JP2003171413A - Modified particle and method for producing the same, carrier, catalyst component for addition polymerization, catalyst for addition polymerization and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide particles useful for preparing a highly active single site catalyst applied to polymerizations (slurry polymerization, gas phase polymerization, bulk polymerization, and the like) accompanying the formation of addition polymer particles, to provide a carrier, to provide a catalyst component for addition polymerization, to provide a method for producing the particles, to provide a highly active catalyst for addition polymerization, and to provide an efficient production method for the addition polymer. <P>SOLUTION: The particles are obtained by bringing the following compounds (a), (b) and (c) into contact with particles (d). (a): M<SP>1</SP>L<SP>1</SP><SB>m</SB>[1], (b): a compound represented by the general formula [2], (c): R<SP>3</SP><SB>t-2</SB>TH<SB>2</SB>[3] [M<SP>1</SP>is a typical metal atom of the group 1, 2, 12, 14 or 15; (m) is the atomic value of M<SP>1</SP>; L<SP>1</SP>is H, a halogen atom or a hydrocarbon group; R<SP>1</SP>is an electron-attracting group or a group having an electron-attracting group; R<SP>2</SP>is H or a hydrocarbon group; R<SP>3</SP>is a hydrocarbon group or a halogenated hydrocarbon group; T is a non-metal atom of the group 15 or 16; (t) is the atomic value of T]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to modified particles useful as a carrier and a catalyst component for addition polymerization, a method for producing the same, a catalyst for addition polymerization obtained using the same, and a method for producing an addition polymer.

[0002]

BACKGROUND OF THE INVENTION Addition polymers such as polypropylene and polyethylene are widely used in various molding fields due to their excellent mechanical properties, chemical resistance, etc., and their excellent balance of properties and economic efficiency. There is. Conventionally, these addition polymers are obtained by combining a solid catalyst component mainly obtained by 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 an olefin or the like using a conventional solid catalyst (multi-site catalyst).

In recent years, olefins and the like are polymerized by using a so-called single-site catalyst, which is a combination of a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) different from a solid catalyst component which has been used for a long time, and an aluminoxane. A method for producing a addition polymer has been proposed. 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, special table 1-5
In 02036, a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate is reported. Addition polymers obtained using these single-site catalysts generally have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, comonomers are copolymerized more uniformly. Therefore, it is known that a more homogeneous addition polymer can be obtained than in the case of using a conventional solid catalyst.

However, since these known single-site catalysts are soluble in the reaction system, when they are applied to polymerization involving the formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), they are generated. The shape of the addition polymer is indefinite, formation of coarse addition polymer particles, lump addition polymer, fine powder addition polymer, etc., decrease of the bulk density of the addition polymer, adhesion of the addition polymer to the polymerization reactor wall It may invite people etc. And these contributed to poor heat transfer in the reactor,
There were problems such as poor heat removal, which made stable operation difficult and reduced productivity. Japanese Patent Laid-Open No. 11-19
Japanese Patent No. 3306 discloses a solution to this problem.

[0005]

However, the solution described in the publication is still insufficient in terms of polymerization activity. It is an object of the present invention to provide particles, carriers and additions useful in the preparation of highly active single-site catalysts that are suitable for polymerizations involving the formation of addition polymer particles (eg slurry polymerization, gas phase polymerization, bulk polymerization, etc.). It is intended to provide a polymerization catalyst component, a method for producing the particles, a highly active catalyst for addition polymerization, and an efficient method for producing an addition polymer.

[0006]

The present invention includes the following (a):
Modified particles obtained by bringing the following (b), the following (c), and the particles (d) into contact, and bringing the following (a), the following (b), the following (c), and the particles (d) into contact: The present invention relates to a method for producing modified particles. (A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1] (b): Compound represented by the following general formula [2] (C): Compound R ³ _t-2 TH ₂ [3] represented by the following general formula [3] (in the above general formulas [1] to [3], M ¹ is the first, second, or periodic table, respectively). Represents a typical metal atom of group 12, 14 or 15, m represents the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when plural L ^1's are present, they are the same as each other. R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and the three R ^1's may be the same as or different from each other, and optionally 2 Two R ¹ 's may be linked together to form a condensed ring structure by connecting to adjacent positions of a benzene ring, and R ^2's represent a hydrogen atom or a hydrocarbon group.
R ³ represents a hydrocarbon group or a halogenated hydrocarbon group.
Each T independently represents a nonmetallic atom of Group 15 or Group 16 of the periodic table, and t represents the valence of T of each compound. )

The present invention also relates to a carrier comprising the modified particles and a catalyst component for addition polymerization comprising the modified particles. Further, the present invention relates to a catalyst for addition polymerization obtained by bringing the modified particles (A) and a transition metal compound (B) of Groups 3 to 11 or lanthanoid series into contact with each other, and The present invention relates to a catalyst for addition polymerization obtained by bringing the modified particles (A), the Group 3 to 11 or lanthanoid series transition metal compound (B), and the organoaluminum compound (C) into contact with each other. The present invention also relates to a method for producing an addition polymer using any one of the above addition polymerization catalysts. Hereinafter, the present invention will be described in more detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (a) has the following general formula [1].
Is a compound represented by. M ¹ L ¹ _m [1] M ¹ in the general formula [1] is the Periodic Table of the Elements (I
UPAC Inorganic Chemistry Nomenclature Revised 1989) 1, 2, 1
It represents a typical metal atom of Group 2, 14 or 15. Specific examples thereof include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, mercury atom, germanium atom, tin atom. , Lead atom, antimony atom, bismuth atom and the like. M ¹ is preferably magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, particularly preferably magnesium atom, zinc atom, tin atom or bismuth atom, and most preferably Is a zinc atom. Also,
M in the general formula [1] represents a valence of M ^1, for example, when M ¹ is a zinc atom and m is 2.

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

The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, such as 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-heptyl group, n-octyl group Group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an 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 or 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 group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group, perbromoeicosyl group, 1H, 1H-perfluoropropyl group A 1H, 1H-perfluorobutyl group,
1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H,
1H-perfluoropentadecyl group, 1H, 1H-perfluoroeicosyl group, 1H, 1H-perchloropropyl group, 1H, 1H-perchlorobutyl group, 1H, 1H-
Perchloropentyl group, 1H, 1H-perchlorohexyl group, 1H, 1H-perchlorooctyl group, 1H, 1H-
Perchlorododecyl group, 1H, 1H-perchloropentadecyl group, 1H, 1H-perchloroeicosyl group, 1
H, 1H-perbromopropyl group, 1H, 1H-perbromobutyl group, 1H, 1H-perbromopentyl group, 1
H, 1H-perbromohexyl group, 1H, 1H-perbromooctyl group, 1H, 1H-perbromododecyl group,
1H, 1H-perbromopentadecyl group, 1H, 1H-
Examples thereof include perbromoeicosyl group. In addition, 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.
Aryl groups are preferred, for example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 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 thereof 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. Each of these aryl groups is a fluorine atom,
Halogen atom such as chlorine atom, bromine atom, 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 has 7 to 2 carbon atoms.
An aralkyl group of 0 is preferable, and examples thereof include a benzyl group and (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, (3,3
4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,3 6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group,
(2,4,6-trimethylphenyl) methyl group, (2
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl 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, (isobutylphenyl) methyl group, (n-pentylphenyl) methyl group,
Examples include (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, and the like. A benzyl group is preferred. All of these aralkyl groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. May be partially substituted with, for example.

L ¹ in the above general formula [1] is preferably a hydrogen atom, an alkyl group or an aryl group,
A hydrogen atom or an alkyl group is more preferable, and an alkyl group is particularly preferable.

The compound (b) is a compound represented by the following general formula [2]. The compound (c) is a compound represented by the following general formula [3]. R ³ _t-2 TH ₂ [3] Each T in the above general formula [2] or [3] is independently a group 15 or a group 16 of the periodic table of elements (IUPAC Inorganic Chemistry Nomenclature Revised 1989). Represents a non-metal atom of. T in the general formula [2] and T in the general formula [3] may be the same or different. Specific examples of the non-metal atom of Group 15 include a nitrogen atom and a phosphorus atom, and specific examples of the non-metal atom of Group 16 include an oxygen atom and a sulfur atom. Preferably as T,
Each is independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom. In the above general formula [2] or [3], t represents the valence of each T, and when T is a non-metal atom of Group 15, t is 3 and T is the first.
In the case of a non-metal atom of Group 6, t is 2.

R ¹ in the above general formula [2] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ^1's may be the same as or different from each other, and optionally. Two R ^1's may be joined together to form a condensed ring structure by connecting to adjacent positions of a benzene ring. As an index of the electron-withdrawing property, the Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's rule substituent constant σ can be mentioned as the 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 groups containing an electron-withdrawing group include halogenated alkyl groups, halogenated aryl groups, (halogenated alkyl) aryl groups, cyanated aryl groups, nitrated aryl groups, ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups, and Aryloxycarbonyl group), an acyl group, an acyl halide 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
-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-triiodoethyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1
H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1
H, 1H-perfluoroeicosyl group, 1H, 1H-perchlorobutyl group, 1H, 1H-perchloropentyl group, 1H, 1H-perchlorohexyl group, 1H, 1H-
Perchlorooctyl group, 1H, 1H-perchlorododecyl group, 1H, 1H-perchloropentadecyl group, 1H, 1
H-perchloroeicosyl group, 1H, 1H-perbromobutyl group, 1H, 1H-perbromopentyl group, 1H,
1H-perbromohexyl group, 1H, 1H-perbromooctyl group, 1H, 1H-perbromododecyl group, 1
H, 1H-perbromopentadecyl group, 1H, 1H-perbromoeicosyl group and the like can be mentioned.

Specific examples of the halogenated aryl group include:
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,
4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group,
2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4
-Pentafluorophenyl phenyl group, perfluoro-
1-naphthyl group, perfluoro-2-naphthyl group, 2-
Chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,
5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2 , 3, 5, 6-
Tetrachloro-4-pentachlorophenylphenyl group,
Perchloro-1-naphthyl group, perchloro-2-naphthyl group, 2-bromophenyl group, 3-bromophenyl group,
4-bromophenyl group, 2,4-dibromophenyl group,
2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 2,4,6-tribromophenyl group, 2,3,5,6-tetrabromophenyl group, pentabromo Phenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,
3,5,6-Tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group, perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2, 4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodophenyl group, 3,5-diiodophenyl group, 2,
4,6-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl group, 2,
3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, periodo-1-naphthyl group, periodo-2-naphthyl group and the like. To be

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 Examples thereof include a 6-tris (trifluoromethyl) phenyl group and a 3,4,5-tris (trifluoromethyl) phenyl group.

