JP2010174208A - Olefin polymerization catalyst, method for producing olefin polymerization catalyst, and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst capable of producing an olefin polymer excellent in molding processability, a method for producing the olefin polymerization catalyst, and a method for producing the olefin polymer using the olefin polymerization catalyst. <P>SOLUTION: The olefin polymerization catalyst is formed by bringing a component (B) into contact with a component (C) in the presence of a component (A) of an olefin. The component (B) is a transition metal compound of Group 3 to 11 or lanthanoid series. The component (C) is a component (C-1) and/or a component (C-2). The component (C-1) is a solid catalyst component formed by bringing a component (a) into contact with a component (b). The component (a) is at least one compound selected from the group consisting of (a-1) organometallic compounds of Group 13, (a-2) organic aluminum oxy compounds, and (a-3) boron compounds. The component (b) is a solid carrier. The component (C-2) is a modified clay mineral formed by bringing an organic compound into contact with a clay mineral. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an olefin polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer, and more specifically, an olefin polymerization catalyst capable of producing an olefin polymer having excellent molding processability, and the olefin polymerization. The present invention relates to a method for producing a catalyst and a method for producing an olefin polymer for polymerizing an olefin in the presence of the olefin polymerization catalyst.

Olefin polymers are widely used in various molded products because they are excellent in mechanical properties and are inexpensive.
Conventionally, as a method for producing an olefin polymer, a method using a catalyst in which a transition metal component composed of a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) and an organometallic component composed of an aluminoxane or the like is used is known. ing.
For example, Patent Document 1 discloses a method for producing a polyolefin in the presence of a solid catalyst component obtained by supporting a transition metal compound and a reaction product of trialkylaluminum and water on an inorganic oxide support. It has been.

JP 61-108610 A (published May 27, 1986)

However, the olefin polymer obtained by the production method described in Patent Document 1 has been required to be further improved in moldability.
An object of the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer having excellent moldability, a method for producing the olefin polymerization catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst.

As a result of intensive studies, the present inventors have found that the present invention can solve the above problems.
That is, the first of the present invention is an olefin polymerization catalyst formed by contacting the following component (B) with the following component (C) in the presence of the following component (A).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier Component (C-2): Organic compound Modified clay mineral formed by contacting clay mineral with water

In the second aspect of the present invention, the following component (A), the following component (B), the following component (C), and the following component (D) are contacted with each other in the presence of the following component (A). An olefin polymerization catalyst formed by contacting the component (B) with the following component (C).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier component (C-2): Organic compound Modified clay mineral component (D) formed by bringing clay into contact with clay mineral: Organoaluminum compound

  A third aspect of the present invention relates to a method for producing an olefin polymerization catalyst in which the component (B) and the component (C) are contacted in the presence of the component (A).

  The fourth aspect of the present invention is a method for producing an olefin polymerization catalyst in which the component (A), the component (B), the component (C), and the component (D) are contacted, The contact is directed to a method for producing an olefin polymerization catalyst including a step of bringing the component (B) into contact with the component (C) in the presence of the component (A).

  A fifth aspect of the present invention relates to a method for producing an olefin polymer for polymerizing an olefin in the presence of the olefin polymerization catalyst of the first invention or the second invention.

  According to the present invention, an olefin polymerization catalyst capable of producing an olefin polymer having excellent moldability and an olefin polymer having excellent moldability can be obtained.

  In the present invention, the term “polymerization” includes not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers.

1) Olefin polymerization catalyst The olefin polymerization catalyst of the present invention is formed by contacting the following component (B) with the following component (C) in the presence of the following component (A).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C-2) )
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier Component (C-2): Organic compound Modified clay mineral formed by contacting clay mineral with water

As an olefin of a component (A), a C2-C20 olefin is mentioned, for example.
Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like. These may be used alone or in combination of two or more.
Among these, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene is preferable.

  As the transition metal compound of Group 3 to Group 11 of the periodic table of the component (B) or the lanthanoid series, a transition metal compound having at least one cyclopentadienine-type anion skeleton is more preferable. , A transition metal compound of Group 4 of the periodic table of elements having at least one cyclopentadienine type anion skeleton.

