an organoaluminum compound used in the organic aluminum compound present invention have the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E is be different even in the same Z is a hydrogen atom or a halogen atom, and all Zs may be the same or different; a represents a number satisfying 0 <a ≦ 3.) . E
Is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group.

[0046] Specific examples of the organic aluminum compound represented by the general formula E _a AlZ _3-a, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; dimethylaluminum chloride, Dialkylaluminum chlorides such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; dimethylaluminum Idoraido, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride. More preferably, it is trialkylaluminum, and still more preferably, trimethylaluminum, triethylaluminum, or triisobutylaluminum.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one of boron compound represented by can be used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ each have at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. And Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as

The general formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

[0054] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{−, the same} as those described above can be mentioned.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

(D) Phenols The phenols used in the present invention are compounds in which a hydroxyl group is directly bonded to an aromatic 6-membered ring, and preferably have the general formula ROH (where R is an aryl group having 6 to 20 carbon atoms). Phenols).

The aryl group having 6 to 20 carbon atoms here includes, for example, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-isopropylphenyl, n-butylphenyl group, 2-sec-butylphenyl group, 2-tert
-Butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2-n-octylphenyl group, 2-n-dodecylphenyl group, 2-phenylphenyl group, 4-phenylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,
6-di-tert-butylphenyl group, 2,4-di-t
tert-butylphenyl group, 2-tert-butyl-4
-Methylphenyl group, 2-tert-butyl-5-methylphenyl group, 2-tert-butyl-6-methylphenyl group, 2-n-dodecyl-4-methylphenyl group, 4
-N-dodecyl-2-methylphenyl group, 2,6-diphenylphenyl group, 2,6-di-tert-butyl-4
-Methylphenyl group, 2,6-di-tert-butyl-
4-ethylphenyl group, 2,4,6-tri-tert-
Butylphenyl group, α-naphthyl group, β-naphthyl group,
Examples include an anthracenyl group and the like, and preferably a phenyl group, a 2,6-di-tert-butylphenyl group, or a 2,6-di-tert-butyl-4-methylphenyl group. All of these aryl groups are a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom,
It may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an araloxy group such as a benzyloxy group.

Examples of the phenol having an aryl group include phenol, 2-methylphenol,
2-ethylphenol, 2-n-propylphenol,
2-isopropylphenol, 2-n-butylphenol, 2-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol,
-Tert-butylphenol, 2-n-octylphenol, 2-n-dodecylphenol, 2-phenylphenol, 4-phenylphenol, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-di-tert- Butylphenol, 2,4-di-tert
-Butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-6-methylphenol, 2-n-dodecyl-4-methylphenol, 4-n
-Dodecyl-2-methylphenol, 2,6-diphenylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-
Ethylphenol, 2,4,6-tri-tert-butylphenol, 3-methylphenol, 4-methylphenol, 3-ethylphenol, 4-ethylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-isobutylphenol , 3-isobutylphenol, 4-isobutylphenol, 2,6-diisopropylphenol, 2,6-diisobutylphenol, 2,4,6-trimethylphenol, 2,6-diethyl-4-methylphenol, 2,6-diisopropyl -4-methylphenol, 2,6-diisobutyl-4
-Methylphenol, α-naphthol, β-naphthol, anthracenol, 2-fluorophenol, 3-
Fluorophenol, 4-fluorophenol, 2,3
-Difluorophenol, 2,4-difluorophenol, 2,5-difluorophenol, 2,6-difluorophenol, 2,3,4-trifluorophenol,
2,3,5-trifluorophenol, 2,3,6-trifluorophenol, 2,4,6-trifluorophenol, 2,3,4,5-tetrafluorophenol,
Pentafluorophenol, 3,5-bis (trifluoromethyl) phenol, 2-methoxyphenol, 3-
Methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-isopropoxyphenol, 3-methoxyphenol
Isopropoxyphenol, 4-isopropoxyphenol, 2-isobutoxyphenol, 3-isobutoxyphenol, 4-isobutoxyphenol, 2-ter
t-butoxyphenol, 3-tert-butoxyphenol, 4-tert-butoxyphenol, 2-
Phenoxyphenol, 3-phenoxyphenol,
Examples thereof include 4-phenoxyphenol, 2-benzyloxyphenol, 3-benzyloxyphenol, and 4-benzyloxyphenol, and particularly preferred are phenol, 2,6-di-tert-butylphenol, and 2,6-di-phenol. tert-butyl-4-methylphenol or pentafluorophenol.