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

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

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

Specific examples of the acyl group include a formyl group,
Ethanoyl group, propanoyl group, butanoyl group, trifluoroethanoyl group, benzoyl group, pentafluorobenzoyl group, perfluoroethanoyl group, perfluoropropanoyl group, perfluorobutanoyl group, perfluoropentanoyl group, perfluorohexahexyl group Examples thereof include a noyl group, a perfluoroheptanoyl group, a perfluorooctanoyl group, a perfluorononanoyl group, a perfluorodecanoyl group, a perfluoroundecanoyl group, and a perfluorododecanoyl group.

R ¹ is preferably a halogen atom, a halogenated alkyl group, a halogenated aryl group, a cyano group,
Cyanated alkyl group, cyanated aryl group, nitro group,
It is a nitrated alkyl group, a nitrated aryl group or an ester group, more preferably a halogen atom, a halogenated alkyl group or a halogenated aryl group. More preferably, fluorine atom, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2. 2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluoro Phenyl group, 2,4-difluorophenyl group, 2,
6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5 6-tetrafluorophenyl group,
Pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3
5,6-Tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloro Ethyl 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, 2,4,6-trichlorophenyl group or pentachlorophenyl group, particularly preferably fluorine atom, fluoroalkyl group or fluoroaryl group, most preferably Is a fluorine atom.

R ² in the above general formula [2] represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group for R ² is preferably an alkyl group, an aryl group, or an aralkyl group, and examples thereof include the same hydrogen atom and hydrocarbon group as described for L ¹ in the general formula [1]. R
² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

R ³ in the above general formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group for R ³ is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbon group as that described for L ¹ in the general formula [1] is used. R ³
Examples of the halogenated hydrocarbon group in include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, and the like, and R ¹ in the above general formula [2]
The halogenated alkyl group, the halogenated aryl group, and the (halogenated alkyl) aryl group similar to those enumerated as the specific examples of the electron-withdrawing group in are used.

R ³ in the above general formula [3] is preferably a halogenated hydrocarbon group, more preferably a fluorinated hydrocarbon group.

Specific examples of the compound (a) include M ¹
When Z is a zinc atom, specific examples thereof include dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc and di-n-hexyl zinc; diphenyl zinc, dinaphthyl zinc, bis (penta Fluoroaryl) zinc and other diarylzinc; diallylzinc and other dialkenylzinc; bis (cyclopentadienyl) zinc; methylzinc chloride, ethylzinc chloride, propylzinc chloride, -n-butylzinc chloride, isobutylzinc chloride, chloride- n-hexyl zinc, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, -n-butyl zinc bromide,
Isobutyl zinc bromide, -n-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide,
Alkyl zinc halides such as iodide-n-butyl zinc, isobutyl zinc iodide and i-n-hexyl zinc iodide; zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide. .

The compound (a) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-n-butylzinc, diisobutylzinc or di-n-hexylzinc. Preferred is dimethyl zinc or diethyl zinc.

Specific examples of the compound (b) include, as phenols, 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol and 3,4,5-tris. (Pentafluorophenyl)
Phenol, 3,5-difluoro-4-pentafluorophenylphenol, 4,5,6,7,8-pentafluoro-2-naphthol, 3,4,5-trichlorophenol, 3,4,5-tris (trichloro) Methyl) phenol, 3,4,5-tris (pentachlorophenyl) phenol, 3,5-dichloro-4-pentachlorophenylphenol, 4,5,6,7,8, -pentachloro-
2-naphthol, 3,4,5-tribromophenol,
3,4,5-tris (tribromomethyl) phenol,
3,4,5-Tris (pentabromophenyl) phenol, 3,5-dibromo-4-pentabromophenylphenol, 4,5,6,7,8-pentabromo-2-naphthol, 3,4,5-tri Iodophenol, 3,4
5-tris (triiodomethyl) phenol, 3,4
5-tris (pentaiodophenyl) phenol, 3,
5-diiodo-4-pentaiodophenylphenol,
4,5,6,7,8-pentaiodo-2-naphthol,
3,5-difluoro-4-nitrophenol, 3,5-
Dichloro-4-nitrophenol, 3,5-dibromo-
4-nitrophenol, 3,5-diiodo-4-nitrophenol, 3,5-difluoro-4-cyanophenol, 3,5-dichloro-4-cyanophenol, 3,5
-Dibromo-4-cyanophenol, 3,5-diiodo-4-cyanophenol and the like can be mentioned. Also,
A thiophenol compound in which an oxygen atom is replaced by a sulfur atom can be similarly exemplified. These thiophenol compounds are compounds represented by rewriting the phenol of the above-mentioned specific examples into thiophenol (in the case of naphthol, compounds represented by rewriting naphthol to naphthylthiol) and the like. In addition, the hydrogen atom at the 2,6-position (in the case of naphthol or naphthylthiol, the hydrogen atom at the 1,3-position) in the above-mentioned specific examples is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Phenol compounds or thiophenol compounds substituted with a butyl group, an isobutyl group, a tert-butyl group, or a phenyl group can be similarly exemplified.

Examples of amines include bis (3,4,5-trifluorophenyl) amine, bis (3,4,5-tris (trifluoromethyl) phenyl) amine and bis (3,4,5-tris ( Pentafluorophenyl) phenyl) amine, bis (3,5-difluoro-4-pentafluorophenylphenyl) amine, bis (4,5,5
6,7,8-pentafluoro-2-naphthyl) amine,
Bis (3,4,5-trichlorophenyl) amine, bis (3,4,5-tris (trichloromethyl) phenyl)
Amine, bis (3,4,5-tris (pentachlorophenyl) phenyl) amine, bis (3,5-dichloro-4)
-Pentachlorophenylphenyl) amine, bis (4,4
5,6,7,8-pentachloro-2-naphthyl) amine, bis (3,4,5-tribromophenyl) amine,
Bis (3,4,5-tris (tribromomethyl) phenyl) amine, bis (3,4,5-tris (pentabromophenyl) phenyl) amine, bis (3,5-dibromo-4-pentabromophenylphenyl) ) Amine, bis (4,5,6,7,8-pentabromo-2-naphthyl)
Amine, bis (3,4,5-triiodophenyl) amine, bis (3,4,5-tris (triiodomethyl) phenyl) amine, bis (3,4,5-tris (pentaiodophenyl) phenyl) Examples thereof include amine, bis (3,5-diiodo-4-pentaiodophenylphenyl) amine, and bis (4,5,6,7,8-pentaiodo-2-naphthyl) amine. Further, a phosphine compound in which a nitrogen atom is replaced with a phosphorus atom can be similarly exemplified. Those phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples into phosphine. Further, in the above-mentioned specific examples, the hydrogen atom at the 2,6-position (in the case of naphthylamine or naphthylphosphine, the hydrogen atom at the 1,3-position) is methyl group, ethyl group, n
An amine compound substituted with a -propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or a phenyl group, or a phosphine compound can be similarly exemplified.

As the compound (b), phenols are preferably 3,4,5-trifluorophenol,
3,4,5-Tris (trifluoromethyl) phenol, 3,4,5-Tris (pentafluorophenyl) phenol, 3,5-difluoro-4-pentafluorophenylphenol, or 4,5,6,7, 8-Pentafluoro-2-naphthol, amines such as bis (3,4,5-trifluorophenyl) amine, bis (3,4,5-tris (trifluoromethyl) phenyl) amine, bis (3,3 4,5-tris (pentafluorophenyl) phenyl) amine, bis (3,5-difluoro-4-pentafluorophenylphenyl) amine,
Or bis (4,5,6,7,8-pentafluoro-2
-Naphthyl) amine.

The compound (b) is more preferably 3,
4,5-trifluorophenol, 4,5,6,7,8
-Pentafluoro-2-naphthol, bis (3,4,5
-Trifluorophenyl) amine, or bis (4,
5,6,7,8-pentafluoro-2-naphthyl) amine, particularly preferably 3,4,5-trifluorophenol.

Specific examples of the compound (c) include water,
Hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine, more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propyl. Amine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-
Pentylamine, neopentylamine, isopentylamine, n-hexylamine, n-octylamine, n-
Decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine,
3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4- Trimethylaniline, 2,3,5-trimethylaniline, 2,
3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3
4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butyl Aniline, sec-butylaniline, tert-butylaniline, n-pentylaniline, neopentylaniline, n-hexylaniline, n-octylaniline, n
-Decylaniline, n-dodecylaniline, n-tetradecylaniline, naphthylamine, anthracenylamine,

Benzylamine, (2-methylphenyl)
Methylamine, (3-methylphenyl) methylamine,
(4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) Methylamine, (3,4-dimethylphenyl) methylamine,
(3,5-dimethylphenyl) methylamine, (2,
3,4-trimethylphenyl) methylamine, (2,
3,5-trimethylphenyl) methylamine, (2,
3,6-trimethylphenyl) methylamine, (3
4,5-trimethylphenyl) methylamine, (2,
4,6-trimethylphenyl) methylamine, (2,
3,4,5-tetramethylphenyl) methylamine,
(2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n- Propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec
-Butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (neopentylphenyl) methylamine,
(N-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine, fluoromethylamine , Chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2 , 2,2-Trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2
-Triiodoethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-Pentaiodopropylamine, 2,2,2-trifluoro-1-
Trifluoromethylethylamine, 2,2,2-trichloro-1-trichloromethylethylamine, 2,2,2
-Tribromo-1-tribromomethylethylamine,
2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl) -2,
2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2
2-tribromoethylamine, 1,1-bis (triiodomethyl) -2,2,2-triiodoethylamine,

Perfluoropropylamine, perchloropropylamine, perbromopropylamine, periodopropylamine, perfluorobutylamine, perchlorobutylamine, perbromobutylamine, periodobutylamine, perfluoropentylamine, perchloropentylamine, perfluorobutylamine Bromopentylamine, periodopentylamine, perfluorohexylamine, perchlorohexylamine, perbromohexylamine,
Periodohexylamine, Perfluorooctylamine, Perchlorooctylamine, Perbromooctylamine, Periodooctylamine, Perfluorododecylamine, Perchlorododecylamine, Perbromododecylamine, Periodododecylamine, Perfluoropentadecylamine , Perchloropentadecylamine,
Perbromopentadecylamine, periodopentadecylamine, perfluoroeicosylamine, perchloroeicosylamine, perbromoeicosylamine, periodoeicosylamine,

2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3
-Chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2
-Iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3 , 5-
Dibromoaniline, 2,6-diiodoaniline, 3,5
-Diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4,6-triiodoaniline,
3,4,5-trifluoroaniline, 3,4,5-trichloroaniline, 3,4,5-tribromoaniline,
3,4,5-triiodoaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline,
Pentaiodoaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4-
(Trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, 3,4,5 -Tri (trifluoromethyl) aniline.

