JP2001181323A - Addition polymerization catalyst component, addition polymerization catalyst, and production method for addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition polymerization catalyst component which, when used as a cocatalyst component for activation, can form an addition polymerization catalyst exhibiting high polymerization activity; an addition polymerization catalyst exhibiting high polymerization activity and prepared by using the catalyst component; and a method for efficiently producing an addition polymer by using the catalyst. SOLUTION: The addition polymerization catalyst component comprises a compound represented by formula [1]: [(R1x-1X)m-1MO]nTR23-n (wherein M is an atom of the group 3-12 or of the lanthanoid series; X is an atom of the group 14, 15, or 16; R1 is an electron-attractive group or a group having an electron-attractive group; T is an atom of the group 13; m is the atomic valence of M; x is the atomic valence of X; and 1<=n<=3). The addition polymerization catalyst is prepared by using the catalyst component. The method for producing an addition polymer uses the polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst component for addition polymerization, a catalyst for addition polymerization using the same, and a method for producing an addition polymer.

[0002]

2. Description of the Related Art Olefin polymers such as polypropylene and polyethylene are widely used in various molding fields because of their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy. I have. Conventionally, these olefin polymers are obtained by combining a solid catalyst component obtained mainly using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride with a Group 13 metal compound represented by an organoaluminum compound. It has been produced by polymerizing olefins using a conventional solid catalyst (multi-site catalyst).

In recent years, transition metal compounds (eg, metallocene complexes) different from solid catalyst components that have been used for a long time
There has been proposed a method of producing an addition polymer in which a monomer capable of addition polymerization is polymerized using a so-called single-site catalyst, which is a combination of a polymer and aluminoxane. For example,
JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported to combine certain boron compounds with such transition metal compounds. For example, Japanese Patent Application Laid-Open No. 1-502036 discloses a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Olefin polymers obtained with these single-site catalysts have narrower molecular weight distributions than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers the comonomers are more uniformly copolymerized. Therefore, it is known that a more homogeneous olefin polymer can be obtained than when a conventional solid catalyst is used.

[0004] Improvements in such addition polymerization catalysts have been studied diligently, and the types of metals used in the main catalyst components have been widely reported in each group of the periodic table. For example, Angew. Chem. Int. Ed. 38 , 4
28 (1999) report that a metallocene complex of a Group 3 to 13 metal or a nonmetallocene compound is effective as a main catalyst component. On the other hand, as an activating co-catalyst component to be combined with a metallocene complex or a non-metallocene compound, an aluminoxane or a boron compound belonging to Group 13 compounds occupies the center of its development.

[0005]

DISCLOSURE OF THE INVENTION In view of the above situation, an object of the present invention is to provide an addition polymerization catalyst component which can form an addition polymerization catalyst having high polymerization activity by using it as an activating co-catalyst component. It is an object of the present invention to provide an addition polymerization catalyst exhibiting high polymerization activity, and a method for efficiently producing an addition polymer using the addition polymerization catalyst.

[0006]

That is, the present invention provides the following general
A catalyst composition for addition polymerization comprising a compound represented by the formula [1]
And a catalyst for addition polymerization using the catalyst component for addition polymerization.
Medium and a method for producing an addition polymer using the addition polymerization catalyst.
Such is the case. [(R¹ _x-1X)_m-1 MO]_nTR^Two _3-n [1] (wherein M is a group 3-12 group of the periodic table or a lanthanoid
Represents an atom in the series, and when there are a plurality of M, they are
They may be the same or different. X is the periodic table
X, X, X or X represents an atom of Group 14, 15 or 16 of
When there are multiple
It may be. R¹Is an electron-withdrawing group or electron-withdrawing
A group containing a functional group;¹If there are multiple
They may be the same or different. T is
Represents an atom of Group 13 of the periodic table, ^TwoIs a hydrogen atom, halo
A hydrogen atom or a hydrocarbon group;^TwoThere are multiple
If they are the same or different from each other
No. m represents the valence of M, and x represents the valence of X. n
Represents a number satisfying 1 ≦ n ≦ 3. Hereinafter, the present invention will be described in more detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION M in the above general formula [1] is
Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 19)
89) represents an atom belonging to Groups 3 to 12 or a lanthanoid series, and when there are a plurality of M, they may be the same or different. Specific examples thereof include scandium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, and palladium atoms. , Platinum, copper, silver, gold, zinc, cadmium, mercury, samarium,
And ytterbium atom. M is particularly preferably a Group 12 atom, and most preferably a zinc atom. In the general formula [1], m represents a valence of M. For example, when M is a zinc atom, m is 2.

X in the above general formula [1] represents an atom belonging to Group 14, 15 or 16 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989), and a plurality of Xs exist. In that case they may be the same or different. Specific examples of Group 14 atoms include a carbon atom and a silicon atom. Specific examples of Group 15 atoms include a nitrogen atom and a phosphorus atom. Specific examples of Group 16 atoms include an oxygen atom and a sulfur atom. Atoms. X is preferably a carbon atom, a nitrogen atom or an oxygen atom, more preferably a nitrogen atom or an oxygen atom, and particularly preferably X is an oxygen atom. In the general formula [1], x represents a valence of X. When X is a group 14 atom, x is 4. When X is a group 15 atom, x is x.
Is 3. When X is a group 16 atom, x is 2.

R ¹ in the general formula [1] represents an electron-withdrawing group or a group containing an electron-withdrawing group. When a plurality of R ¹ are present, they may be the same or different. Good. As an index of electron withdrawing property, a substituent constant σ according to Hammett's rule is known, and a functional group having a positive substituent constant σ according to Hammett's rule is mentioned as an electron withdrawing group.

Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group) and the like.

Specific examples of the halogenated alkyl group include:
Fluoromethyl group, chloromethyl group, bromomethyl group,
Iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group trifluoromethyl group, trichloromethyl group, tribromomethyl group,
Triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group,
2,2,3,3,3-pentafluoropropyl group, 2,
2,3,3,3-pentachloropropyl group, 2,2
3,3,3-pentabromopropyl group, 2,2,3
3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2
A trichloro-1-trichloromethylethyl group, 2,
2,2-tribromo-1-tribromomethylethyl group,
2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2
-Trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1, 1-bis (triiodomethyl) -2,2,2
-A triiodoethyl group and the like.

Specific examples of the halogenated aryl group include:
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4
-Iodophenyl group, 2,6-difluorophenyl group,
3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-
Diiodophenyl group, 3,5-diiodophenyl group,
2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl Group, pentabromophenyl group, pentaiodophenyl group and the like.

Specific examples of the (halogenated alkyl) aryl group include a 2- (trifluoromethyl) phenyl group,
3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4 And a 6-tris (trifluoromethyl) phenyl group.

Specific examples of the cyanated aryl group include 2
-Cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.

Specific examples of the nitrated aryl group include 2
-Nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.

Specific examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a trifluoromethoxycarbonyl group and a pentafluorophenoxycarbonyl group.

R ¹ is preferably a halogenated hydrocarbon group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2
3,3,3-pentafluoropropyl group, 2,2,2-
Trifluoro-1-trifluoromethylethyl group, 1,
1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 4-fluorophenyl group, 2,6-
Difluorophenyl group, 3.5-difluorophenyl group, 2,4,6-trifluorophenyl group, pentafluorophenyl group, chloromethyl group, dichloromethyl group,
Trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group,
2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis (trichloromethyl) -2,2,2-
Trichloroethyl group, 4-chlorophenyl group, 2,6
-Dichlorophenyl group, 3.5-dichlorophenyl group,
A 2,4,6-trichlorophenyl group or a pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, most preferably a trifluoromethyl group, a 2,2,2-trifluoro-1 group; —Trifluoromethylethyl, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl or pentafluorophenyl.