Examples of the transition metal compounds of Group 3 to Group 11 of the periodic table of the component (B) or the lanthanoid series include transition metal compounds represented by the following formula [1] or μ-oxo type transition metal compounds thereof Of the dimer.
L ¹ _a M ¹ X ¹ _b [1]
(In the formula, M ¹ represents a transition metal atom of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series. L ¹ represents a group having a cyclopentadiene type anion skeleton or a group containing a hetero atom, When there are a plurality of L ^{1 s} , they may be the same as or different from each other, and the plurality of L ¹ are directly bonded to each other, or a carbon atom, silicon atom, nitrogen atom, oxygen atom, sulfur atom or X ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), a hydrocarbon oxy group, substituted silyl group, hydrocarbon thio group, a disubstituted amino group or a hydrocarbon phosphino group, if X ¹ is more, they may be different from one another identical .a 0 < Represents an integer satisfying ≦ 8, b represents an integer satisfying 0 <b ≦ 8.)

As M ^{1 in the} formula [1], for example, 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. Among these, preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, particularly preferably. Is a zirconium atom.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{1 in} the formula [1] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1-methyl-2-ethylcyclopentadienyl group, 1-methyl-3-ethylcyclopentadienyl group, 1-tert-butyl-2-methyl Cyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3-isopropylcyclopentadienyl group, 1-methyl 2-n-butylcyclopentadienyl group, 1-methyl-3-n-butylcyclopentadienyl group, 1,2, -Trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindene Nyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group, 2-tert-butyl Indenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert-butylindenyl group, 2 , 3-dimethylindenyl group, 4,7-dimethylindenyl group, 2,4,7-trimethylindenyl group, 2-methyl 4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl-4-phenyl Examples thereof include indenyl group, 2-methyl-4-naphthylindenyl group, fluorenyl group, 2,7-dimethylfluorenyl group and 2,7-di-tert-butylfluorenyl group.

The polydentate η of the group having a cyclopentadiene type anion skeleton used for L ¹ in the formula [1] is not particularly limited and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

Examples of the hetero atom in the group containing the hetero atom of L ¹ in the formula [1] include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group and an aryl group. Selected from the group consisting of oxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, oxygen atom, sulfur atom, nitrogen atom and phosphorus atom Examples thereof include an aromatic heterocyclic group or an aliphatic heterocyclic group having at least one kind in the ring, a group represented by the following formula [2], a group represented by the following formula [3], and the like.

R ¹ ₃ P = N --- [2]
(In the formula, each R ¹ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the three R ^{1 s} may be the same or different from each other, and any two of the three R ^{1 s} The above may be bonded to each other and may form a ring structure.N --- represents a bonding site with M ^1. )

（式中、Ｒ^２はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、複数のＲ²は互いに同じであっても異なっていてもよく、複数のＲ²のうち、隣接する２つの置換基は任意に結合して環を形成していてもよい。Ｏ---は、Ｍ¹との結合部位を表す。）

(In the formula, each R ² independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group, and a plurality of R ² may be different be the same as each other, among the plurality of R ^2, two adjacent substituents may be bonded to form a ring optionally .O --- is, M ¹ Represents the binding site.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
As the aryloxy group, for example, 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-methyl Phenoxy group, 2,6-di-tert-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 Aminophenoxy group, 2-hydroxyphenoxy group, 2-hydroxy-4-isopropylphenoxy group, 2-hydroxy-3-methoxyphenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group 2- (2-oxy-1-propyl) phenoxy group, 3-hydroxyphenoxy group, 8-hydroxy-1-naphthyloxy group, 2-hydroxy-1-naphthyloxy group, 2′-hydroxy-2-naphthyloxy group, 2'-hydroxy-1,1'-bi-2-naphthyloxy group, 2'-hydroxy-6,6'-dimethyl-2-biphenyloxy group, 4,4 ', 6,6'-tetra-tert- Examples include butyl-2,2′methylenediphenoxy group, 4,4 ′, 6,6′-tetramethyl-2,2′-isobutylidenediphenoxy group, and the like. It is done.
Examples of the alkylthio group include a methylthio group.
Examples of the arylthio group include a 4-aminophenylthio group.
Examples of the alkylamino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a diphenylamino group, an isopropylamino group, and a tert-butylamino group.
Examples of the arylamino group include a diphenylamino group.
Examples of the alkylphosphino group include a dimethylphosphino group.
Examples of the arylphosphino group include a diphenylphosphino group.

A chelating ligand refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, and triethylene. Examples include tetramine, porphyrin, crown ether, and cryptate.
Examples of the aromatic heterocyclic group having at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom in the ring include, for example, a pyrrolyl group, a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. And an indazolyl group.
Examples of the aliphatic heterocyclic group having at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom in the ring include a piperidino group and a pyrrolidinyl group.