[Polymerization of olefin] In the present invention,
An olefin polymerization catalyst comprising the above (A), (B), (C) and (D) is used. In the present invention, at the time of polymerization of the olefin, each of the above-mentioned components can be added and used in an arbitrary order during the polymerization. May be. In the present invention, an olefin polymerization catalyst comprising (A) and (C), and a reaction product obtained by previously bringing (B) and (D) into contact with each other, is more preferable.

The amount of each component used is usually such that the molar ratio of (B) / [transition metal atom contained in the transition metal compound (A)] is from 0.1 to 10,000, preferably from 5 to 2,000.
The molar ratio of (C) / [the transition metal atom contained in the transition metal compound (A)] is 0.01 to 100, preferably 0.5.
Each component may be used such that the molar ratio of (D) / (the transition metal atom contained in the transition metal compound (A)) is from 0.1 to 10,000, and preferably from 1 to 500. desirable.

The concentration when each component is used in the form of a solution or a suspension or slurry in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. Usually 0.001 to 200 mm in terms of transition metal atoms contained in the transition metal compound (A).
ol / L, more preferably 0.001 to 100 mm
ol / L, more preferably 0.05 to 50 mmol
/ L, (B) is usually 0.01 to 5000 mmol / L
And more preferably, 0.1 to 2500 mmol / L,
More preferably, 0.1 to 2000 mmol / L,
(C) is usually 0.001 to 500 mmol / L, more preferably 0.01 to 250 mmol / L, still more preferably 0.05 to 100 mmol / L, and (D)
Is preferably 0.01 to 5000 mmol / L, more preferably 0.1 to 2500 mmol / L, and still more preferably 0.1 to 1000 mmol / L.

The olefins applicable to the polymerization in the present invention include olefins having 2 to 20 carbon atoms, especially ethylene, α-olefins having 3 to 20 carbon atoms, and diolefins having 4 to 20 carbon atoms. And the like, and two or more types of monomers can be used at the same time. Specific examples of the olefin include linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, and 3-methylbutene-. Examples include branched olefins such as 1,3-methylpentene-1, 4-methylpentene-1, and 5-methylhexene-1, and vinylcyclohexane, but the present invention is not limited to the above compounds. . Specific examples of the combination of monomers when performing the copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, propylene and butene-1, and the like. The invention should not be limited to these combinations.

The present invention is particularly useful for the production of copolymers of ethylene with α-olefins, especially propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1 and other α-olefins. Applicable.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and methylene dichloride and the like can be used. Solvent polymerization using a halogenated hydrocarbon as a solvent, or slurry polymerization, or a method called high-pressure ionic polymerization, in which the olefin polymer formed into an olefin in a supercritical fluid state under high temperature and pressure without solvent is melted. The polymerization can be carried out in a state in which the polymerization has been carried out, and furthermore, a gas phase polymerization in a gaseous monomer or the like is possible, and both continuous polymerization and batch polymerization are possible.

The polymerization temperature can range from -50 ° C to 350 ° C, preferably from 0 ° C to 300 ° C, particularly preferably from 50 ° C to 300 ° C. Polymerization pressure is normal pressure ~
Although it can be in the range of 350 MPa, it is preferably normal pressure to 3 MPa.
00 MPa, particularly preferably normal pressure to 200 MPa.

The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, and there is no particular condition to be restricted, but it can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0067]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The properties of the polymers in the examples were measured by the following methods.

(1) Melting point of copolymer: Determined by using an SSC5000 thermal analysis system manufactured by Seiko Denshi Kogyo KK under the following conditions. Temperature rise: Raise the temperature to 150 ° C, hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

(2) α-Olefin content: Determined from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FTIR1600 series manufactured by PerkinElmer), the number of short-chain branches per 1000 carbons (SCB ).