The compound (c) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-.
Butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2,6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine,
Perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline,
3-fluoroaniline, 4-fluoroaniline, 2,6
-Difluoroaniline, 3,5-difluoroaniline,
2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline ,
2,6-bis (trifluoromethyl) aniline, 3,5
-Bis (trifluoromethyl) aniline, or 2,
4,6-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine,
Perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6- Trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5 -Bis (trifluoromethyl) aniline, 2,4,6-tris (trifluoromethyl) aniline, or 3,4,5-trifluoroaniline, most preferably water or pentafluoroaniline.

As the particles (d), those generally used as a carrier are preferably used, a porous substance having a uniform particle size is preferable, an inorganic substance or an organic polymer is preferably used, and an inorganic substance is more preferable. It is preferably used. From the viewpoint of the particle size distribution of the polymer obtained, the particles (d) preferably have a volume-based geometric standard deviation of the particle diameter of the particles (d) of 2.5 or less, more preferably 2.0 or less,
More preferably, it is 1.7 or less.

Of the inorganic substances which can be used as particles (d)
Examples include inorganic oxides, clay and clay minerals.
It can be used if there is no problem. These are mixed for use
It doesn't matter. Specific examples of the inorganic oxide include Si
O₂, Al₂O₃, MgO, ZrO₂, TiO ₂, B₂O₃,
CaO, ZnO, BaO, ThO₂Etc, and these
Mixture, eg SiO₂-MgO, SiO₂-Al
₂O₃, SiO₂-TiO₂, SiO₂-V₂O _Five, SiO₂−
Cr₂O₃, SiO₂-TiO₂-Examples of MgO
You can Among these inorganic oxides, SiO₂Oh
And / or Al₂O₃Is preferred, especially SiO₂(Ie
Silica) is preferred. In addition, a small amount of the above inorganic oxide
Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂
SO_Four, Al₂(SO_Four)₃, BaSO_Four, KNO₃, Mg
(NO₃)₂, Al (NO₃)₃, Na₂O, K₂O, Li₂
Contains carbonates, sulfates, nitrates, oxides such as O
I don't care.

As the clay or clay mineral, kaolin,
Bentonite, kibushi clay, gyrome clay, allophane,
Hissingelite, bilophyllite, talc, ummo group,
Examples include montmorillonite group, vermiculite, ryokdee stone group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Of these, smectite, montmorillonite, hectorite, laponite and saponite are preferable, and montmorillonite and hectorite are more preferable.

Among these inorganic substances, inorganic oxides are preferably used. It is preferable that these inorganic substances are dried to substantially remove water, and those dried by heat treatment are preferable. The heat treatment is usually performed at a temperature of 100 to 100 for inorganic substances whose water content cannot be visually confirmed.
At 1,500 ° C, preferably 100-1,000 ° C,
More preferably, it is carried out at 200 to 800 ° C. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate, a method of reducing the pressure, or the like can be used, but the method is not limited to this.

Further, a hydroxyl group is usually formed and present on the surface of the inorganic oxide, but as the inorganic oxide, a modified inorganic oxide in which active hydrogen of the surface hydroxyl group is substituted with various substituents is used. You may. In this case, the substituent is preferably a silyl group. Specific examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldisilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as chlorosilane and methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxy such as dimethyldimethoxysilane. Diaryldialkoxysilanes such as silane and diphenyldimethoxysilane, alkyltria such as methyltrimethoxysilane Kokishishiran, aryltrialkoxysilanes such as phenyltrimethoxysilane,
Tetraalkoxysilane such as tetramethoxysilane,
Examples thereof include inorganic oxides which have been contact-treated with alkyldisilazanes such as 1,1,1,3,3,3-hexamethyldisilazane and tetrachlorosilane.

The average particle size of the inorganic substance is preferably
5 to 1000 μm, more preferably 10 to 500
μm, and more preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 10
It is 0 to 500 m ² / g.

As the organic polymer which can be used as the particles (d), any organic polymer may be used, and plural kinds of organic polymers may be used as a mixture.
As the organic polymer, a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group is preferable.

The functional group having active hydrogen is not particularly limited as long as it has active hydrogen, and specific examples thereof include primary amino group, secondary amino group, imino group, amide group, hydrazide group and amidino group. , Hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group,
Examples thereof include piperidyl group, indazolyl group, carbazolyl group and the like. Preferably, a primary amino group, a secondary amino group,
It is an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group. Particularly preferred is a primary amino group, a secondary amino group, an amido group or a hydroxy group. In addition, these groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The aproton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base moiety having no active hydrogen atom, and specific examples include a pyridyl group and an N-substituted imidazolyl group. N-substituted indazolyl group, nitrile group, azido group, N-substituted imino group, N,
N-substituted amino group, N, N-substituted aminooxy group, N,
N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group,
Examples thereof include N, N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. A heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable. Particularly preferred are pyridyl group, N-substituted imidazolyl group and N-substituted indazolyl group, and most preferred is pyridyl group. In addition, these groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The amount of the functional group having active hydrogen or the non-proton donating Lewis basic functional group is not particularly limited, but preferably 0.01 to 50 mmol as a molar amount of the functional group per unit gram of the polymer. / G,
It is more preferably 0.1 to 20 mmol / g.

The polymer having such a functional group is, for example,
By homopolymerizing a monomer having an active hydrogen-containing functional group or an aproton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or another monomer having a polymerizable unsaturated group It can be obtained by copolymerizing with a monomer. At this time, it is preferable to additionally copolymerize a crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups together.

As the monomer having such a functional group having active hydrogen or an aproton-donating Lewis basic functional group and at least one polymerizable unsaturated group, the above-mentioned functional group having active hydrogen and at least one Examples thereof include a monomer having a polymerizable unsaturated group, or a monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such a polymerizable unsaturated group include a vinyl group, an alkenyl group such as an allyl group, and an alkynyl group such as an ethyne group. Examples of the monomer having a functional group having active hydrogen and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine,
Vinyl group-containing secondary amine, vinyl group-containing amide compound,
Mention may be made of vinyl group-containing hydroxy compounds.
Specific examples include N- (1-ethenyl) amine and N-
(2-propenyl) amine, N- (1-ethenyl) -N
-Methylamine, N- (2-propenyl) -N-methylamine, 1-ethenylamide, 2-propenylamide,
N-methyl- (1-ethenyl) amide, N-methyl-
(2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like can be mentioned. Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole. Can be mentioned.

Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefins, aromatic vinyl compounds and the like. Specific examples are ethylene, propylene, 1-butene, 1-hexene, 4- Methyl-1-pentene, styrene and the like can be mentioned. Preferred is ethylene or styrene. Two or more kinds of these monomers may be used. Further, specific examples of the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene and the like.

The average particle diameter of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 5 μm.
It is 00 μm. The pore volume is preferably 0.1 m
It is 1 / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² /
g, more preferably 50 to 500 m ² / g.

It is preferable that these organic polymers are dried to substantially remove water, and those dried by heat treatment are preferable. The heat treatment is usually performed at a temperature of 30 to 40 for an organic polymer whose water content cannot be visually confirmed.
It is carried out at 0 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate, a method of reducing the pressure, or the like can be used, but the method is not limited to this.

The modified particles of the present invention are the modified particles obtained by bringing the above-mentioned (a), (b), (c) and (d) into contact with each other. The order in which (a), (b), (c) and (d) are brought into contact with each other is not particularly limited, and examples thereof include the following order. <1> A contact product obtained by bringing (a) and (b) into contact with (c) is brought into contact with (d). <2> A contact product obtained by bringing (a) and (b) into contact with (d) is brought into contact with (c). <3> A contact product obtained by bringing (a) and (c) into contact with (b) is brought into contact with (d). <4> A contact product of (a) and (c) is contacted with a contact product obtained by contacting (d) with (b). <5> A contact product obtained by bringing (a) and (d) into contact with (b) is brought into contact with (c). <6> The contact product of (a) and (d) is contacted with the contact product obtained by contacting (c) with (b). <7> The contact product of (b) and (c) is contacted with the contact product obtained by contacting (a) with (d). <8> A contact product obtained by bringing (b) and (c) into contact with (d) is brought into contact with (a). <9> The contact product of (b) and (d) is contacted with the contact product obtained by contacting (a) with (c). <10> The contact product of (b) and (d) is contacted with the contact product obtained by contacting (c) with (a). <11> The contact product of (c) and (d) is contacted with the contact product obtained by contacting (a) with (b). <12> A contact product obtained by bringing (c) and (d) into contact with (b) is brought into contact with (a). The contact order is preferably <1>, <2>, <3 above.
>, <11> or <12>.

Such contact treatment is preferably carried out in an inert gas atmosphere. Processing temperature is usually -100 to 3
The temperature is 00 ° C, preferably -80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 1
It is 0 minutes to 100 hours. Further, such a treatment may use a solvent or may directly treat these compounds without using them.

As the solvent, a solvent which does not react with each of the components to be contacted when the solvent is used and the contact product obtained by the contact is usually used. As described above, when the components are brought into contact with each other stepwise, for example, the above (a)
Even if it is a solvent that reacts with, the contact product obtained by contacting (a) with other components may no longer react with the solvent. The solvent can be used as a solvent at the time of the contacting operation with one component. Examples of the solvent are shown below, but the solvent may be appropriately used in this way. Examples of the solvent that can be used are aliphatic hydrocarbon solvents, non-polar solvents such as aromatic hydrocarbon solvents, or halide solvents, ether solvents,
Examples thereof include polar solvents such as alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amine solvents and sulfur compounds.
Specific examples include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, aliphatic hydrocarbon solvents such as cyclohexane, benzene, toluene, aromatic hydrocarbon solvents such as xylene, dichloromethane, difluoromethane, Halide solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, etc., Dimethyl ether, diethyl ether, diisopropyl ether, di-
n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether,
Tetrahydrofuran, ether solvent such as tetrahydropyran, methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-butanol,
Alcoholic solvents such as 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol and glycerin. , Phenol, phenol solvents such as p-cresol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N -Methyl-2
-Carbonyl solvent such as pyrrolidone, hexamethylphosphoric triamide, phosphoric acid derivative such as triethyl phosphate, acetonitrile, propionitrile, succinonitrile,
Examples thereof include nitrile solvents such as benzonitrile, nitro compounds such as nitromethane and nitrobenzene, amine solvents such as pyridine, piperidine and morpholine, and sulfur compounds such as dimethyl sulfoxide and sulfolane.