When L ¹ represents a group containing a hetero atom, it is preferably a group in which the hetero atom and M ¹ are bonded, and when it contains a plurality of the hetero atoms, at least one hetero atom And a group to which M ¹ is bonded.

Examples of the halogen atom for R ¹ in the formula [2] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cycloheptyl group, cyclohexyl group, A phenyl group, 1-naphthyl group, 2-naphthyl group, benzyl group, etc. are mentioned.

Examples of the halogen atom of R ² in the formula [3] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. .

Examples of the hydrocarbon group for R ² include an alkyl group, an aralkyl group, and an aryl group, and preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or the number of carbon atoms. 6 to 20 aryl groups.

Examples of the alkyl group having 1 to 20 carbon atoms of R ² include 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, tert-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.
Examples of the alkyl group having 1 to 20 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, and a perfluoropropyl group. Perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group, perbromopropyl group and the like.

The alkyl group having 1 to 20 carbon atoms of R ² is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group or a tert-pentyl group.

Examples of the aralkyl group having 7 to 20 carbon atoms of R ² include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl Group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl Group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-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, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) ) Methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. Is mentioned.
Any of these aralkyl groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aralkyl group having 7 to 20 carbon atoms of R ² is preferably a benzyl group.

Examples of the aryl group having 6 to 20 carbon atoms of R ² 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-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert- Tylphenyl 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 Etc.
Any of these aryl groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aryl group having 6 to 20 carbon atoms of R ² is preferably a phenyl group.

The substituted silyl group of R ^{2 is} a silyl group substituted with a hydrocarbon group, and the hydrocarbon group may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.
As said hydrocarbon group, a C1-C20 alkyl group, an aryl group, etc. are mentioned, for example. 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, tert-butyl group, isobutyl group, and n-pentyl group. , An n-hexyl group, a cyclohexyl group, and the like, and an aryl group includes a phenyl group and the like.

Examples of the substituted silyl group of R ² include a 1-substituted silyl group having 1 to 20 carbon atoms, a 2-substituted silyl group having 2 to 20 carbon atoms, and a 3-substituted silyl group having 3 to 20 carbon atoms. . Examples of the monosubstituted silyl group having 1 to 20 carbon atoms include a methylsilyl group, an ethylsilyl group, and a phenylsilyl group. Examples of the disubstituted silyl group having 2 to 20 carbon atoms include a dimethylsilyl group, Examples of the trisubstituted silyl group having 3 to 20 carbon atoms include, for example, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-propylsilyl group, and the like. n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl Group, triphenylsilyl group and the like.
The substituted silyl group is preferably a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group.

Examples of the hydrocarbon oxy group for R ² include an alkoxy group, an aralkyloxy group, and an aryloxy group, and preferably an alkoxy group having 1 to 20 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms. Or an aryloxy group having 6 to 20 carbon atoms.

Examples of the alkoxy group having 1 to 20 carbon atoms of R ² include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, and n-pentyl. Examples thereof include an oxy group, a neopentyloxy group, an n-hexyloxy group, an n-octyloxy group, an n-dodecyloxy group, an n-pentadecyloxy group, and an n-eicosyloxy group.
Any of these alkoxy groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The alkoxy group for R ² is preferably a methoxy group, an ethoxy group, an isopropoxy group, or a tert-butoxy group.

Examples of the aralkyloxy group having 7 to 20 carbon atoms of R ² include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, ( 2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) ) Methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) ) Methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5- Limethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethyl) Phenyl) 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, naphthylmethoxy group, anthracenylmethoxy group, etc. Is mentioned.
Any of these aralkyloxy groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aralkyloxy group having 7 to 20 carbon atoms of R ² is preferably a benzyloxy group.

Examples of the aryloxy group having 6 to 20 carbon atoms of R ² include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2, 4 -Dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2 -Tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5 -Trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6- Limethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6 -Di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethyl Phenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl -3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenol Noxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy Group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy Group, anthracenoxy group and the like.
Any of these aryloxy groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aryloxy group having 6 to 20 carbon atoms of R ² is preferably a phenoxy group.

The disubstituted amino group of R ^{2 is} an amino group substituted with two hydrocarbon groups or an amino group substituted with two silyl groups, and the hydrocarbon group or the silyl group includes a fluorine atom, a chlorine atom A halogen atom such as bromine atom or iodine atom; an alkoxy group such as methoxy group or ethoxy group; an aryloxy group such as phenoxy group; an aralkyloxy group such as benzyloxy group; Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. Group, an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group; Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butyl. Amino group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, etc. Preferably, it is a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group or a bistrimethylsilylamino group.