Specific examples of XR ¹ _x-1 which is a combination of X and R ¹ include, when X is a carbon atom, a tri (fluoromethyl) methyl group, a tri (chloromethyl) methyl group,
Tri (bromomethyl) methyl group, tri (iodomethyl)
Methyl group, tri (difluoromethyl) methyl group, tri (dichloromethyl) methyl group, tri (dibromomethyl)
Methyl group, tri (diiodomethyl) methyl group, tri (trifluoromethyl) methyl group, tri (trichloromethyl) methyl group, tri (tribromomethyl) methyl group, tri (triiodomethyl) methyl group, tri (2,2 , 2-
Trifluoroethyl) methyl group, tri (2,2,2-trichloroethyl) methyl group, tri (2,2,2-tribromoethyl) methyl group, tri (2,2,2-triiodoethyl) methyl group , Tri (2,2,3,3,3-pentafluoropropyl) methyl group, tri (2,2,3,3
3-pentachloropropyl) methyl group, tri (2,2,
3,3,3-pentabromopropyl) methyl group, tri (2,2,3,3,3-pentaiodopropyl) methyl group, tri (2,2,2-trifluoro-1-trifluoromethylethyl) Methyl group, tri (2,2,2-trichloro-1-trichloromethylethyl) methyl group, tri (2,2,2-tribromo-1-tribromomethylethyl) methyl group, tri (2,2,2- Triiodo-1-triiodomethylethyl) methyl group, tri (1,1-di (trifluoromethyl) -2,2,2-trifluoroethyl) methyl group, tri (1,1-di (trichloromethyl)- 2,2,2-trichloroethyl) methyl group, tri (1,1-di (tribromomethyl) -2,2,2-tribromoethyl) methyl group, tri (1,1-di (triiodomethyl) −2,2,2- Riyodoechiru) methyl group, tri (2-fluorophenyl) methyl group, a tri (3
-Fluorophenyl) methyl group, tri (4-fluorophenyl) methyl group, tri (2-chlorophenyl) methyl group, tri (3-chlorophenyl) methyl group, tri (4-
A chlorophenyl) methyl group, a tri (2-bromophenyl) methyl group, a tri (3-bromophenyl) methyl group,
Tri (4-bromophenyl) methyl group, tri (2-iodophenyl) methyl group, tri (3-iodophenyl) methyl group, tri (4-iodophenyl) methyl group, tri (2,6-difluorophenyl) methyl Group, bird (3,
5-difluorophenyl) methyl group, tri (2,6-dichlorophenyl) methyl group, tri (3,5-dichlorophenyl) methyl group, tri (2,6-dibromophenyl)
Methyl group, tri (3,5-dibromophenyl) methyl group, tri (2,6-diiodophenyl) methyl group, tri (3,5-diiodophenyl) methyl group, tri (2
4,6-trifluorophenyl) methyl group, tri (2,
4,6-trichlorophenyl) methyl group, tri (2,
4,6-tribromophenyl) methyl group, tri (2,
4,6-triiodophenyl) methyl group, tri (pentafluorophenyl) methyl group, tri (pentachlorophenyl) group, tri (pentabromophenyl) methyl group, tri (pentaiodophenyl) methyl group, tri (2- ( Trifluoromethyl) phenyl) methyl group, tri (3-
(Trifluoromethyl) phenyl) methyl group, tri (4
-(Trifluoromethyl) phenyl) methyl group, tri (2,6-di (trifluoromethyl) phenyl) methyl group, tri (3,5-di (trifluoromethyl) phenyl) methyl group, tri (2,4 , 6-tri (trifluoromethyl) phenyl) methyl, tri (2-cyanophenyl) methyl, tri (3-cyanophenyl) methyl, tri (4-cyanophenyl) methyl, tri (2-nitrophenyl) Examples include a methyl group, a tri (3-nitrophenyl) methyl group, and a tri (4-nitrophenyl) methyl group. Further, a functional group obtained by substituting X for a silicon atom from a carbon atom, and which is represented by rewriting a methyl group in the above specific example to a silyl group, can also be exemplified.

Similarly, when X is a nitrogen atom, di (fluoromethyl) amino, di (chloromethyl) amino, di (bromomethyl) amino, di (iodomethyl) amino
Amino group, di (difluoromethyl) amino group, di (dichloromethyl) amino group, di (dibromomethyl) amino group, di (diiodomethyl) amino group, di (trifluoromethyl) amino group, di (trichloromethyl) amino group ,
Di (tribromomethyl) amino group, di (triiodomethyl) amino group, di (2,2,2-trifluoroethyl)
Amino group, di (2,2,2-trichloroethyl) amino group, di (2,2,2-tribromoethyl) amino group, di (2,2,2-triiodoethyl) amino group, di (2 ,
2,3,3,3-pentafluoropropyl) amino group,
Di (2,2,3,3,3-pentachloropropyl) amino group, di (2,2,3,3,3-pentabromopropyl) amino group, di (2,2,3,3,3- Pentaiodopropyl) amino group, di (2,2,2-trifluoro-
1-trifluoromethylethyl) amino group, di (2,
2,2-trichloro-1-trichloromethylethyl) amino group, di (2,2,2-tribromo-1-tribromomethylethyl) amino group, di (2,2,2-triiodo-1-triiodomethyl) Ethyl) amino group, di (1,1
-Di (trifluoromethyl) -2,2,2-trifluoroethyl) amino group, di (1,1-di (trichloromethyl) -2,2,2-trichloroethyl) amino group, di (1,1 -Di (tribromomethyl) -2,2,2-tribromoethyl) amino group, di (1,1-di (triiodomethyl) -2,2,2-triiodoethyl) amino group,
Di (2-fluorophenyl) amino group, di (3-fluorophenyl) amino group, di (4-fluorophenyl) amino group, di (2-chlorophenyl) amino group, di (3-
Chlorophenyl) amino group, di (4-chlorophenyl)
Amino group, di (2-bromophenyl) amino group, di (3
-Bromophenyl) amino group, di (4-bromophenyl) amino group, di (2-iodophenyl) amino group, di (3-iodophenyl) amino group, di (4-iodophenyl) amino group, di (2 , 6-difluorophenyl) amino group, di (3,5-difluorophenyl) amino group,
Di (2,6-dichlorophenyl) amino group, di (3,5
-Dichlorophenyl) amino group, di (2,6-dibromophenyl) amino group, di (3,5-dibromophenyl)
An amino group, a di (2,6-diiodophenyl) amino group,
Di (3,5-diiodophenyl) amino group, di (2
4,6-trifluorophenyl) amino group, di (2,
4,6-trichlorophenyl) amino group, di (2,4,
6-tribromophenyl) amino group, di (2,4,6-
Triiodophenyl) amino group, di (pentafluorophenyl) amino group, di (pentachlorophenyl) amino group, di (pentabromophenyl) amino group, di (pentaiodophenyl) amino group, di (2- (trifluoromethyl) amino group ) Phenyl) amino group, di (3- (trifluoromethyl) phenyl) amino group, di (4- (trifluoromethyl) phenyl) amino group, di (2,6-di (trifluoromethyl) phenyl) amino group A di (3,5-di (trifluoromethyl) phenyl) amino group, a di (2,4,
6-tri (trifluoromethyl) phenyl) amino group,
Di (2-cyanophenyl) amino group, (3-cyanophenyl) amino group, di (4-cyanophenyl) amino group,
Examples thereof include a di (2-nitrophenyl) amino group, a di (3-nitrophenyl) amino group, and a di (4-nitrophenyl) amino group. Further, a functional group obtained by substituting X from a nitrogen atom to a phosphorus atom, which is represented by rewriting the amino group in the above specific example to a phosphino group, can also be exemplified.