When the contact product (e) obtained by contacting (a), (b) and (c) with the particle (d) is contacted, that is, <1>, <3> and <7 described above. In the case of>, the solvent (s1) for producing the contact product (e) is preferably the above-mentioned aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) for bringing the contact substance (e) and the particles (d) into contact with each other.
As an index representing the polarity of the solvent, E _T ^N value (C.Reic
hardt, “Solvents and Solve
nts Effects in Organic Ch
"", 2nd ed., VCH Ve
rlag (1988). ) Etc. are known and 0.8
A solvent satisfying ≧ E _T ^N ≧ 0.1 is particularly preferable. Examples of such polar solvents include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane,
1,2-dibromoethane, 1,1,2-trichloro-
1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-
tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol. , 2-butanol, 2-methyl-1-propanol, 3-methyl-1-
Butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-
Methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone,
Ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, phosphorus Examples thereof include triethyl acid, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide and sulfolane. Solvent (s2)
More preferably as dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane,
Bis (2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol,
1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,
3-Methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl-tert. With butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol. And most preferably tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

As the solvent (s2), it is also possible to use a mixed solvent of these polar solvents and a hydrocarbon solvent. As the hydrocarbon solvent, the above-exemplified aliphatic hydrocarbon solvent or aromatic hydrocarbon solvent is used. Specific examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent. , Heptane / ethanol mixed solvent, heptane / 1
-Propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene /
Ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, xylene /
2-propanol mixed solvent etc. can be illustrated.
Preferably hexane / methanol mixed solvent, hexane /
Ethanol mixed solvent, heptane / methanol mixed solvent,
Heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene /
They are a methanol mixed solvent and a xylene / ethanol mixed solvent. More preferably, it is a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent, or a toluene / ethanol mixed solvent. Most preferably, it is a toluene / ethanol mixed solvent. The preferred range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, and more preferably 15 to 30% by volume.

A method of bringing the contact product (e) obtained by bringing (a), (b) and (c) into contact with (d);
That is, in the cases of <1>, <3>, and <7> above,
A hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2), but in this case (a), (b)
After contacting (c) and (c), it is preferable that the time interval between contacting the obtained contact product (e) and particles (d) is short. The time interval is preferably 0 to 5 hours,
More preferably 0 to 3 hours, most preferably 0.
~ 1 hour. The temperature at which the contact product (e) and the particles (d) are contacted is usually -100 ° C to 40 ° C, preferably -20 ° C to 20 ° C, and most preferably -10 ° C to 10 ° C. ℃.

The above <2>, <5>, <6>, <8>,
In the case of <9>, <10>, <11>, and <12>, any of the above nonpolar solvents and polar solvents can be used, but nonpolar solvents are more preferable. This is because the contact product of (a) and (c) or the contact product of (a) and (b) with (c) generally has a solubility in a nonpolar solvent. Since it is low, when (d) is present in the reaction system when these contact products are produced, it is more stable to deposit the produced contact product on the surface of (d) than to exist in the nonpolar solvent. It is preferable because it is considered that the particles are more easily immobilized.

The amount of each compound used in (a), (b) and (c) is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: When the molar ratio of y: z is satisfied, it is preferable that y and z substantially satisfy the following formula (1). | M−y−2z | ≦ 1 (1) (In the above formula (1), m represents the valence of M ¹ ) In the above formula (1), y is preferably 0.01 to.
The number is 1.99, more preferably 0.10 to 1.8.
It is a number of 0, more preferably a number of 0.20 to 1.50, most preferably a number of 0.30 to 1.00, and a similar preferable range of z in the above formula (1) is , M, y and equation (1) above.

In the actual contact treatment of each compound, even if it is attempted to use each compound so as to completely satisfy the above formula (1), the amount used may be slightly changed, and It is common practice to appropriately increase or decrease the amount used in consideration of the amount of the compound remaining in the reaction. As used herein, "substantially satisfying the equation (1)" means that the above equation (1) is not completely satisfied.
It is meant to include when the compound is intended to be obtained by contacting each compound at a molar ratio satisfying

In preparing the modified particles of the present invention,
As the amount of (d) used with respect to (a), typical metal atoms derived from (a) contained in the particles obtained by contacting (a) and (d) are contained in 1 g of the obtained particles. In terms of the number of moles of the typical metal atom, the amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol. Therefore, it may be appropriately determined to fall within the range.

After the contact treatment as described above, heating is also preferably carried out in order to further promote the reaction. Since the temperature is higher during heating, it is preferable to use a solvent having a higher boiling point. Therefore, the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.

The modified particles of the present invention are the raw materials (a), (b),
(C) and / or (d) may remain as an unreacted material. However, in the case of applying the polymerization involving the formation of addition polymer particles, it is preferable to previously perform a washing treatment for removing unreacted substances. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably performed under an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 20.
It is 0 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

After such contact treatment or washing treatment, it is preferable that the solvent is distilled off from the product, and then the product is dried at a temperature of 25 ° C. or higher under reduced pressure for 1 to 24 hours.
More preferably at a temperature of 40 ° C to 200 ° C for 1 hour to 24
Time, more preferably 60 to 200 ° C for 1 to 24 hours, particularly preferably 60 to 160 ° C for 2 to 18 hours, most preferably 80 to 160 ° C.
It is preferable to perform drying at the temperature of 4 hours to 18 hours.

A specific example of the method for producing modified particles of the present invention is as follows. M ¹ is a zinc atom, and compound (b) is 3, 4,
It will be described in more detail below for the case of 5-trifluorophenol, the compound (c) is water and the particles (d) are silica. Tetrahydrofuran was used as a solvent, a hexane solution of diethylzinc was added thereto, and the mixture was cooled to 3 ° C., and an equimolar amount of 3,4,5
-Drop trifluorophenol for 10 minutes at room temperature
After stirring for 24 hours, 0.5 times the molar amount of water with respect to diethyl zinc is added dropwise, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, the solvent is distilled off, and the product is dried at 120 ° C. under reduced pressure for 8 hours. Tetrahydrofuran and silica were added to the solid component obtained by the above operation, and the solid content was adjusted to 2 at 40 ° C.
Stir for hours. After washing the solid component with tetrahydrofuran, it is dried at 120 ° C. under reduced pressure for 8 hours. Thus, the modified particles of the present invention can be produced.

The modified particles of the present invention can be used as a carrier for carrying a catalyst component for addition polymerization consisting of a transition metal compound forming a single site catalyst, and are suitably used for polymerization accompanied by formation of addition polymer particles. To be done. Further, the modified particles of the present invention are useful as a catalyst component for addition polymerization (among others, a catalyst component for olefin polymerization). Specific examples of the addition polymerization catalyst of the present invention include the above modified particles (A) and addition polymerization obtained by contacting the transition metal compound (B) of Groups 3 to 11 or lanthanoid series. Examples include a catalyst, and addition polymerization obtained by contacting the modified particles (A), the Group 3 to 11 or lanthanoid series transition metal compound (B), and the organoaluminum compound (C). For example, the latter is more active and preferable. Hereinafter, the addition polymerization catalyst will be described in more detail.

(B) Group 3-11 or lanthanoid series transition metal compound A single-site catalyst is formed as the group 3-11 or lanthanoid series transition metal compound (B) used in the catalyst for addition polymerization of the present invention. Group 3 to 11 or a lanthanoid exhibiting addition polymerization activity by using the above-mentioned modified particles (A) (or further organoaluminum compound (C)) as a co-catalyst component for activation. There is no particular limitation as long as it is a series of transition metal compounds. The single-site catalyst here is a concept that is distinguished from conventional solid catalysts, and has a narrow molecular weight distribution and, in the case of copolymerization, not only a narrowly defined single-site catalyst that gives an addition polymer with a narrow composition distribution, but also A catalyst obtained by an adjustment method similar to such a single-site catalyst in a narrow sense includes an addition polymer having a wide molecular weight distribution, and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization. .

As the transition metal compound (B), a transition metal compound represented by the following general formula [4] or its μ
-Oxo type transition metal compound dimers are preferred. L ² _a M ² X ¹ _b [4] (In the formula, M ² is a transition metal atom of Groups 3 to 11 of the periodic table or a lanthanoid series. L ² is a group having a cyclopentadiene type anion skeleton or a hetero atom. And a plurality of L ² 's 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.
¹ is a halogen atom or a hydrocarbon group (excluding groups having a cyclopentadiene type anion skeleton).
a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. )

In the general formula [4], M ² is a transition metal atom of Groups 3 to 11 of the Periodic Table (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atom, ytterbium atom and the like. M in the general formula [4]
² , preferably titanium atom, zirconium atom,
It is a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom.

In the general formula [4], L ² is a group having a cyclopentadiene type anion skeleton or a group containing a hetero atom, and a plurality of L ² may be the same or different. Further, a plurality of L ² 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.