(3) Intrinsic Viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and an Ubbelohde viscometer set in a water bath maintained at 135 ° C. was used. And the falling speed of the tetralin solution in which the sample was dissolved.

(4) Molecular weight and molecular weight distribution: Determined using gel permeation chromatograph (150, C manufactured by Waters) under the following conditions. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-ortho-dichlorobenzene

Reference Example 1 (Transition metal compound: dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-
Example of synthesis of 5-methyl-2-phenoxy) titanium dimethoxide <compound> 0.131 g (4.1 mmol) of methanol in 10 ml of anhydrous ether in a Schlenk tube
Is dissolved at −78 ° C. in an ether solution of methyllithium having a concentration of 1.05 mol / L (3.9 ml, 4.1 mmol).
l) was added dropwise. The temperature was raised to 20 ° C., and the completion of gas generation was confirmed, whereby the formation of lithium methoxide was confirmed, and the mixture was cooled again to −78 ° C. It prepared in advance to another Schlenk tube, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride
A suspension of 919 g (2.0 mmol) of 20 ml of anhydrous ether was transferred to the above reaction solution, and then gradually heated to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were filtered off. The filtrate was concentrated, dimethylsilylene the following structural formula - were obtained (eta ^{5-tetramethylcyclopentadienyl)} (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide as yellow crystals. (0.86 g, 95%) ¹ H-NMR (270 MHz, C ₆ D ₆ ) δ7.26
(M, 2H), 4.13 (s, 6H), 2.33 (s,
3H), 1.97 (s, 6H), 1.89 (s, 6
H), 1.59 (s, 9H), 0.55 (s, 6H)

Example 1 After replacing an autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter with argon, 185 ml of cyclohexane was used as a solvent and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa, and after the system was stabilized, 0.2 mmol of triisobutylaluminum and 10 μmol of 2,6-di-tert-butylphenol (heptane solution, 10 μmol / m2)
l), a heptane solution in which the compound and triisobutylaluminum are mixed (the concentration of the compound is 1 μmol / m
l, the concentration of triisobutylaluminum is 50 μmol
/ Ml) is 0.5 ml (ie, the compound is 0.5 μmo
l, triisobutylaluminum (25 μmol) was charged, and subsequently, a liquid in which 1.5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was slurried in heptane (slurry concentration: 1 μmo)
1 / ml). Polymerization was performed for 2 minutes. As a result of polymerization, ethylene having [η] of 1.00, SCB of 31.8, melting point of 79.3 ° C. and 89.6 ° C., Mw of 59,300, and molecular weight distribution (Mw / Mn) of 2.1 was used. 3.16 g of a copolymer with hexene-1 was obtained. The polymerization activity per mole of Ti atom is 6.3 × 10 ⁶ g / T per 2 minutes.
imol.

COMPARATIVE EXAMPLE 1 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.2 mmol of triisobutylaluminum, a heptane solution in which the compound and triisobutylaluminum were mixed (the concentration of the compound was 1 μm
ol / ml, the concentration of triisobutylaluminum is 50
μmol / ml) was added to 0.5 ml (that is, the compound was added at 0.
5 μmol, 25 μmo triisobutylaluminum
l) Charge, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 1.5 μm
ol in heptane (slurry concentration, 1
μmol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 1.07 and SCB was 31.
7, melting point 76.3 ° C, 88.4 ° C, Mw 6580
2.30 g of a copolymer of ethylene and hexene-1 having a molecular weight distribution (Mw / Mn) of 2.05 was obtained. Ti
The polymerization activity per mole of atom is 4.6 × per 2 minutes.
Was 10 ⁶ g / Timol.

Example 2 (1) Preparation of Compound A dropping funnel was attached to a 100 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. 10 mmol of triisobutylaluminum (10 ml of a 1 mmol / ml heptane solution) and 10 ml of heptane
Was charged into a flask and stirred. 2,6-di-tert
-Butylphenol 10 mmol (concentration 0.2 mmol)
/ Ml toluene solution was charged into the dropping funnel, and the solution was dropped while keeping the internal temperature at 5 to 10 ° C, and the dropping funnel was washed away with 5 ml of toluene. After the completion of the dropwise addition, the mixture was stirred at 5 to 10 ° C for 0.5 hour and then at 25 ° C to 30 ° C for 1 hour.
Triisobutylaluminum and 2,6-di-tert-
A reaction product (compound) of butylphenol was obtained, and its Al concentration was 0.13 mmol / ml.