When X is an oxygen atom, a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, an iodomethoxy group, a difluoromethoxy group, a dichloromethoxy group, a dibromomethoxy group, a diiodomethoxy group, a trifluoromethoxy group , Trichloromethoxy, tribromomethoxy, triiodomethoxy, 2,2,2-
Trifluoroethoxy group, 2,2,2-trichloroethoxy group, 2,2,2-tribromoethoxy group, 2,2
2-triiodoethoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2,3,3,3-pentachloropropoxy group, 2,2,3,3,3-pentabromopropoxy Group, 2,2,3,3,3-pentaiodopropoxy group, 2,2,2-trifluoro-1-trifluoromethylethoxy group, 2,2,2-trichloro-1-
Trichloromethylethoxy group, 2,2,2-tribromo-1-tribromomethylethoxy group, 2,2,2-triiodo-1-triiodomethylethoxy group, 1,1-di (trifluoromethyl) -2, 2,2-trifluoroethyl group, 1,1-di (trichloromethyl) -2,2,2
-Trichloroethyl group, 1,1-di (tribromomethyl) -2,2,2-tribromoethyl group, 1,1-di (triiodomethyl) -2,2,2-triiodoethyl group, 2 -Fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2-chlorophenoxy group, 3-chlorophenoxy group, 4-chlorophenoxy group, 2-bromophenoxy group, 3-bromophenoxy group, 4-bromo Phenoxy, 2-iodophenoxy, 3-iodophenoxy, 4-iodophenoxy, 2,6-difluorophenoxy, 3,5-difluorophenoxy, 2,6-dichlorophenoxy,
3,5-dichlorophenoxy group, 2,6-dibromophenoxy group, 3,5-dibromophenoxy group, 2,6-diiodophenoxy group, 3,5-diiodophenoxy group,
2,4,6-trifluorophenoxy group, 2,4,6-
Trichlorophenoxy group, 2,4,6-tribromophenoxy group, 2,4,6-triiodophenoxy group, pentafluorophenoxy group, pentachlorophenoxy group,
Pentabromophenoxy group, pentaiodophenoxy group, 2- (trifluoromethyl) phenoxy group, 3-
(Trifluoromethyl) phenoxy group, 4- (trifluoromethyl) phenoxy group, 2,6-di (trifluoromethyl) phenoxy group, 3,5-di (trifluoromethyl) phenoxy group, 2,4,6- Examples thereof include a tri (trifluoromethyl) phenoxy group, a 2-cyanophenoxy group, a 3-cyanophenoxy group, a 4-cyanophenoxy group, a 2-nitrophenoxy group, a 3-nitrophenoxy group, and a 4-nitrophenoxy group. Further, a functional group obtained by substituting X for an oxygen atom by a sulfur atom, which is expressed by rewriting the oxy group in the above specific example to a thioxy group, can also be exemplified.

XR ¹ _x-1 is preferably a tri (fluoroalkyl) methyl group, a tri (fluoroaryl) methyl group, a di (fluoroalkyl) amino group, a di (fluoroaryl) amino group, a fluoroalkyloxy group or a fluoroalkyloxy group. An aryloxy group, more preferably a tri (trifluoromethyl) methyl group, a tri (pentafluorophenyl) methyl group, a di (trifluoromethyl) amino group, a di (pentafluorophenyl) amino group, a trifluoromethoxy group , A 2,2,2-trifluoro-1-trifluoromethylethoxy group, a 1,1-di (trifluoromethyl) -2,2,2-trifluoroethyl group, or a pentafluorophenoxy group, particularly preferred. Is a fluoroalkyloxy group or a fluoroaryloxy group, Preferably, 2,2,2-trifluoro-1-trifluoromethyl ethoxy, 1,1
A di (trifluoromethyl) -2,2,2-trifluoroethyl group or a pentafluorophenoxy group.

R ² in the general formula [1] represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of R ² are present, they may be the same or different. Specific examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable. As the hydrocarbon group for R ² , an alkyl group, an aryl group, or an aralkyl group is preferable.

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl Groups, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group or isobutyl 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 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like. 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 aryl group has 6 to 20 carbon atoms.
Are preferred, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6
-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, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable. 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 aralkyl group may have 7 to 2 carbon atoms.
An aralkyl group of 0 is 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-dimethylphenyl) 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, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like, and more preferably 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.

R ² in the general formula [1] is preferably an aryl group or an alkyl group, and more preferably an alkyl group. T in the general formula [1]
Represents an atom belonging to Group 13 of the periodic table, and specific examples thereof include a boron atom, an aluminum atom, and a gallium atom, and a boron atom is particularly preferable. N in the general formula [1] represents a number satisfying 1 ≦ n ≦ 3, and preferably n
Is 2. In the present invention, two or more molecules of the compound represented by the general formula [1] may be associated with each other.

Specific examples of the compound represented by the above general formula [1] when M is a zinc atom include, for example, bis (trifluoromethoxyzincoxy) methylboron, bis (2,2,2) -Trifluoroethoxyzincoxy) methylboron, bis (1,1,3,3,3-pentafluoro-2-trifluoromethylpropoxyzincoxy) methylboron, bis (2,2,2-trifluoro-
1-trifluoromethylethoxyzincoxy) methylboron, bis (2,2,3,3,3-pentafluoropropoxyzincoxy) methylboron, bis (2,4,6-
Trifluorophenoxyzincoxy) methylboron, bis (pentafluorophenoxyzincoxy) methylboron, bis (4-trifluoromethylphenoxyzincoxy) methylboron, bis (trifluoromethylamidozincoxy) methylboron, bis (2 2,2-trifluoroethylamidozincoxy) methylboron, bis (pentafluoroanilidezincoxy) methylboron, bis (N-trifluoromethylanilidezincoxy) methylboron and the like can be mentioned.

The compound represented by the above general formula [1] is particularly preferably bis (fluoroalkyloxyzincoxy) alkylboron or bis (fluoroaryloxyzincoxy) alkylboron, and more preferably bis (fluoroaryloxyzincoxy) alkylboron. 2,2,2-trifluoro-1-trifluoromethylethoxyzincoxy) methylboron, bis (pentafluorophenoxyzincoxy) methylboron, or bis (1,1,3,3,3-pentafluoro-2-) Trifluoromethylpropoxyzincoxy) methylboron.

The method for producing the compound represented by the general formula [1] is not particularly limited.
After treating an organometallic compound such as an alkyl metal or an alkyl metal halide with an inorganic acid such as alkylboric acid, an alkyloxylithium compound having an electron-withdrawing substituent or an aryloxylithium compound having an electron-withdrawing substituent A compound represented by LiXR ¹ _X-1 such as an aminolithium compound having an electron-withdrawing substituent, or an alcohol having an electron-withdrawing substituent, a phenol having an electron-withdrawing substituent, A method of treating with a compound represented by HXR ¹ _X-1 such as an amine having an attractive substituent is exemplified. Preferably, an organic metal compound such as an alkyl metal or an alkyl metal halide is converted from an alcohol having an electron-withdrawing substituent, a phenol having an electron-withdrawing substituent, or an amine having an electron-withdrawing substituent. This is a method of treating with a selected compound.