L² Cyclopentadiene Form Anio
(Substituted) cyclopentadiene
Lu group, η^Five -(Substituted) indenyl group, η^Five -(Replace)
Examples thereof include a louenyl group. To give a concrete example,
η^Five -Cyclopentadienyl group, η^Five -Methylcyclope
Ntadienyl group, η^Five -Ethylcyclopentadienyl
Base, η^Five -N-butylcyclopentadienyl group, η^Five −
tert-butylcyclopentadienyl group, η^Five -1,
2-dimethylcyclopentadienyl group, η^Five -1,3-
Dimethylcyclopentadienyl group, η^Five -1-methyl-
2-ethylcyclopentadienyl group, η^Five -1-methyl
-3-ethylcyclopentadienyl group, η ^Five -1-te
rt-butyl-2-methylcyclopentadienyl group, η
^Five -1-tert-butyl-3-methylcyclopentadi
Phenyl group, η^Five -1-methyl-2-isopropylcyclo
Pentadienyl group, η^Five -1-methyl-3-isopropyi
Rucyclopentadienyl group, η^Five -1-methyl-2-n
-Butylcyclopentadienyl group, η^Five -1-methyl-
3-n-butylcyclopentadienyl group, η^Five -1,
2,3-trimethylcyclopentadienyl group, η^Five −
1,2,4-trimethylcyclopentadienyl group, η^Five 
-Tetramethylcyclopentadienyl group, η^Five -Penta
Methylcyclopentadienyl group, η^Five An indenyl group,
η^Five −4,5,6,7-tetrahydroindenyl group, η
^Five -2-methylindenyl group, η^Five -3-methylindene
Nyl group, η^Five -4-methylindenyl group, η^Five -5
Tylindenyl group, η^Five -6-methylindenyl group, η
^Five -7-methylindenyl group, η^Five -2-tert-bu
Tylindenyl group, η^Five -3-tert-butyl inde
Nyl group, η^Five -4-tert-butylindenyl group, η
^Five -5-tert-butylindenyl group, η^Five -6-t
ert-butylindenyl group, η^Five -7-tert-bu
Tylindenyl group, η^Five -2,3-dimethylindenyl
Base, η^Five -4,7-Dimethylindenyl group, η^Five -2
4,7-trimethylindenyl group, η^Five -2-methyl-
4-isopropylindenyl group, η^Five -4,5-Benz
Indenyl group, η ^Five -2-methyl-4,5-benzyne
Denyl group, η^Five -4-phenylindenyl group, η^Five -2
-Methyl-5-phenylindenyl group, η^Five -2-Met
Lu-4-phenylindenyl group, η^Five -2-methyl-4
-Naphthylindenyl group, η^Five -Fluorenyl group, η^Five 
-2,7-Dimethylfluorenyl group, η^Five -2,7-di
-Tert-butyl fluorenyl group, and these groups
Examples include a substitute. In this specification, transition
For the name of the metal compound, see “η^Five Omission of "-"
There is.

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 are an alkoxy group, an aryloxy group, a thioalkoxy group and a thioaryloxy group. Group, alkylamino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic having oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom in the ring Heterocyclic groups are preferred.

Specific examples of the group containing a hetero atom include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 2-methylphenoxy group, 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'-biphenyldiol Group, 1,1'-bee
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'-isobutyryl Examples thereof include a dendiphenoxy group.

As the group containing a hetero atom, a group represented by the following general formula [5] can be exemplified. R ⁴ ₃ P = N- [5] (In the formula, R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, and they may be the same or different from each other. The above may be bonded to each other or may form a ring.)

Specific examples of R ⁴ in the above general formula [5] include hydrogen atom, fluorine atom, chlorine atom, bromine atom,
Iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cycloheptyl group,
Cyclohexyl group, phenyl group, 1-naphthyl group, 2-
Examples thereof include, but are not limited to, a naphthyl group and a benzyl group.

Further, as the group containing a hetero atom, a group represented by the following general formula [6] can be exemplified. (In the formula, R ⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group in each case, and they may be the same or different. Or two or more of them may be bonded to each other and may form a ring.)

Specific examples of R ⁵ in the general formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom,
Iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-
Trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-
Phenylethyl group, 1,1-dimethylpropyl group, 2-
Examples thereof include chlorophenyl group and pentafluorophenyl group, but are not limited thereto.

The chelating ligand refers to a ligand having a plurality of coordination sites, and specific examples thereof include acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, and triethylene. Examples thereof include ethylene tetramine, porphyrin, crown ether and cryptate.

Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, preferably a pyridyl group.

The groups having a cyclopentadiene type anion skeleton, the groups having a cyclopentadiene type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom may be directly linked 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. Such a residue is preferably a divalent residue in which the atom bonded to two L ² is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 An atom bonded to one L ² is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and the minimum number of atoms between the atoms bonded to two L ² is 3 or less. A residue (this includes a single atom bonded to two L ^{2 s} ). Specifically, methylene group, ethylene group, alkylene group such as propylene group, dimethylmethylene group (isopropylidene group), substituted alkylene group such as diphenylmethylene group, or silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene. Group, a tetramethyldisililen group, a substituted silylene group such as a dimethoxysilylene group, or a nitrogen atom, an oxygen atom, a sulfur atom, a hetero atom such as a phosphorus atom, and the like, and particularly preferably a methylene group, an ethylene group, a dimethylmethylene group. (Isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, or dimethoxysilylene group.

X ¹ in the general formula [4] is a halogen atom or a hydrocarbon group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, an alkenyl group and the like, and preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the number of carbon atoms. An aryl group having 6 to 20 or an alkenyl group having 3 to 20 carbon atoms is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and ter.
t-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. Of these, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group or an amyl group is more preferable. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples thereof include perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group and perbromopropyl group. In addition, 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.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group and (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, (2,3,4,5-tetramethylphenyl) methyl group, ( 2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propyl) (Phenyl) methyl group, (isopropylphenyl) methyl group,
(N-Butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) Examples thereof include a methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group and anthracenylmethyl group, and more preferably benzyl group. is there. All of these aralkyl groups are fluorine atom, chlorine atom,
It may be partially substituted with a halogen atom such as a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group,
4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 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,
Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like can be mentioned, and phenyl group is more preferable. All of these aryl groups are fluorine atom, chlorine atom, bromine atom,
It may be partially substituted with a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the alkenyl group having 3 to 20 carbon atoms include allyl group, methallyl group, crotyl group, 1,3
-Diphenyl-2-propenyl group and the like, and more preferably an allyl group or a methallyl group.

More preferably, X ¹ is chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n
A butyl group, a benzyl group, an allyl group or a methallyl group.

In the general formula [4], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and M ²
Is appropriately selected according to the valence of.

Among the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride and bis. (Methylcyclopentadienyl) titanium dichloride,
Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium Dichloride, bis (1,
3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl -2-n-butylcyclopentadienyl)
Titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopenta) Dienyl) titanium dichloride,
Bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-
Butyl-3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-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-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoro). Methylphenyl) 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, pentamethylcyclopentadienyl (indenyl) titanium dichloride, Pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-
Phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindenyl) 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 (3,3)
4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,
5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethyl Silylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethyl silylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindene) Nyl) titanium dichloride, dimethyl silylene bis (2,
4,7-trimethylindenyl) titanium dichloride,
Dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (4,5-benzindenyl) titanium dichloride,
Dimethylsilylenebis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylenebis (2-phenylindenyl) titanium dichloride, dimethylsilylenebis (4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl) -4-
Phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) 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, dimethylsilylene bis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (Tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy)
Titanium dichloride, cyclopentadienyl (2,6-
Dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-te)
rt-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,

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 (cyclopentadienyl) (3-phenyl 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (1
-Naphthoxy-2-yl) 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 (methylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2
-Yl) 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 (n-butylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) 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 (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (1 -Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta) 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
ert-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 (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, di Chirushiriren (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) 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 (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (1-naphthoxy-2 -Yl) 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 (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (1-naphthoxy-2-yl) 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 (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1- Naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopenta Dienyl-1,2-ethanediyl titanium dichloride, (te
(rt-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (tert-butylamide ) Indenyl-
1,2-ethanediyl titanium dichloride, (tert
-Butylamido) tetrahydroindenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) indenyl dimethylsilane titanium dichloride, (tert-butylamido) tetrahydro Indenyldimethylsilane titanium dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium ( II
I) dichloride, (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B
-Dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride,

2,2'-thiobis [4-methyl-6-t
ert-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 , 2′-Sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2 ′-(4,4 ′, 6,6′-tetra-t
ert-Butyl-1,1'biphenoxy) titanium dichloride, (di-tert-butyl-1,3-propanediamido) titanium dichloride, (dicyclohexyl-
1,3-propanediamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-propanedidiamide] titanium dichloride, [bis (te
rt-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, [hydrotris (3 , 5-Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-
Butylpyrazolyl) borate] titanium trichloride,
[Tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [Tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [Tris (3,3
5-di-tert-butylpyrazolyl) methyl] titanium trichloride, etc., and compounds in which titanium of these compounds is changed to zirconium or hafnium, (2-
Phenoxy) to (3-phenyl-2-phenoxy),
(3-trimethylsilyl-2-phenoxy), or a compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilylene is methylene,
Compounds in which ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene are changed, compounds in which dichloride is changed to difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, or dibenzyl, Trichloride, trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl,
Examples thereof include compounds that are changed to triphenyl or tribenzyl.

Of the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom is a nickel atom include 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 [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-phenyl-5,5'-dicyclohexyloxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-phenyl-5,
5'-dimethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4 -Phenyl-5,5'-diphenyloxazoline] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,
2'-methylenebis [(4R) -4-methyl-5,5-
Di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel Dibromide,
2,2'-methylenebis [(4R) -4-methyl-5,
5-Di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2 ′ -Methylenebis [spiro {(4R) -4-methyloxazoline-
5,1'-Cyclopentane}] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-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], 2,2′-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 [(4
R) -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 [(4
R) -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 [(4
R) -4-Isopropyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,

2,2'-methylenebis [spiro {(4
R) -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 [(4R) -4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-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 {(4
R) -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 [(4R) -4-te
rt-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, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-
(2-Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-te
rt-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-t
ert-Butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-tert-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 {( Four
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 {(4
R) -4-Phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-
5,1'-Cyclopentane}] nickel dibromide,
2,2′-methylenebis [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 {(4
R) -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 the antipodes of the above compounds. In addition, a compound in which the steric configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline type compound is reversed, or dibromide of these compounds is difluoride, dichloride, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, or The compound etc. which changed to dibenzyl can be illustrated.

Further, specific examples of the nickel compound include:
[Hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride,
[Hydrostris (3,5-di-tert-butylpyrazolyl) borate] Nickel chloride and compounds in which the chlorides of these compounds are changed to bromide, iodide, methyl, ethyl, allyl, or methallyl.

Examples of nickel compounds include compounds represented by the following structural formulas. (In the formula, R ⁶ and R ⁷ are each a 2,6-diisopropylphenyl group, R ⁸ and R ⁹ are each a hydrogen atom or a methyl group, or R ⁸ and R ⁹ together are an acenaphthene group, X ² is a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-
A propyl group, an isopropyl group, an n-butyl group, a phenyl group, or a benzyl group. ) Further, in the above nickel compound, a compound in which nickel is replaced by palladium, cobalt, rhodium, or ruthenium can be similarly exemplified.