Examples of the hydrocarbon thio group for R ² include an alkylthio group, an aralkylthio group, and an arylthio group, and preferably an alkylthio group having 1 to 20 carbon atoms, an aralkylthio group having 7 to 20 carbon atoms, or It is an arylthio group having 6 to 20 carbon atoms.

Examples of the alkylthio group having 1 to 20 carbon atoms of R ² include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, and an n-pentylthio group. Group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
Any of these alkylthio groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The alkylthio group having 1 to 20 carbon atoms of R ² is preferably a methylthio group, an ethylthio group, an isopropylthio group, or a tert-butylthio group.

Examples of the aralkylthio group having 7 to 20 carbon atoms of R ² include benzylthio group, (2-methylphenyl) methylthio group, (3-methylphenyl) methylthio group, (4-methylphenyl) methylthio group, (2 , 3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) Methylthio group, (3,5-dimethylphenyl) methylthio group, (2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6-trimethylphenyl) Methylthio group, (2,4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methyl Thio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2 , 3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) ) Methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group, (n-octylphenyl) methylthio group, (n-decylphenyl) methylthio group, naphthyl Examples thereof include a methylthio group and an anthracenylmethylthio group.
Any of these aralkylthio groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aralkylthio group having 7 to 20 carbon atoms of R ² is preferably a benzylthio group.

Examples of the arylthio group having 6 to 20 carbon atoms of R ² include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl -3-methylphenylthio group, 2-tert-butyl-4-methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3 , 4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-tri Tylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethylphenylthio group, 2-tert-butyl-3,5-dimethylphenylthio group, 2-tert- Butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4,5-dimethylphenylthio group, 2,6-di-tert -Butyl-4-methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl-3,4,5-trimethylphenylthio Group, 2,3,4,6-tetramethylphenylthio group, 2-tert-butyl-3,4,6-trimethylphenylthio group, 2,6-di-tert-butyl-3, 4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2-tert-butyl-3,5,6-trimethylphenylthio group, 2,6-di-tert-butyl-3, 5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec-butylphenylthio group, tert-butylphenylthio group N-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n-tetradecylphenylthio group, naphthylthio group, anthracenylthio group and the like.
Any of these arylthio groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The arylthio group having 6 to 20 carbon atoms of R ² is preferably a phenylthio group.

Examples of the hydrocarbon seleno group for R ² include an alkyl seleno group, an aralkyl seleno group, an aryl seleno group, and the like, and preferably an alkyl seleno group having 1 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. A seleno group or an arylseleno group having 6 to 20 carbon atoms.

Examples of the alkylseleno group having 1 to 20 carbon atoms of R ² include, for example, methylseleno group, ethylseleno group, n-propylseleno group, isopropylseleno group, n-butylseleno group, sec-butylseleno group, tert-butylseleno group, n -Pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like.
Any of these alkylseleno groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The alkylseleno group having 1 to 20 carbon atoms of R ² is preferably a methylseleno group, an ethylseleno group, an isopropylseleno group or a tert-butylseleno group.

Examples of the aralkylseleno group having 7 to 20 carbon atoms of R ² include benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group, ( 2,3-dimethylphenyl) methylseleno group, (2,4-dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) ) Methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) methylseleno group, (2,3,6-trimethylphenyl) ) Methylseleno group, (2,4,5-trimethylphenyl) methylseleno group, (2,4 6-trimethylphenyl) methylseleno group, (3,4,5-trimethylphenyl) methylseleno group, (2,3,4,5-tetramethylphenyl) methylseleno group, (2,3,4,6-tetramethylphenyl) Methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (N-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (n-hexylphenyl) methylseleno group, (n-octylphenyl) methylseleno group, (n-decylphenyl) ) Methylseleno group, naphthylmethyl Examples include a luseleno group and an anthracenylmethylseleno group.
Any of these aralkylseleno groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The aralkylseleno group having 7 to 20 carbon atoms of R ² is preferably a benzylseleno group.