Such a treatment is preferably performed in an inert gas atmosphere. Processing temperature is -100 ° C to 200
° C, preferably -80 ° C to 150 ° C. The processing time is generally 1 minute to 36 hours, preferably 10 minutes to 24 hours. In such a treatment, a solvent may be used, or these compounds may be directly treated without using a solvent. Solvents used are organometallic compounds, LiX
It is preferably an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent that is inert to the compound represented by R ¹ _x-1 or the compound represented by HXR ¹ _x-1 ; specific examples of the solvent Examples include butane, hexane, heptane, benzene, toluene and the like.

In this treatment, an organometallic compound, Li
XR¹ _x-1And HXR represented by ¹ _x-1Compound represented by
There is no restriction on the order of dropping the objects.
May be added dropwise after mixing two or more types of solutions.
Is also good. LiXR used here¹ _x-1Or a compound represented by
HXR¹ _x-1For organometallic compounds represented by
By adjusting the number of moles, any amount of (X
R¹ _x-1), R^TwoCan be introduced. Also like this
Organic metal compound, LiXR¹ _x
-1And HXR represented by¹ _x-1The compound represented by
It may remain as an unreacted substance. Obtained by such processing
The compound represented by the above general formula [1] is obtained by recrystallization or the like.
After isolation and purification, use as a catalyst component for addition polymerization.
However, this reaction solution can be used as it is as a catalyst for addition polymerization.
It is also possible to use as a component. Preferably a reaction solution
The solvent is distilled off from the solution, and at a temperature of 25 ° C.
Drying is preferably performed. More preferably, 60 to 2
1 hour to 24 hours at a temperature of 00C, most preferably 80 to 1 hour
It is preferable to dry at a temperature of 60 ° C. for 4 to 18 hours.
No.

A specific example of a method for producing the compound represented by the general formula [1] will be described below in the case where M is a zinc atom, the inorganic acid is alkyl boric acid, and the treating agent is a phenol. Toluene slurry of alkyl boric acid
Cool to 8 ° C. While the slurry is being vigorously stirred, a prescribed amount of a hexane solution of dialkyl zinc is added dropwise. After completion of the dropwise addition, the temperature is gradually raised to room temperature, and the mixture is further stirred for a specified time. A method of gradually dropping a prescribed amount of phenols and stirring for a prescribed time can be adopted. Of course, the compounds used in these treatments are not limited to alkylboric acid, dialkylzinc, and phenols.

The compounds of the present invention described in detail above are useful as catalyst components for addition polymerization (among others, catalyst components for olefin polymerization). Specific examples of the addition polymerization catalyst of the present invention include an addition polymerization catalyst component (A) composed of the compound represented by the general formula [1] and a Group 3 to Group 13 or lanthanoid-based metal compound (B). A catalyst for addition polymerization brought into contact with the catalyst, an addition polymerization catalyst component (A) comprising a compound represented by the general formula [1], a Group 3 to 13 or lanthanoid-based metal compound (B), and organoaluminum A catalyst for addition polymerization obtained by contacting the compound (C) is exemplified. Hereinafter, the addition polymerization catalyst will be described in more detail.

(B) Group 3-13 or lanthanoid series metal compound The group 3-13 or lanthanoid series metal compound (B) used in the catalyst for addition polymerization of the present invention is represented by the above general formula [1]. A compound different from the above compound is used, and the compound represented by the above general formula [1] (or further, an organoaluminum compound (C)) is used as an activating co-catalyst component. 1
There is no particular limitation as long as it is a compound of a Group 3 or lanthanoid metal. As such a metal compound (B), for example, a metal compound represented by the following general formula [4] or a μ-
Oxo-type metal compounds and the like can be mentioned. L _a MX _b [4] (wherein, M is a metal atom of the periodic table 3-13 or the lanthanoid series .L is a group containing a group or a hetero atom having a cyclopentadiene type anion skeleton, A plurality of Ls may be linked directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X is a halogen atom or a hydrocarbon group. A represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.)

In the general formula [4], M is the periodic table (I
(UPAC 1989) Group 3 to 13 or lanthanoid series metal atom. Specific examples thereof include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, and palladium atoms. , Samarium atom, ytterbium atom,
Examples include an aluminum atom and a boron atom. M in the general formula [4] is preferably a transition metal atom, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom.

In the general formula [4], L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of Ls may be the same or different. A plurality of Ls may be connected directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group and a substituted fluorenyl group. Groups having a cyclopentadiene-type anion skeleton include, for example, η ^5- (substituted) cyclopentadienyl group, η ^5-
(Substituted) indenyl group and η ^5- (substituted) fluorenyl group. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵
-Tert-butylcyclopentadienyl group, η ^5-
1,2-dimethyl cyclopentadienyl group, η ⁵ -1,
3-dimethyl cyclopentadienyl group, η ⁵ -1-te
rt-butyl-2-methylcyclopentadienyl group, η
⁵ -1-tert-butyl-3-methylcyclopentadienyl group, eta ^{5-1-methyl-2-isopropyl-cyclopentadienyl} group, eta ^{5-1-methyl-3-isopropyl-cyclopentadienyl} group, eta ⁵ 1,2,3-trimethyl cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl enyl, eta ⁵ - indenyl group, η ⁵ -4,5,6,
7-tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-5-methylindenyl} group, eta ⁵
6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, eta ⁵ -
3-tert-butyl indenyl group, η ⁵ -4-ter
t- butyl indenyl group, η ⁵ -5-tert- butyl-indenyl group, η ⁵ -6-tert- butyl indenyl group, η ⁵ -7-tert- butyl indenyl group, eta ⁵ -
2,3-dimethyl indenyl group, eta ^{5-4,7-dimethyl-indenyl} group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ^5-4,5 benzindenyl group, eta ^{5-2-methyl-4,5-benzindenyl} group, eta ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ⁵ - 2-methyl-4-phenyl-indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group, eta ⁵
- fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl-fluorenyl group, and substituted versions thereof, and the like.

Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, an aryloxy group, a thioalkoxy group and a thioalkoxy group. An aryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, or an aromatic or aliphatic heterocyclic group having an oxygen atom, a sulfur atom, a nitrogen atom and / or a phosphorus atom in a ring, Chelating ligands and the like.

Specific examples of the group containing a hetero atom include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6
-Dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6
-Diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,
6-di-sec-butylphenoxy group, 2-tert-
Butyl-4-methylphenoxy group, 2,6-di-ter
t-butylphenoxy group, 4-methoxyphenoxy group,
2,6-dimethoxyphenoxy group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothio Phenoxy group, 2,3,6-trichlorophenoxy group,
2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-hyphenyldiol Group, 1,1'-bi-
2-naphthol group, 2,2'-dihydroxy-6,6 '
-Dimethylbiphenyl group, 4,4 ', 6,6'-tetra-tert-butyl-2,2'methylenediphenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutylyl A dendiphenoxy group and the like can be exemplified.

Further, examples of the group containing a hetero atom include a group represented by the following general formula [5]. _{R 3 P = N- [5]} ( wherein a hydrogen atom when R is each a halogen atom, a hydrocarbon group, they may be different be the same as each other, the two or more They may be bonded to each other or form a ring.)

Specific examples of R in the general formula [5] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Group, tert-butyl group, cyclopropyl group, cyclobutyl group, cycloheptyl group, cyclohexyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, benzyl group and the like, but are not limited thereto. Absent.

Further, examples of the group containing a hetero atom include a group represented by the following general formula [6]. (In the formula, R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbonoxy group, a silyl group, or an amino group in each case. Or two or more of them may be bonded to each other to form a ring.)