Among the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom is iron include 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 and the like, and compounds obtained by changing the dichloride of these compounds to difluoride, dibromide, diiodide, dimethyl, or diethyl are mentioned.

Further, specific examples of the iron compound include [hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride and [hydrotris (3,3
5-di-tert-butylpyrazolyl) borate] iron chloride and the like, and compounds in which the chloride of these compounds is changed to fluoride, bromide, iodide, methyl, ethyl, allyl, or methallyl. Further, in the above iron compound, a compound in which iron is replaced with cobalt or nickel can be similarly exemplified.

Specific examples of the μ-oxo type transition metal compound of the transition metal compound represented by the general formula [4] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride. ], Μ
-Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride] ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopenta) Dienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (3 -Tert-butyl-5-methyl-2
-Phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl)]
(2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl)]
(3-tert-Butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetra Methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium chloride] and the like. In addition, the chlorides of these compounds are changed to fluoride, bromide,
Examples thereof include compounds modified to iodide, methyl, ethyl, isopropyl, phenyl, or benzyl.

In addition to the transition metal compound represented by the general formula [4] and the μ-oxo type transition metal compound thereof exemplified above, examples of the compound used as the transition metal compound (B) include a transition metal atom. As a compound in which is a nickel atom, nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate,
Nickel acetate, 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,
Carbonyl tris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel,
Diacetobis (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 transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride and the like. Further, specific examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran. Specific examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

These transition metal compounds may be used alone or in combination of two or more.

Among the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably the transition metal compound represented by the above general formula [4]. Among them, a transition metal compound in which M ² in the general formula [4] is a Group 4 atom is preferable, and a transition metal compound having at least one group having a cyclopentadiene type anion skeleton as L ² in the general formula [4] is particularly preferable. Is preferred.

(C) Organoaluminum Compound As the component (C) organoaluminum compound used in the catalyst for addition polymerization of the present invention, known organoaluminum compounds can be used. Preferred are organoaluminum compounds represented by the following general formula [7]. R ¹⁰ _c AlY _3-c [7] (In the formula, R ¹⁰ represents a hydrocarbon group, and all R ¹⁰ 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 all Y's may be the same or different. C represents a number satisfying 0 <c ≦ 3.)

R ¹⁰ in the general formula [7] representing an organoaluminum compound preferably has 1 to 2 carbon atoms.
A hydrocarbon group having 4 carbon atoms, more preferably 1 to 1 carbon atoms.
24 alkyl groups. As a specific example, a methyl group,
Examples thereof include an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a 2-methylhexyl group and an n-octyl group, preferably an ethyl group, an n-butyl group, an isobutyl group, n. A hexyl group or an n-octyl group.

Further, when Y is a halogen atom, specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. The alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms, and specific examples include, for example, a methoxy group,
Ethoxy group, n-propoxy group, isopropoxy group, n
-Butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-
Pentadesoxy group, n-icosoxy group and the like,
Preferred is a methoxy group, an ethoxy group or a tert-butoxy group.

The aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms, and specific examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6
-Dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group , 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,
Examples thereof include sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group.

The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms, and specific examples thereof include benzyloxy group, (2-methylphenyl) methoxy group and (3-methylphenyl) methoxy group. , (4-methylphenyl) methoxy group, (2,3-
Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group,
(3,4-dimethylphenyl) methoxy group, (3,5-
Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) 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 group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. , And preferably a benzyloxy group.

Specific examples of the organoaluminum compound represented by the general formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum and tri-n-hexyl. Aluminum, tri-
Trialkyl aluminum such as n-octyl aluminum; Dialkyl aluminum chloride such as dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, di-n-hexyl aluminum chloride. Alkyl aluminum dichlorides such as methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum Hydride, -n- butyl aluminum hydride, diisobutylaluminum hydride, di -n
-Dialkyl aluminum hydride such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy)
Aluminum, dialkyl (alkoxy) aluminums such as dimethyl (ethoxy) aluminum, dimethyl (tert-butoxy) aluminum; methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum. Alkyl (diaryloxy) aluminum such as; dimethyl (phenoxy)
Examples include aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dialkyl (aryloxy) aluminum such as dimethyl (2,6-diphenylphenoxy) aluminum, and the like.

Of these, trialkylaluminum is preferable, and trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum is more preferable. And particularly preferably triisobutylaluminum or tri-n-octylaluminum. Even if only one kind of these organoaluminum compounds is used,
You may use it in combination of 2 or more types.

The amount of component (B) used is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol, per 1 g of component (A). is there. The amount of the component (C) used is 0.0 as the molar ratio (C) / (B) of the aluminum atom of the organoaluminum compound of the component (C) to the transition metal atom of the transition metal compound of the component (B).
It is preferably 1 to 10,000, and 0.1 to 5,
It is more preferably 000, most preferably 1 to 2,000.

As the addition polymerization catalyst of the present invention, a reaction product obtained by previously contacting the components (A) and (B), and optionally the component (C), may be used. You may throw in separately and may be used. When using the components (A), (B) and (C), any two of them may be pre-contacted with each other, and then the other component may be contacted.

The method for supplying each catalyst component to the catalyst preparation reactor or the polymerization reactor is not particularly limited. Method of supplying each component in a solid state, method of supplying in a solution state dissolved in a hydrocarbon solvent in which components that deactivate catalyst components such as water and oxygen are sufficiently removed, or in a state of suspension or slurry Etc. As the solvent at this time, butane, pentane, hexane, heptane, an aliphatic hydrocarbon solvent such as octane, benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene, and halogenated hydrocarbons such as methylene chloride, and aliphatic hydrocarbons and aromatic hydrocarbons are preferable.

When each catalyst component is supplied in a solution state or in a state of being suspended or slurried, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. Is. The concentration of the component (C) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atom. The concentration of the component (B) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter in terms of transition metal atom.

The polymerization method is not particularly limited, either.
Gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization and the like are possible. Solvents used for solution polymerization or slurry polymerization include butane, pentane, hexane, heptane, octane and other aliphatic hydrocarbon solvents, benzene, toluene and other aromatic hydrocarbon solvents, and methylene chloride and other halogenated hydrocarbon solvents. Alternatively, the olefin itself can be used as a solvent (bulk polymerization). The polymerization method may be either batchwise polymerization or continuous polymerization, and the polymerization may be carried out in two or more stages under different reaction conditions. Generally, the polymerization time is appropriately determined depending on the kind of the desired olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

The present invention is particularly preferably applied to polymerization (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) involving formation of addition polymer particles. Slurry polymerization may be performed according to known slurry polymerization methods and polymerization conditions, but is not limited thereto. As a preferable polymerization method in the slurry method, a monomer (and a comonomer), a feed,
A continuous reactor in which a diluent or the like is continuously added as needed and a polymer product is continuously or at least periodically taken out is included. Examples of the reactor include a method using a loop reactor and a method using a stirring reactor. Further, a plurality of stirring reactors having different reactors or different reaction conditions may be used in series or in parallel, or a combination thereof.

As the diluent, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature of the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably 30 ° C to 100 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. The catalyst can be held in suspension, the medium and at least some of the monomers and comonomers can be maintained in the liquid phase, and pressure can be applied to bring the monomers and comonomers into contact. Therefore, the medium, temperature, and pressure may be selected so that the addition polymer is produced as solid particles and recovered in that form.

The molecular weight of the addition polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen. Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and a monomer (and a comonomer) to the reaction zone, a method of sequentially adding them, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contacting the monomer (and comonomer).

The gas phase polymerization may be carried out according to known gas phase polymerization methods and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction device, a fluidized bed type reaction tank, preferably a fluidized bed type reaction tank having an enlarged portion is used.
There is no problem even with a reaction apparatus in which a stirring blade is installed in the reaction tank. As a method for supplying each component to the polymerization tank, nitrogen, an inert gas such as argon, hydrogen, ethylene or the like is usually used, and the solution is supplied in a water-free state or is dissolved or diluted in a solvent to prepare a solution or slurry. A method such as supplying in the state can be used. Each catalyst component may be supplied individually, or any component may be contacted in advance in any order and supplied.

As polymerization conditions, the temperature is lower than the temperature at which the polymer melts, preferably 0 ° C to 150 ° C, particularly preferably 30 ° C to 100 ° C. Further, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In addition, an inert gas may coexist in the mixed gas during the polymerization.

In the present invention, the following pre-polymerization may be carried out before such polymerization (main polymerization).

The prepolymerization is carried out by the above modified particles (A).
And in the presence of the transition metal compound (B), or further in the presence of the organoaluminum compound (C), a small amount of olefin is supplied, and it is preferably carried out in a slurry state. Examples of the solvent used for making the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. In addition, liquid olefin can be used in place of a part or all of the inert hydrocarbon solvent at the time of slurry formation.

The amount of the organoaluminum compound (C) used during the prepolymerization can be selected within a wide range such as 0.5 to 700 mol per mol of the transition metal compound (B), but 0.8 to 500 mol. Is preferable, and 1 to 200 mol is particularly preferable.

The amount of olefin prepolymerized is
Usually 0.01 to 100 per gram of the above-mentioned modified particles
0 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g.

The slurry concentration at the time of prepolymerization is 0.
1-50 g-modified particles / liter-solvents are preferred, especially 0.5-20 g-modified particles / liter-
Solvents are preferred. The prepolymerization temperature is -20 ° C to 100 ° C.
Is preferable, and 0 ° C to 80 ° C is particularly preferable. The partial pressure of the olefin in the gas phase during the prepolymerization is 0.001M.
Pa to 2 MPa is preferable, and 0.01 MPa to 1 M is particularly preferable.
Pa is preferable, but this is not the case for olefins that are liquid at the pressure and temperature of prepolymerization. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is suitable.

When carrying out the prepolymerization, the modified particles (A), the transition metal compound (B), the organoaluminum compound (C), and the olefin are supplied as the above-mentioned modified particles. After the (A) and the transition metal compound (B) are brought into contact with each other, or, if necessary, the organoaluminum compound (C) is also brought into contact therewith, a method for supplying an olefin, the above-mentioned reforming is performed. Particles (A), transition metal compound (B) and olefin are brought into contact with each other, and then organoaluminum compound (C) is supplied, organoaluminum compound (C) and transition metal compound (B) in the presence of olefin Any method such as a method of supplying the modified particles (A) described above after contacting the above may be used, but the modified particles (A) and the organoaluminum compound (C It is preferable that the olefin is present in advance when contacting and. Further, as the olefin supply method, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying all of a predetermined amount of olefin may be used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the obtained polymer.