(2) Polymerization After purging the autoclave type reactor with a stirring blade with an inner volume of 0.4 liter with argon, 185 ml of cyclohexane was used as a solvent, and hexene-1 was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.2 mmol of the compound and a heptane solution in which the compound and triisobutylaluminum were mixed (the concentration of the compound was 1 μmol / ml, 0.5 ml of triisobutylaluminum (concentration of 50 μmol / ml) (that is, 0.5 μmol of the compound and 25 μmol of triisobutylaluminum) were added, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. 5 μmol was fed as a liquid (slurry concentration, 1 μmol / ml) slurried in heptane. Polymerization was performed for 2 minutes. As a result of polymerization,
[Η] 0.77, SCB 34.4, melting point 78.4
C., 84.1 ° C., Mw 42600, molecular weight distribution (M
(w / Mn) of 2.3 obtained 6.15 g of a copolymer of ethylene and hexene-1. The polymerization activity was 1.2 × 10 ⁷ g / Timo per mole of Ti atom per 2 minutes.
l.

Example 3 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, the compound was 0.2 mmol, a heptane solution in which the compound and the compound were mixed (the concentration of the compound was 1 μmol / ml, The concentration is 50 μm
ol / ml) in 0.5 ml (i.e., 0.5 μl of compound).
mol, 25 μmol of the compound), followed by N,
1.5 μmol of N-dimethylanilinium tetrakis (pentafluorophenyl) borate was slurried in heptane (slurry concentration, 1 μmol / ml). Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.90, SCB was 34.5, melting point was 79.1 ° C., 8
At 4.5 ° C., the Mw was 51700 and the molecular weight distribution (Mw / M
4.56 g of a copolymer of ethylene and hexene-1 in which n) was 2.1 was obtained. The polymerization activity was 9.1 × 10 ⁶ g / Timol per 2 minutes per mole of Ti atom.

Example 4 (1) Preparation of Compound After a 100 ml four-necked flask was purged with nitrogen, a thermometer was attached. Triisobutyl aluminum 10mm
ol (10 mM heptane solution with a concentration of 1 mmol / ml)
l) and 5 ml of heptane were charged into a flask and stirred. 10 mmol of pentafluorophenol (5 ml of a toluene solution having a concentration of 2 mol / l) was added at an internal temperature of 5-1.
It was kept at 0 ° C and added dropwise. After dropping, 0.5 at 5-10 ° C
The mixture was stirred for 0.5 hour and then at 25 ° C to 30 ° C for 0.5 hour. A reaction product (compound) of triisobutylaluminum and pentafluorophenol was obtained, and its Al concentration was 0.5.
mmol / ml.

(2) Polymerization After purging the autoclave type reactor with a stirring blade with an inner volume of 0.4 liter with argon, 185 ml of cyclohexane as a solvent and 1 of hexene-1 as an α-olefin were added.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.2 mmol of the compound and a heptane solution in which the compound and triisobutylaluminum were mixed (the concentration of the compound was 1 μmol / ml, 0.5 ml of triisobutylaluminum (concentration of 50 μmol / ml) (that is, 0.5 μmol of the compound and 25 μmol of triisobutylaluminum) were added, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. 5 μmol was fed as a liquid (slurry concentration, 1 μmol / ml) slurried in heptane. Polymerization was performed for 2 minutes. As a result of polymerization,
[Η] is 0.95, SCB is 33.3, and melting point is 78.1.
C., 83.8 ° C., Mw 53500, molecular weight distribution (M
4.61 g of a copolymer of ethylene and hexene-1 having a ratio (w / Mn) of 2.6 was obtained. The polymerization activity was 9.2 × 10 ⁶ g / Timo per mole of Ti atom per 2 minutes.
l.