Specific examples of R in the general formula [6] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a 1-naphthyl group, a 2-naphthyl group and a tert-butyl group. , 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-
Trifluoromethylphenyl, 4-methoxyphenyl, 4-pyridyl, cyclohexyl, 2-isopropylphenyl, benzyl, methyl, triethylsilyl, diphenylmethylsilyl, 1-methyl-1-
Phenylethyl group, 1,1-dimethylpropyl group, 2-
Examples include, but are not limited to, chlorophenyl groups.

The above-mentioned chelating ligand refers to a ligand having a plurality of coordination sites, and specific examples thereof include acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylene Examples include ethylenetetramine, porphyrin, crown ether, cryptate and the like.

Groups having a cyclopentadiene-type anion skeleton, groups having a cyclopentadiene-type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom may be directly connected to each other,
It may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of such residues include ethylene groups, alkylene groups such as propylene groups, dimethylmethylene groups, substituted alkylene groups such as diphenylmethylene groups, or silylene groups, dimethylsilylene groups, diphenylsilylene groups,
Examples include a substituted silylene group such as a tetramethyldisilylene group, and a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

X in the general formula [4] is a halogen atom or a hydrocarbon group. Specific examples of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group as a hydrocarbon group,
Examples include a phenyl group and a benzyl group. X is preferably a halogen atom, an alkyl group having 1 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms.

In the general formula [4], a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valency of M.

Among the metal compounds represented by the general formula [4],
Specific examples of the compound in which the metal atom is a titanium atom include:
Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclo) (Pentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride, bis [2- (bis- , 5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2-
(4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2-
(4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride,

Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride, pentamethylcyclopentadiene Enyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindenyl) titanium dichloride,

Ethylene bis (cyclopentadienyl) titanium dichloride, ethylene bis (2-methylcyclopentadienyl) titanium dichloride, ethylene bis (3
-Methylcyclopentadienyl) titanium dichloride,
Ethylene bis (2-n-butylcyclopentadienyl)
Titanium dichloride, ethylene bis (3-n-butylcyclopentadienyl) titanium dichloride, ethylene bis (2,3-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,4-dimethylcyclopentadienyl) titanium dichloride , Ethylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (3,4-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2
3-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (3 , 5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylene Bis (tetramethylcyclopentadienyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2
-Phenylindenyl) titanium dichloride, ethylenebis (fluorenyl) titanium dichloride,

Ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium dichloride,
Ethylene (cyclopentadienyl) (indenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (n
-Butylcyclopentadienyl) (indenyl) dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) ) Titanium dichloride, ethylene (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (tetramethylpentadienyl) (fluorenyl) titanium dichloride, ethylene (Indenyl) (fluorenyl) titanium dichloride,

Isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (2
-Methylcyclopentadienyl) titanium dichloride,
Isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-
n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2 , 4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3
4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,
5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, isopropylidene Redidenbis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (4,5,6 , 7-tetrahydroindenyl) titanium dichloride, isopropylidenebis (2-phenylindenyl) titanium dichloride, isopropylidenebis (fluorenyl) titanium dichloride,

Isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl)
(Indenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (indenyl) dichloride, isopropylidene (tetramethylcyclopentadienyl) (indenyl) Dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (n
-Butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl)
Titanium dichloride,

Dimethylsilylenebis (cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2
-Methylcyclopentadienyl) titanium dichloride,
Dimethylsilylenebis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-
n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2 , 4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3
4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,
5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethyl Silylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (4,5,6 , 7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethyl Silylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butyl) Cyclopentadienyl)
(Fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (indenyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride,

Cyclopentadienyl (dimethylamide)
Titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,
6-dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-
tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2 ,
6-tert-butylphenyl) titanium dichloride,
Indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Methylene (cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride Methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-) 2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl)
(3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2 -Phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-
Butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 −
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl- 5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl- 5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert
-Butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (ter
t-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene Ridene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert −
Butyl-5-chloro-2-phenoxy) titanium dichloride,

The isopropylidene (fluorenyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2)
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-
5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (te
rt-butylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butyl) Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium Dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy)
Titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5- Methyl-
2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (fluorenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5 -Chloro-2
-Phenoxy) titanium dichloride

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Silylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-te
rt-butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) ) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (n-butylcyclopentadienyl)
(3-methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (n-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene ( n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl- 3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-diamyl-2-
Phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- Butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2
-Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butyl) Cyclopentadienyl)
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentane) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Silylene (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadiene) Enil)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclo) Pentadienyl) (5-methyl-3-trimethylsilyl-2
-Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) )
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-di-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, dimethylsilylene (indenyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-
Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-chloro-2
-Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)) (1-naphthoxy-2-
Il) titanium dichloride,

(Tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdimethyl, (tert-butylamido) Tetramethylcyclopentadienyl-1,2-ethanediyltitanium dibenzyl, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl-1,
2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dimethyl, (tert-butylamido) tetramethylcyclopentadienyl Dimethylsilanetitanium dibenzyl, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl,

(Tert-butylamido) indenyl-
1,2-ethanediyl titanium dichloride, (tert
-Butylamido) indenyl-1,2-ethanediyltitanium dimethyl, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dimethyl, (Tert
-Butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dimethyl, (t
(tert-butylamido) indenyldimethylsilanetitanium dichloride, (tert-butylamido) indenyldimethylsilanetitaniumdimethyl, (tert-butylamido) tetrahydroindenyldimethylsilanetitanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilanetitaniumdimethyl, ( ter
(t-butylamido) fluorenyldimethylsilanetitanium dichloride, (tert-butylamido) fluorenyldimethylsilanetitanium dimethyl,

(Dimethylaminomethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyltitanium ( II
I) dichloride, (N-pyrrolidinylethyl) tetramethylcyclopentadienyltitanium dichloride, (B
-Dimethylaminoborabenzene) cyclopentadienyl zirconium dichloride, cyclopentadienyl (9
-Mesityl boraanthracenyl) zirconium dichloride,

2,2'-thiobis [4-methyl-6-t
tert-butylphenoxy] titanium dichloride, 2,
2'-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2'-thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl- 6-tert-
Butylphenoxy) titanium dichloride, 2,2′-methylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, , 2'-Sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2 '-(4,4', 6,6'-tetra-t
tert-butyl-1,1'biphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-ter
t-butylphenoxy) titanium diisopropoxide,
2,2′-methylenebis (4-methyl-6-tert-
Butylphenoxy) titanium diisopropoxide, 2,
2′-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, 2,2 ′
-Sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide,

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride,
[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl)-
1,3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-
Di-tert-butylphenyl) -1,3-propanediamide] titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride,
[Bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dibromide,

[Hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium triiotate Dyed, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-diethylpyrazolyl) borate] titanium triiodide , [Hydrotris (3,5-di-
tert-butylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium tribromide,
[Hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium triiodide, [tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-dimethylpyrazolyl) methyl] titanium Tribromide, [tris (3,5-dimethylpyrazolyl) methyl] titanium triiodide,
[Tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [Tris (3,5-diethylpyrazolyl) methyl] titanium tribromide, [Tris (3,5
[5-diethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, [tris (3,3
5-di-tert-butylpyrazolyl) methyl] titanium tribromide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium triiodide, and the like, in which titanium of these compounds is changed to zirconium or hafnium Compound (2-phenoxy) is converted to (3-
Compounds changed to (phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilylene changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene Compound, dichloride difluoride, dibromide, diiodide dimethyl, dimethyl, diethyl, diisopropyl,
Examples include bis (dimethylamide), bis (diethylamide), dimethoxide, diethoxide, di-n-butoxide, diisopropoxide, and compounds modified to bis (diacetoxy).