In the present invention, the thus obtained prepolymerized product is used as a catalyst component or a catalyst. The prepolymerized catalyst component according to the present invention comprises the above-mentioned modified particles (A), and the third to first particles.
Group 1 or lanthanoid series transition metal compounds (B)
In the presence of a primary catalyst obtained by contacting the olefins with each other, a prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin, or the above-mentioned modified particles (A), Nos. 3 to 1
A prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting a Group 1 or lanthanoid series transition metal compound (B) and an organoaluminum compound (C). is there.
The prepolymerized catalyst according to the present invention is in the presence of a primary catalyst obtained by contacting the above-mentioned modified particles (A) with a transition metal compound (B) of Groups 3 to 11 or a lanthanoid series. In addition, a catalyst for addition polymerization obtained by prepolymerizing an olefin, or the above-mentioned modified particles (A), Group 3 to 11 or lanthanoid series transition metal compound (B), and organoaluminum compound (C). The catalyst for addition polymerization obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting
The catalyst using the prepolymerized addition polymerization catalyst component according to the present invention is an addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C).

The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which an addition-polymerizable monomer is subjected to addition polymerization in the presence of the above-mentioned addition polymerization catalyst of the present invention. Examples of the monomer used for the polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like, and two or more kinds of monomers can be used at the same time.

Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-.
Pentene, 5-methyl-1-hexene, 1-hexene,
Olefins such as 1-heptene, 1-octene, 1-nonene, 1-decene; 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, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3- Butadiene, isoprene, 1,3-
Diolefins such as hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2 −
Norbornene, 5-phenyl-2-norbornene, 5-
Benzyl-2-norbornene, tetracyclododecene,
Tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene , 5-methoxycarbonyl-
2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-
Norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-
Cyclic olefins such as 8-tetracyclododecene and 8-cyanotetracyclododecene; alkenylbenzenes such as styrene, 2-phenylpropylene, 2-phenylbutene and 3-phenylpropylene, p-methylstyrene, m-
Methyl styrene, o-methyl styrene, α-methyl styrene, p-ethyl styrene, m-ethyl styrene, o-
Ethylstyrene, 2,4-dimethylstyrene, 2,5-
Dimethyl styrene, 3,4-dimethyl styrene, 3,5
-Alkyl styrenes such as dimethyl styrene, 3-methyl-5-ethyl styrene, 1,1-diphenyl ethylene, p-tertiary butyl styrene and p-secondary butyl styrene, bis alkenyl benzenes such as divinyl benzene,
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-2,3-
Α, β-unsaturated carboxylic acids such as dicarboxylic acids, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium and calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic Α-β-unsaturated carboxylic acid ester such as t-butyl acidate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Unsaturated dicarboxylic acids such as maleic acid and itaconic acid, vinyl acetate,
Vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc., unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconic acid ester, etc. And polar monomers such as

The present invention applies 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 ethylene and 1-.
Examples include octene, propylene and 1-butene, ethylene and propylene and butene, ethylene and propylene and 1-hexene, but the present invention is not limited thereto.

The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst and is preferably used in a method for producing an olefin polymer. As such an olefin polymer, a copolymer of ethylene and α-olefin is particularly preferable, and among them, a copolymer of ethylene and α-olefin having a polyethylene crystal structure is preferable. The α-olefin referred to herein preferably has 3 to 8 carbon atoms.
Α-olefin, specifically 1-butene, 1-butene
Examples include hexene and 1-octene.

[0157]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The measured value of each item in the examples was measured by the following method.

(1) The content of the repeating unit derived from α-olefin in the copolymer was measured by using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation) to measure the characteristic absorption of ethylene and α-olefin. The number of short chain branches per 1000 carbon atoms (SC
Represented as B).

(2) Intrinsic viscosity = [η]: Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer (unit: dl / g).

(3) Melt flow rate = MFR: JI
According to the method defined in SK7210-1995, 1
It is a melt flow rate value measured at a load of 21.18 N (2.16 kg) at 90 ° C. (unit: g / 10 minutes).

(4) Swell ratio = SR: Strand diameter obtained during MFR measurement is 2.095 m, which is the inner diameter of the die.
It is a value divided by m.

(5) Melt flow rate ratio = MFRR:
According to the method specified in JIS K7210-1995, 190 ° C, load 211.82N (21.60kg)
The melt flow rate value measured by
It is a value divided by the melt flow rate value (MFR) measured by N (2.16 kg). For the above melt flow rate measurement, 1000 pp of antioxidant was previously prepared.
A polymer compounded with m was used.

(6) Molecular weight and molecular weight distribution: Measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was created using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). Model: Millipore Outers 150C type column: TSK-GEL GMH-HT 7.5 × 6
00 × 2 Measuring temperature: 140 ° C Solvent: Orthodichlorobenzene, Measuring concentration: 5mg / 5ml

(7) Elemental analysis: Zn: A sample was thrown into a sulfuric acid aqueous solution (1 mol / liter), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry. F: A combustion gas generated by burning a sample in a flask filled with oxygen was absorbed in a sodium hydroxide aqueous solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

[Example 1] (1) Synthesis of contact product (e) In a 200 ml four-necked flask purged with nitrogen, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of a solution of diethylzinc in hexane (2 mol / l) were placed, and 5 Cooled to ° C. To this, a tetrahydrofuran solution of 3,4,5-trifluorophenol (2.33mo
1 / l) 34.3 ml (80 mmol) of 120
Dropped in minutes. After the dropping was completed, the mixture was further stirred at 5 ° C. for 90 minutes and then at 40 ° C. for 70 minutes. After that, the temperature was lowered to 20 ° C. in an ice bath, and 0.72 ml of H ₂ O (40 m
(mol) was added dropwise over 80 minutes. After completion of the dropping, stirring was further performed at 20 ° C. for 60 minutes and then at 40 ° C. for 120 minutes. As a result, it was divided into a transparent liquid material and a yellow gel material. After left standing overnight at room temperature, the volatile components were distilled off, and the product was dried under reduced pressure at 120 ° C. for 8 hours. As a result, 17.05 g of a yellow solid product was obtained.

(2) Synthesis of component (A) In a nitrogen-substituted 50 ml four-necked flask, 5.98 of the yellow solid products synthesized in the above Example 1 (1) were used.
g and 30 ml of tetrahydrofuran were added, and the mixture was stirred. 3.15 g of silica (Sylopol 948, manufactured by Devison Co .; average particle diameter = 61 µm; pore volume = 1.61 ml / g; specific surface area = 296 m ² / g) was heat-treated at 300 ° C under nitrogen flow. 2 at 40 ° C
Stir for hours. After removing the liquid component with a glass filter, it was washed 5 times with 30 ml of tetrahydrofuran. By drying under reduced pressure at 120 ° C. for 8 hours, 4.45 g of component (A) was obtained. Elemental analysis results, Z
It was n = 2.1 mmol / g and F = 2.4 mmol / g.

(3) Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, hydrogen was added so that the partial pressure was 0.009 MPa, and 700 parts of butane was added.
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.36 mol.
%, 1-butene = 2.67 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and subsequently, the component (A) 16 obtained in Example 1 (2) above. 0.6 mg was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.25 mol% of hydrogen so as to keep the total pressure constant.
As a result, 78 g of an olefin polymer was obtained. Polymerization activity per zirconium atom is 1.6 × 10 ⁸ g / m
Polymerization activity per solid catalyst component was 47 at olZr / hour.
It was 00 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 16.3 and MFR = 1.
99, MFRR = 50.4, SR = 1.36, Mw =
9.51 × 10 ⁴ , Mw / Mn = 8.99, [η] =
It was 1.26.

Example 2 (1) Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, and hydrogen was added so that the partial pressure thereof became 0.012 MPa. To 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.51 mol.
%, 1-butene = 2.91 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, followed by Example 1.
18.0 mg of the component (A) obtained in (2) was added as a solid catalyst component. Hydrogen was added to keep the total pressure constant.
Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of 25 mol% of ethylene and hydrogen. As a result, 75 g of an olefin polymer was obtained. Polymerization activity per zirconium atom is 1.5 × 10 ⁸ g / mo
Polymerization activity per solid catalyst component was 417 at 1 Zr / hour.
It was 0 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 17.2 and MFR = 7.0.
3, MFRR = 39.9, SR = 1.45, Mw = 6.
83 × 10 ⁴ , Mw / Mn = 7.32, [η] = 1.0
It was 4.

Example 3 (1) Synthesis of contact product (e) In a nitrogen-substituted 200 ml four-necked flask, 40 ml of tetrahydrofuran and 40 ml (80 mmol) of a hexane solution of diethylzinc (2 mol / liter) were placed, and Cooled to ° C. To this, a tetrahydrofuran solution of 3,4,5-trifluorophenol (2.33mo
1 / l) 13.7 ml (32 mmol) was added dropwise over 45 minutes. 90 minutes at 5 ° C after the dropping, and then 4
Further stirring was carried out at 0 ° C. for 70 minutes. Then 2 in an ice bath
The temperature was lowered to 0 ° C and 1.30 ml of H ₂ O (72 mm
ol) was added dropwise over 145 minutes. After completion of the dropping, stirring was further performed at 20 ° C. for 60 minutes and then at 40 ° C. for 120 minutes. As a result, it was divided into a transparent liquid material and a yellow gel material. After left standing overnight at room temperature, the volatile components were distilled off, and the product was dried under reduced pressure at 120 ° C. for 8 hours. As a result, 10.39 g of a yellow solid product was obtained.

(2) Synthesis of component (A) A nitrogen-purged 50 ml four-necked flask was charged with 3.65 of the yellow solid product synthesized in Example 3 (1) above.
g, tetrahydrofuran 30 ml, Example 1 above
3.08 g of heat-treated silica in the same lot as used in (2) was added, and the mixture was stirred at 40 ° C. for 2 hours. After removing the liquid component with a glass filter, it was washed 5 times with 30 ml of tetrahydrofuran. By drying under reduced pressure at 120 ° C. for 8 hours, 4.76 g of component (A) was obtained. As a result of elemental analysis, Zn = 3.
It was 1 mmol / g and F = 2.4 mmol / g.