Example 5 (1) Preparation of Compound After a dropping funnel was attached to a 100 ml four-necked flask, nitrogen replacement was performed, and a thermometer was attached. Triisobutylaluminum 10 mmol (concentration 1 mmol / ml
Was added to a flask and stirred. 20 mmol of pentafluorophenol (10 ml of 2 mmol / ml of a toluene solution having a concentration of 10 mmol) was charged into the dropping funnel, dropped while maintaining the internal temperature at 5 to 10 ° C., and the dropping funnel was washed away with 5 ml of toluene. After dropping, 5
The mixture was stirred at 10 ° C for 0.5 hour and at 25 ° C to 30 ° C for 0.5 hour. A reaction product (compound) of triisobutylaluminum and pentafluorophenol was obtained as a white slurry. Its Al concentration was 0.4 mmol / ml.

(2) Polymerization After purging the autoclave type reactor with a stirring blade with an inner volume of 0.4 liter with argon, 185 ml of cyclohexane as a solvent and 1 of hexene-1 as an α-olefin were added.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.1 mmol of the compound, 0.1 mmol of triisobutylaluminum, and a heptane solution in which the compound and triisobutylaluminum were mixed ( The concentration of the compound is 1 μmol / ml and the concentration of triisobutylaluminum is 50 μmol / ml).
ml (ie, 0.5 μmol of compound and 25 μmol of triisobutylaluminum), followed by N, N
-Dimethylanilinium tetrakis (pentafluorophenyl) borate (1.5 μmol) was added as a liquid (slurry concentration, 1 μmol / ml) made into a slurry in heptane. Polymerization was performed for 2 minutes. As a result of polymerization, [η] was 0.79, SCB was 34.8, melting point was 74.8 ° C., 8
At 8.0 ° C., Mw was 42,300, and molecular weight distribution (Mw / M
6.82 g of an ethylene-hexene-1 copolymer having n) of 3.0 was obtained. The polymerization activity was determined per mole of Ti atom,
It was 1.4 × 10 ⁷ g / Timol per 2 minutes.

[0082]

As described in detail above, according to the present invention,
A highly active catalyst for olefin polymerization using a metallocene-based transition metal compound, particularly a highly active olefin polymerization catalyst at an efficient reaction temperature in an industrial process of olefin polymerization is provided. According to the present invention, a method for producing an olefin polymer using the catalyst for olefin polymerization is provided, and its utility value is extremely large.

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J028 AA01A AB01A AC01A AC09A AC10A AC26A AC27A BA00A BA02B BB00A BB01B BC12B BC15B BC16B BC17B BC27B CB25C EA01 EB02 EB04 EB05 EB07 EB08 EC01 FA01 EC02

Claims (6)

[Claims] 1. The following (A), (B), (C) and (D)
An olefin polymerization catalyst characterized by comprising: (A): a transition metal compound represented by the following general formula [I], [II] or [III] (In the general formulas [I], [II] and [III], M represents a transition metal atom of Group 4 of the periodic table of the element, and A represents an atom of Group 16 of the periodic table of the element.) Show, J
Represents an atom belonging to Group 14 of the periodic table of the elements. Cp represents a group having a cyclopentadiene-type anion skeleton.
X ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group. An aryloxy group, a disubstituted amino group,
Alkylthio group, aralkylthio group, arylthio group,
It represents an alkylseleno group, an aralkylseleno group, or an arylseleno group. X ² represents an atom of Group 16 of the periodic table of the element. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. Multiple M, A, J, C
p, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. ) (B) the general formula E _a AlZ _3-a (where, E is a hydrocarbon group, all of E may or may not be the same.
Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a is a number satisfying 0 <a ≦ 3. (C): a boron compound represented by any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ (C2) a general formula G ⁺ (BQ ^{1 Q 2 Q 3 Q 4)} - boron compound represented by (C3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent atom And Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid.) (D): Phenols 2. The olefin polymerization catalyst according to claim 1, wherein (B) is trimethylaluminum, triethylaluminum or triisobutylaluminum. 3. The olefin polymerization catalyst according to claim 1, wherein (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 4. The method according to claim 1, wherein (D) is a phenol represented by the general formula ROH (where R represents an aryl group having 6 to 20 carbon atoms). The olefin polymerization catalyst according to any one of the above. 5. A process for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 1. 6. The method for producing an olefin polymer according to claim 5, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.