Among the metal compounds represented by the general formula [4], specific examples of the compound in which the metal atom is a nickel atom include 2,2'-methylenebis [(4R) -4-phenyl-5,5 ' -Dimethyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5 , 5'-Diethyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-
Phenyl-5,5'-diethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4
-Phenyl-5,5'-di-n-propyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-di-n-propyloxazoline] nickel dibromide, , 2′-methylenebis [(4R) -4-phenyl-5,5′-diisopropyloxazoline] nickel dichloride, 2,
2′-methylenebis [(4R) -4-phenyl-5,
5'-diisopropyloxazoline] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Phenyl-5,5'-dicyclohexyloxazoline]
Nickel dichloride, 2,2′-methylenebis [(4
R) -4-phenyl-5,5'-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethoxyoxazoline] nickel dichloride, 2,2'- Methylenebis [(4R) -4-phenyl-5,5'-dimethoxyoxazoline] nickel dibromide, 2,2'-
Methylenebis [(4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dichloride, 2,
2′-methylenebis [(4R) -4-phenyl-5,
5'-diethoxyoxazoline] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Phenyl-5,5'-diphenyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R)-
4-phenyl-5,5'-diphenyloxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R)-
4-methyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4
R) -4-Methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel Dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3
-Methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-
Di- (4-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [spiro {(4R) -4-
Methyloxazoline-5,1'-cyclobutane}] nickel dibromide, methylenebis [spiro {(4R)-
4-methyloxazoline-5,1'-cyclopentane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, methylenebis [spiro} (4R) -4-methyloxazoline-5
1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-isopropyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-Isopropyl-5,5-di-n-propyloxazoline], methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4
-Isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-
(2-Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′- Methylenebis [(4R) -4-isopropyl-5,5-di- (4-
Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [( 4R) -4-Isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxy Phenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-
5,1′-cyclobutane}] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclopentane}]
Nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,
1'-cyclohexane}] nickel dibromide, 2,
2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Isobutyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4
-Isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide,
2,2'-methylenebis [(4R) -4-isobutyl-
5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide,
2,2'-methylenebis [(4R) -4-isobutyl-
5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-Isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide,
2′-methylenebis [(4R) -4-isobutyl-5,
5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R)
-4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-
Methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-isobutyloxazoline-5,1'-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-
5,1′-cyclohexane｝] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-tert-Butyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] Nickel dibromide,
2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide,
2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methylphenyl) oxazoline]
Nickel dibromide, 2,2′-methylenebis [(4
R) -4-tert-butyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide,
2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert- Butyl-5,5-di- (2
-Methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-ter
t-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methoxyphenyl) ) Oxazoline] nickel dibromide, 2,2′-methylenebis [spiro} (4
R) -4-tert-Butyloxazoline-5,1'-
Cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro} ( 4
R) -4-tert-Butyloxazoline-5,1'-
Cyclohexane｝] nickel dibromide, 2,2'-
Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Phenyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-phenyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-phenyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-phenyl-5,5-di-
(2-Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-phenyl-5,5
-Di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-phenyl-5,5-di- (3-methoxyphenyl)
Oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4
-Methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4
-Phenyloxazoline-5,1'-cyclobutane}]
Nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-
Cyclopentane}] nickel dibromide, 2,2'-
Methylene bis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Benzyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-benzyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-benzyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-benzyl-5,5-di-
(2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′- Methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-benzyl-5,5
-Di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-benzyl-5,5-di- (3-methoxyphenyl)
Oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (4
-Methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4
-Benzyloxazoline-5,1'-cyclobutane}]
Nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1'-
Cyclopentane}] nickel dibromide, 2,2'-
Methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide and enantiomers of the above compounds. Compounds in which the configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline-type compound is reversed, or a compound in which dibromide of these compounds is changed to dichloride, dimethyl, dimethoxide, or bis (acetoxy) Is mentioned.

Further, specific examples of the nickel compound include:
[Hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel bromide,
[Hydrotris (3,5-dimethylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-dimethylpyrazolyl) borate]
Dimethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-dimethylpyrazolyl) borate]
Nickel ethyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel allyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel methallyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [ Hydrotris (3,5-diethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-diethylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-diethylpyrazolyl) borate] nickel methyl, [hydrotris (3 5-diethylpyrazolyl)
Borate] nickel ethyl, [hydrotris (3,5-
Diethylpyrazolyl) borate] nickel allyl, [hydrotris (3,5-diethylpyrazolyl) borate]
Nickel methallyl, [hydrotris (3,5-di-te
[rt-butylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel iodide, [ Hydrotris (3,5
-Di-tert-butylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel ethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel allyl , [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel methallyl,

Compounds represented by the following structural formulas are exemplified. (In the formula, R ⁷ and R ⁸ are each a 2,6-diisopropylphenyl group, and X, R ⁹ and R ¹⁰ are any of combinations of substituents shown in Table 1 below.)

[Table 1] Further, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium in the above nickel compounds can also be exemplified.

Among the metal compounds represented by the general formula [4], specific examples of the compound in which the metal atom is iron include 2,2.
6-bis- [1- (2,6-dimethylphenylimino)
Ethyl] pyridine iron dichloride, 2,6-bis- [1
-(2,6-diisopropylphenylimino) ethyl]
Pyridine iron dichloride, 2,6-bis- [1- (2-
[tert-butyl-phenylimino) ethyl] pyridine iron dichloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3,5- [Dimethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-dimethylpyrazolyl) borate] iron methyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-dimethylpyrazolyl) borate] Iron allyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron methallyl, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron bromide, Hydrotris (3,5-diethyl pyrazolyl) borate] iron iodide, [hydrotris (3,5-diethyl pyrazolyl) borate] iron methyl, [hydrotris (3,5-diethyl pyrazolyl)
Borate] iron ethyl, [hydrotris (3,5-diethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-diethylpyrazolyl) borate] iron methallyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate ] Iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3,5-di-te
rt-butylpyrazolyl) borate] iron iodide,
[Hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methyl, [hydrotris (3,5-
Di-tert-butylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron allyl, [hydrotris (3
5-di-tert-butylpyrazolyl) borate] iron methallyl and the like. In the above-mentioned iron compounds, compounds in which iron is replaced with cobalt or nickel can also be exemplified.

Specific examples of the metal compound of the μ-oxo type of the metal compound represented by the general formula [4] include μ-oxo metal compounds.
Oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (cyclopentadienyl)]
(2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (cyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium methoxide], μ-
Oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-
Oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide], μ-
Oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy)
Titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium methoxide],

Μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium methoxide],
μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-
Phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl)
(2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene ( Tetramethylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium methoxide],

Di-μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl- 2-phenoxy) titanium], di-μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-
Phenoxy) titanium], di-μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium],
Di-μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium],
Di-μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-
Phenoxy) titanium], di-μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di-μ
-Oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) Titanium], di-μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium] and the like.

In addition to the metal compound represented by the general formula [4] exemplified above and its μ-oxo type metal compound,
Examples of the compound used as the metal compound (B) include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate as a compound in which the metal atom is a nickel atom.
Nickel trifluoroacetate, nickel cyanide, nickel oxalate, nickel acetylacetonate, bis (allyl)
Nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel,
Dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2 -Bis (diphenylphosphino) ethane] nickel, bis [1,2-
Bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenylphosphino) propane] nickel, tetraamine nickel nitrate, tetrakis ( (Acetonitrile) nickel tetrafluoroborate, nickel phthalocyanine and the like.