(3) Polymerization After drying under reduced pressure, the inside of the autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, hydrogen was added so that the partial pressure thereof became 0.004 MPa, and butane 690 was added.
60 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.17 mol.
%, 1-butene = 2.85 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and subsequently, the component (A) 9 obtained in Example 3 (2) above. 0.8 mg was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.22 mol% of hydrogen so as to keep the total pressure constant.
As a result, 87 g of an olefin polymer was obtained. Polymerization activity per zirconium atom is 1.7 × 10 ⁸ g / m
The polymerization activity per solid catalyst component is 88 at olZr / hour.
It was 80 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 17.6 and MFR = 2.
62, MFRR = 45.4, SR = 1.36, Mw =
9.93 × 10 ⁴ , Mw / Mn = 4.53, [η] = 1.
It was 32.

Comparative Example 1 (1) A 5-liter four-necked flask purged with nitrogen was equipped with a stirrer, a dropping funnel and a thermometer. Silica heat-treated in the flask at 300 ° C. under nitrogen flow (Sylopol 948 manufactured by Devison; average particle diameter = 64 μm; pore volume = 1.62 ml / g; specific surface area =
382 g of (312 m ² / g) was collected. Toluene (3.3 liters) was added thereto to form a slurry, which was cooled to 5 ° C using an ice bath, and then the concentration of the toluene solution of trimethylaluminum was adjusted to 2.1 mmol / ml (375 m).
1 was gradually added dropwise. At that time, generation of gas was observed.
After stirring at 5 ° C for 30 minutes and at 80 ° C for 2 hours, the supernatant was removed, and the remaining solid product was washed 4 times with 3.3 liters of toluene. Then, 3.3 liters of toluene was added again to form a slurry.

(2) The slurry obtained in Comparative Example 1 (1) above was cooled to 5 ° C. in an ice bath, and then the concentration was adjusted to 2 mm.
420 ml of a toluene solution of pentafluorophenol adjusted to ol / ml was slowly added. At that time, generation of gas was observed. After stirring at 5 ° C for 30 minutes and at 80 ° C for 2 hours, the supernatant was filtered, and the remaining solid product was washed 4 times with 3.3 liters of toluene and twice with 3.3 liters of hexane. Then, the solid product was dried under reduced pressure to obtain 434 g of a fluid solid product. As a result of elemental analysis, Al = 1.2 mmol / g, F = 4.6 mmol /
It was g.

(3) Polymerization After drying under reduced pressure, the inside of the autoclave equipped with a stirrer and having an internal volume of 5 liters, which had been replaced with argon, was evacuated, hydrogen was added so that the partial pressure thereof would be 0.007 MPa, and 1145 g of butane was added. 55 g of butene was charged and the temperature was raised to 70 ° C. Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized.
As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.37 mol%, 1-butene = 1.55 m.
It was ol%. In addition to this, a solution of triisobutylaluminum in heptane adjusted to a concentration of 1 mmol / ml.
1.5 ml was added. Next, change the concentration to 2 μmol / ml
0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to 1. was charged, and subsequently 36 mg of the solid product obtained in Comparative Example 1 (2) above was charged as a solid catalyst component. While feeding a mixed gas of ethylene and hydrogen containing 0.22 mol% of hydrogen so as to keep the total pressure constant, at 70 ° C., 6
Polymerization was carried out for 0 minutes. As a result, olefin polymer 1
35 g were obtained. The polymerization activity per zirconium atom was 1.4 × 10 ⁸ g / mol Zr / hour, and the polymerization activity per solid catalyst component was 3720 g / g solid catalyst component / hour. The obtained olefin polymer has SCB =
12.4, MFR = 2.55, MFRR = 48, SR =
It was 1.35.

Example 4 (1) Prepolymerization An autoclave equipped with a stirrer having an internal volume of 0.4 liter was evacuated, then hydrogen was charged at a pressure of 0.002 MPa at room temperature, and 90 g of butane was charged as a solvent, and the autoclave was charged. Was heated to 50 ° C. Further, ethylene was added so that the partial pressure thereof would be 0.15 MPa to stabilize the system.
As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.02 mol%. To this was added 0.5 ml of a hexane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml. Next, 0.2 ml of a hexane solution of racemic-ethylenebis (1-indenyl) zirconium dichloride and triisobutylaluminum adjusted to a zirconium concentration of 150 μmol / ml and an aluminum concentration of 1.0 mmol / ml.
Then, 0.42 g of the component (A) obtained in Example 1 (2) above was charged to start polymerization. During the polymerization, a mixed gas of ethylene and hydrogen containing 0.24 mol% of hydrogen was continuously supplied while adjusting the gas phase pressure in the autoclave to maintain 0.68 MPa. 7
After 2 minutes, ethylene, butane, and hydrogen gas were purged, and the solid remaining in the autoclave was vacuum dried at room temperature for 30 minutes to prepolymerize addition polymerization in which 51 g of polyethylene was prepolymerized per 1 g of component (A). A catalyst component for use was obtained. The polyethylene has an intrinsic viscosity [η] of 1.16 dl.
/ G, MFR was 4.2 g / 10 minutes.

(2) Main Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, hydrogen was added so that its partial pressure was 0.008 MPa, and butane was added to 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.32 mol
%, 1-butene = 2.75 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.427 g of the prepolymerized addition polymerization catalyst component obtained in Example 4 (1) above was added. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.25 mol% of hydrogen so as to keep the total pressure constant. As a result, 48 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component (component (A) obtained in Example 1 (2) above) was 5750 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 17.8, MFR = 22.8 and [η] = 0.
It was 89.

[0177]

As described in detail above, according to the present invention, polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization,
Particles useful for the preparation of highly active single-site catalysts suitably used for gas phase polymerization, bulk polymerization, etc., carriers and catalyst components for addition polymerization, a method for producing the particles, and preliminarily polymerized using the particles Provided are a catalyst component for addition polymerization, a highly active catalyst for addition polymerization, and an efficient method for producing an addition polymer. Further, according to the present invention, for addition polymerization which gives an addition polymer excellent in shape and particle properties when applied to polymerization accompanied by formation of addition polymer particles (eg slurry polymerization, gas phase polymerization, bulk polymerization, etc.) Particles useful for preparing a catalyst, a carrier and a catalyst component for addition polymerization, a method for producing the particles, a prepolymerized addition polymerization catalyst component using the particles, polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization). , Gas phase polymerization, bulk polymerization, etc.), a catalyst for addition polymerization that gives an addition polymer excellent in shape and particle properties, and polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization). , Bulk polymerization, etc.), a method for producing an addition polymer excellent in shape and particle properties is also provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J015 DA02 DA03 DA10                 4J028 AA01A AB01A AC01A AC02A                       AC22A AC49A BC01B BC09B                       BC14B CA14C CA16C CB64C                       CB82C CB87C EB02 EB03

Claims (14)

[Claims] 1. Modified particles obtained by bringing the following (a), (b), (c) and particles (d) into contact with each other. (A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1] (b): Compound represented by the following general formula [2] (C): Compound R ³ _t-2 TH ₂ [3] represented by the following general formula [3] (in the above general formulas [1] to [3], M ¹ is the first, second, or periodic table, respectively). Represents a typical metal atom of group 12, 14 or 15, m represents the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when plural L ^1's are present, they are the same as each other. R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and the three R ^1's may be the same as or different from each other, and optionally 2 Two R ¹ 's may be linked together to form a condensed ring structure by connecting to adjacent positions of a benzene ring, and R ^2's represent a hydrogen atom or a hydrocarbon group.
R ³ represents a hydrocarbon group or a halogenated hydrocarbon group.
Each T independently represents a nonmetallic atom of Group 15 or Group 16 of the periodic table, and t represents the valence of T of each compound. ) 2. The modified particle according to claim 1, wherein the particle (d) is a porous substance. 3. The particles (d) have a particle size of 10 at 100 to 1500 ° C.
The modified particles according to claim 1 or 2, wherein the modified particles are an inorganic substance that has been heat-treated for about 50 minutes to 50 hours. 4. The modified particle according to claim 1, wherein the particle (d) is silica heat-treated at 200 to 800 ° C. for 1 to 30 hours. 5. A method for producing modified particles, which comprises contacting the following (a), (b), (c) and particles (d): (A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1] (b): Compound represented by the following general formula [2] (C): Compound R ³ _t-2 TH ₂ [3] represented by the following general formula [3] (in the above general formulas [1] to [3], M ¹ is the first, second, or periodic table, respectively). Represents a typical metal atom of group 12, 14 or 15, m represents the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when plural L ^1's are present, they are the same as each other. R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and the three R ^1's may be the same as or different from each other, and optionally 2 Two R ¹ 's may be linked together to form a condensed ring structure by connecting to adjacent positions of a benzene ring, and R ^2's represent a hydrogen atom or a hydrocarbon group.
R ³ represents a hydrocarbon group or a halogenated hydrocarbon group.
Each T independently represents a nonmetallic atom of Group 15 or Group 16 of the periodic table, and t represents the valence of T of each compound. ) 6. A solvent is used in contacting (a), (b), (c) and (d), the solvent is distilled off after the contact treatment, and then at a temperature of 25 ° C. or higher for 1 hour. The method for producing modified particles according to claim 5, wherein the drying is performed under reduced pressure for 24 hours. 7. A carrier comprising the modified particles according to any one of claims 1 to 4. 8. A catalyst component for addition polymerization, comprising the modified particles according to any one of claims 1 to 4. 9. Addition polymerization obtained by contacting the modified particles (A) according to any one of claims 1 to 4 with a transition metal compound (B) of Group 3 to 11 or lanthanoid series. catalyst. 10. The modified particles (A) according to any one of claims 1 to 4, a transition metal compound (B) of Groups 3 to 11 or a lanthanoid series, and an organoaluminum compound (C) are contacted. A catalyst for addition polymerization obtained by the above. 11. The addition polymerization according to claim 9 or 10, wherein the group 3 to 11 or lanthanoid series transition metal compound (B) is a transition metal compound having at least one group having a cyclopentadiene type anion skeleton. catalyst. 12. A method for producing an addition polymer using the catalyst for addition polymerization according to claim 9. 13. The method for producing an addition polymer according to claim 12, wherein the addition polymer is an olefin polymer. 14. The method for producing an addition polymer according to claim 12, wherein the addition polymer is a copolymer of ethylene and α-olefin.