Similarly, specific examples of the compound in which the metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride and the like. Specific examples of the compound in which the metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran. Specific examples of the compound in which the metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

Examples of the compound in which the metal atom is an aluminum atom include compounds represented by the following general formula. (In the formula, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group in each case; they may be the same or different, and two or more of them may be bonded to each other; X is a hydrogen atom,
Represents a halogen atom or a hydrocarbon group, which may be the same or different, may be bonded to each other, or may form a ring; )

These metal compounds (B) may be used alone or in combination of two or more. Among the metal compounds exemplified above, the metal compound (B) used in the present invention is preferably a metal compound represented by the above general formula [4]. Among them, a metal compound in which M in the general formula [4] is a transition metal atom is preferable, and a metal compound having at least one group having a cyclopentadiene-type anion skeleton as L in the general formula [4] is particularly preferable.

(C) Organoaluminum Compound As the component (C) organoaluminum compound used in the catalyst for addition polymerization of the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [7]. R ⁴ _b AlY _3-b [7] (wherein, R ⁴ represents a hydrocarbon group, and all R ⁴ may be the same or different. Y is a hydrogen atom, a halogen atom, an alkoxy group, Represents an aralkyloxy group or an aryloxy group, and b represents a number satisfying 0 <b ≦ 3.)

R ⁴ in the general formula [7] representing an organoaluminum compound is preferably a group having 1 to 2 carbon atoms.
4 hydrocarbon groups, more preferably 1 to 1 carbon atoms.
24 alkyl groups. Specific examples include a methyl group,
Examples include an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a normal octyl group and the like, and preferably an ethyl group, a normal butyl group, an isobutyl group or a normal hexyl group.

Specific examples of the case where Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. As the alkoxy group for Y, an alkoxy group having 1 to 24 carbon atoms is preferable, and specific examples include, for example, a methoxy group,
Ethoxy, n-propoxy, isopropoxy, n
-Butoxy group, sec-butoxy group, t-butoxy group,
n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadeoxy group, n-icosoxy group and the like, preferably methoxy group, ethoxy group or t-butoxy group. is there. Any of these alkoxy groups may be substituted with 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, and an aryloxy group such as a phenoxy group.

The aryloxy group for Y is preferably an aryloxy group having 6 to 24 carbon atoms. Specific examples thereof include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6
-Dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy , 2,4
5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,
2,3,4,5-tetramethylphenoxy group, 2,3
4,6-tetramethylphenoxy group, 2,3,5,6-
Tetramethylphenoxy 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-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. Any of these aryloxy groups may be substituted with 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, and an aryloxy group such as a phenoxy group.

The aralkyloxy group for Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Specific examples thereof include a benzyloxy group, a (2-methylphenyl) methoxy group and a (3-methylphenyl) methoxy group. , (4-methylphenyl) methoxy group, (2,3-
A (dimethylphenyl) methoxy group, a (2,4-dimethylphenyl) methoxy group, a (2,5-dimethylphenyl) methoxy group, a (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) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl)
Methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl)
Methoxy group, (pentamethylphenyl) 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, (n-octylphenyl) methoxy, (n-decylphenyl) methoxy, (n-tetradecylphenyl) methoxy, naphthylmethoxy, anthracenylmethoxy and the like. And preferably a benzyloxy group. Any of these aralkyloxyl groups may be substituted with 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, and an aryloxy group such as a phenoxy group.

Specific examples of the organoaluminum compound represented by the general formula [7] include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum,
Trialkylaluminum such as trinormal octyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dinormal propyl aluminum chloride, dinormal butyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum chloride such as dinormal hexyl aluminum chloride, methyl aluminum dichloride, ethyl Alkyl aluminum dichloride such as aluminum dichloride, normal propyl aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride,
Dialkyl aluminum hydrides such as dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, di normal hexyl aluminum hydride, trialkoxy aluminum such as trimethoxy aluminum, triethoxy aluminum, tri (t-butoxy) aluminum, methyl ( Alkyl (dialkoxy) aluminum such as dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-t-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t
Dialkyl (alkoxy) aluminum such as -butoxy) aluminum, triphenoxy aluminum, tris (2,6-diisopropylphenoxy) aluminum, triaryloxy aluminum such as tris (2, 6-diphenylphenoxy) aluminum, methyl (diphenoxy) aluminum, Alkyl (diaryloxy) aluminum such as methyl bis (2,6-diisopropylphenoxy) aluminum and methyl bis (2,6-diphenylphenoxy) aluminum, dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2 ,
Examples thereof include dialkyl (aryloxy) aluminum such as 6-diphenylphenoxy) aluminum.

Of these, preferred are trialkylaluminums, more preferred are trimethylaluminum, triethylaluminum, trinormal butylaluminum, triisobutylaluminum and trinormal hexylaluminum, and particularly preferred are triisobutylaluminum and trinormal hexylaluminum. Aluminum. These organoaluminum compounds may be used alone or in combination of two or more.

The ratio (molar ratio) of each catalyst component used in the present invention is not particularly limited, but the molar ratio between component (A) and component (B) is usually (A) :( B) = 1: 1 to 1
Molar ratios in the range of 0000: 1, preferably 1: 1
To 5000: 1, and more preferably 1: 1 to 10
The molar ratio is in the range of 00: 1. When the component (C) is used, the amount used is usually (B) :( C) = 0.1: 1 to 1:
Molar ratio in the range of 10,000, preferably 1: 1 to 1
The molar ratio is in the range of 1: 1000.

As the addition polymerization catalyst of the present invention, a reaction product obtained by previously contacting the component (A) and the component (B), and if necessary, the component (C) may be used. They may be separately charged and used. Any two of the components may be pre-contacted, followed by another component.

When each of the catalyst components is used in the form of a solution, the concentration of component (A) and component (C) is usually 0.0001 to 100 mol / l, preferably 0.01 to 10 mmol / l in terms of metal atom. It is. The concentration of the component (B) is usually 0.0001 to 1 in terms of metal atoms.
It is 00 mmol / l, preferably 0.01 to 10 mmol / l.

The method for supplying each catalyst component to the reactor is not particularly limited. A method in which each component is supplied in a solid state, a solution in which a component that deactivates a catalyst component such as moisture or oxygen is dissolved in a hydrocarbon solvent sufficiently removed,
Alternatively, there may be mentioned a method of supplying in a suspended or slurry state.

The polymerization method is not particularly limited. For example, butane, pentane, hexane,
Heptane, aliphatic hydrocarbons such as octane, benzene, aromatic hydrocarbons such as toluene, or solvent polymerization or slurry polymerization using a halogenated hydrocarbon such as methylene dichloride as a solvent, bulk polymerization to perform polymerization in a liquid monomer, Examples include a gas phase polymerization in which polymerization is performed in a gaseous monomer, and a high pressure method in which polymerization is performed in a supercritical fluid state under high temperature and high pressure. The polymerization system may be either a batch system or a continuous system.

The polymerization temperature is generally -100 ° C to 350 ° C, preferably -20 ° C to 300 ° C, more preferably 20 ° C to 300 ° C.
300 ° C. The polymerization pressure is usually 1-3500 kg / c.
m ² G, preferably 1 to 3000 kg / cm ² G, more preferably 1 to 2000 kg / cm ² G. Generally, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can be in a range of 1 minute to 20 hours.

As the monomer that can be used, any of olefins having 2 to 100 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, and polar monomers can be used. It can also be used. Specific examples of these include:
Ethylene, propylene, 1-butene, 1-pentene, 4
-Methyl-1-pentene, 5-methyl-1-hexene,
Olefins such as 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and vinylcyclohexane; 1,5-hexadiene, 1,4-hexadiene;
1,4-pentadiene, 1,7-octadiene, 1,8
-Nonadiene, 1,9-decadiene, 4-methyl-1,
4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2- Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, Diolefins such as 1,3-cyclooctadiene and 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene , Tricyclodecene, tricycloun Sen, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8
Cyclic olefins such as -methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene and 8-cyanotetracyclododecene; alkenyls such as styrene, 2-phenylpropylene, 2-phenylbutene and 3-phenylpropylene Benzene, p-methylstyrene,
m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene,
2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-secondary Alkyl styrenes such as butylstyrene, bisalkenylbenzenes such as divinylbenzene, alkenyl aromatic hydrocarbons such as alkenylnaphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride , Bicyclo (2,2,1) -5-heptene-
Α, β-unsaturated carboxylic acids such as 2,3-dicarboxylic acid,
And metal salts thereof such as sodium, potassium, lithium, zinc, magnesium and calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid Α, β-unsaturated carboxylic esters such as methyl, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; acetic acid Vinyl, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate,
Examples include polar esters such as vinyl esters such as vinyl trifluoroacetate, and unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

The present invention can be applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and propylene and 1
-Butene and the like are exemplified, but the present invention should not be limited to these. In order to control the molecular weight of the polymer, a chain transfer agent such as hydrogen can be added.

The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is suitably used in a method for producing an olefin polymer. As such an olefin polymer, a copolymer of ethylene and an α-olefin is particularly preferred, and among them, a linear low-density polyethylene (LLDP)
E) is preferred.

[0125]

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.

Example 1 (1) Synthesis of Bis (pentafluorophenoxyzincoxy) methylboron Compound 655.4 mg of methyl boric acid (97%) in a 200 ml four-necked flask purged with argon.
(10.6 mmol) and 50 ml of toluene.
Cooled to ° C. 20.8 ml of ZnEt ₂ (1.02 M, hexane solution) while vigorously stirring this slurry.
(21.2 mmol) was added dropwise. As the dropping amount was increased, a white gel-like precipitate was formed. After completion of the dropwise addition, the temperature was gradually raised to room temperature, and the mixture was further stirred for 2 hours. Pentafluorophenol (1.78 M, hexane solution) 1
1.9 ml (21.2 mmol) was gradually added dropwise, and the mixture was further stirred for 11 hours. The solvent was distilled off under reduced pressure and the residue was dried to obtain 6.06 g of a white powder.

(2) Polymerization An autoclave with a stirrer having a capacity of 400 ml was vacuum-dried and purged with argon.
1, 10 ml of 1-hexene was charged as a comonomer,
The reactor was heated to 70 ° C. After raising the temperature, the ethylene pressure was increased to 6
The feed was adjusted to kg / cm ^2, and after the inside of the system was stabilized, 0.25 mmol of triisobutylaluminum was added, then 1.0 μmol of ethylenebis (indenyl) zirconium dichloride was added, and the zinc obtained above was further added. The polymerization was started by charging 34.2 mg (61.7 μmol) of the compound. Polymerization was performed for 30 minutes. As a result of the polymerization, 3.42 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 6.8 × 10 ⁶ g / mol / h.

[Comparative Example 1]  (1) Polymerization An autoclave with a stirrer having an internal volume of 400 ml is vacuum-dried.
After drying and purging with argon, hexane 190 m
1, 10 ml of 1-hexene was charged as a comonomer,
The reactor was heated to 70 ° C. After raising the temperature, the ethylene pressure was increased to 6
kg / cm^TwoFeed while adjusting
After that, 0.25 mmol of triisobutylaluminum
And then ethylene bis (indenyl) zirconium
1.0 μmol of mudichloride was added, and ZnE was added.
t_Two(1.02 M hexane solution) 0.1 ml (100
μmol) was added to initiate polymerization. 30 minutes polymerization
went. As a result of polymerization, only trace amounts of polymer were obtained
Was.

[0129]

As described above in detail, according to the present invention, an addition polymerization catalyst component capable of forming an addition polymerization catalyst having high polymerization activity by using as an activating co-catalyst component,
It is intended to provide an addition polymerization catalyst using the compound and exhibiting high polymerization activity, and a method for efficiently producing an addition polymer using the addition polymerization catalyst.

Continued on the front page F-term (reference) 4J015 DA03 DA05 DA06 DA07 DA08 DA09 DA10 DA13 DA14 DA15 DA16 DA17 DA18 DA19 DA20 DA21 DA22 DA23 DA25 DA26 DA37 4J100 AA02P AA03P AA03Q AA04P AA04Q AA07P AA15P AA16AP ABP AAB16P AG02P AG04P AG05P AG08P AJ02P AJ08P AJ09P AK20P AK21P AK32P AL03P AL10P AL46P AR11P AR22P AS02P AS03P AS04P AS11P BA05P BA06P BA14P BA20P BA40P BB18P BC54P CA01 CA04 FA09 FA10

Claims (13)

[Claims] (1) a compound represented by the following general formula (1):
Catalyst component for addition polymerization. [(R¹ _x-1X)_m-1 MO]_nTR^Two _3-n [1] (wherein M is a group 3-12 group of the periodic table or a lanthanoid
Represents an atom in the series, and when there are a plurality of M, they are
They may be the same or different. X is the periodic table
X, X, X or X represents an atom of Group 14, 15 or 16 of
When there are multiple
It may be. R¹Is an electron-withdrawing group or electron-withdrawing
A group containing a functional group;¹If there are multiple
They may be the same or different. T is
Represents an atom of Group 13 of the periodic table, ^TwoIs a hydrogen atom, halo
A hydrogen atom or a hydrocarbon group;^TwoThere are multiple
If they are the same or different from each other
No. m represents the valence of M, and x represents the valence of X. n
Represents a number satisfying 1 ≦ n ≦ 3. ) 2. The catalyst component for addition polymerization according to claim 1, wherein X is a nitrogen atom or an oxygen atom. 3. The catalyst component for addition polymerization according to claim 1, wherein R ¹ is a halogenated hydrocarbon group. 4. The catalyst component for addition polymerization according to claim 1, wherein T is a boron atom. 5. The method according to claim 1, wherein M is a Group 12 atom.
The catalyst component for addition polymerization according to any one of the above. 6. The catalyst component for addition polymerization according to claim 1, wherein n is 2. 7. The compound represented by the general formula [1] is bis (fluoroalkyloxyzincoxy) alkylboron or bis (fluoroaryloxyzincoxy)
The catalyst component for addition polymerization according to claim 1, which is an alkyl boron. 8. An addition polymerization catalyst obtained by contacting the addition polymerization catalyst component (A) according to any one of claims 1 to 7 with a Group 3 to 13 or lanthanoid metal compound (B). 9. A catalyst component (A) for addition polymerization according to any one of claims 1 to 7, a metal compound of group 3 to 13 or a lanthanoid series (B), and an organoaluminum compound (C). Catalyst for addition polymerization. 10. The catalyst for addition polymerization according to claim 8, wherein the Group 3 to 13 or lanthanoid metal compound (B) is a metallocene metal compound. 11. A process for producing an addition polymer using the catalyst for addition polymerization according to claim 8. 12. The method for producing an addition polymer according to claim 11, wherein the addition polymer is an olefin polymer. 13. The method for producing an addition polymer according to claim 11, wherein the addition polymer is a copolymer of ethylene and an α-olefin.