Examples of the arylseleno group having 6 to 20 carbon atoms of R ² include phenylseleno group, 2-methylphenylseleno group, 3-methylphenylseleno group, 4-methylphenylseleno group and 2,3-dimethylphenylseleno Group, 2,4-dimethylphenylseleno group, 2,5-dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert -Butyl-3-methylphenylseleno group, 2-tert-butyl-4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2 , 3,4-trimethylphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethyl Phenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2-tert-butyl-3,4-dimethylphenylseleno group, 2-tert-butyl-3,5 -Dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenyl Seleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethylphenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl -3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenylseleno group, 2-tert-butyl-3,4,6- Trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group, 2,3,5,6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6- Trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butyl Phenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno group, n-octylphenylseleno group, n-decylphenylseleno group, n-tetradecylphenylseleno group, naphthylseleno group And anthracenyl seleno group.
Any of these arylseleno groups may be substituted with a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the oxy group include a benzyloxy group.

The arylseleno group having 6 to 20 carbon atoms of R ² is preferably a phenylseleno group.

In the formula [1], when a plurality of L ¹ are bonded via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, a cyclopentadiene anion When a group having a skeleton is bonded through the residue, a group containing a hetero atom is bonded through the residue, or a group having a cyclopentadiene anion skeleton and a hetero atom If the group containing is coupled via the residues), as preferably the residues, two of L ¹ and the atoms connecting the carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or It is a phosphorus atom and is a divalent residue having a minimum atomic number of 3 or less for bonding two L ¹ . Examples of the residue include alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group and diphenylsilylene group. And substituted silylene groups such as tetramethyldisilylene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom of X ¹ in the formula [1] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for X ¹ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group, and preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkenyl group having 3 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms of X ¹ include the same ones as exemplified in the above R ^2. it can.

Examples of the alkenyl group having 3 to 20 carbon atoms of X ¹ include an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group, and preferably an allyl group or a methallyl group. is there.

Examples of the hydrocarbon oxy group, the substituted silyl group, the hydrocarbon thio group, and the disubstituted amino group represented by X ¹ include the same groups as those exemplified above for R ² .

The hydrocarbon phosphino group X ^1, and the like triphenylphosphine group.

X ¹ is preferably a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group, and more preferably a chlorine atom, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, 2,6-di-tert -Butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxy group or benzyl group.

In the formula [1], a is an integer that satisfies 0 <a ≦ 8, b is an integer that satisfies 0 <b ≦ 8, and is appropriately selected according to the valence of M ¹ . When M ¹ is a transition metal compound of Group 4 of the periodic table of elements, a is an integer that satisfies 1 ≦ a ≦ 3, b is an integer that satisfies 1 ≦ b ≦ 3, and a + b ≦ 4 Preferably, a is 2 and b is 2.

  Examples of the compound represented by the formula [1] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, 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 , Screw (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-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopenta) Dienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium Dichloride, bis (pentameth Lucyclopentadienyl) 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-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-phenylcyclopentadienyl) tita Dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (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-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, 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, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-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-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, 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-tert-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-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (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-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (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-diamil- -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-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, 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 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-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 (tetramethylcyclopentadienyl) (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, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (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 Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (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, dimethyl Silylene (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-butyl) Rudimethylsilyl-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-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (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, dimethyl Silylene (fluorenyl) (3-tert-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) ( -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-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert- Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert- Butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride (Tert- butylamido) fluorenyl dimethylsilane titanium dichloride,

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

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3 -Propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [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, and [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, and these A compound in which “titanium” is replaced with “zirconium” or “hafnium”, “(2-phenoxy)” is “(3-phenyl-2-phenoxy)”, “(3-trimethylsilyl-2-phenoxy)” Or “(3-tert-butyldi Compound substituted with “methylsilyl-2-phenoxy)”, “dimethylsilylene” with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or "Dimethoxysilylene" compound, "Dichloride" replaced with "Difluoride", "Dibromide", "Diiodide", "Dimethyl," Diethyl "," Diisopropyl "," Diphenyl "," Dibenzyl "," Dimethoxide "," “Diethoxide”, “di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide”, or “di (pentafluorophenoxide)” as well as “trichloride” as “trifluoride” ”,“ Tribromide ”,“ Tria Iodide, Trimethyl, Triethyl, Triisopropyl, Triphenyl, Tribenzyl, Trimethoxide, Triethoxide, Tri (n-propoxide), Tri (Isopropoxide) , “Triphenoxide”, or “tri (pentafluorophenoxide)”.

  Examples of the compound represented by the formula [1] whose 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′- Methoxyoxazoline] 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) Xazoline] 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 Bromide, 2,2′-methylenebis [(4R) -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- Sopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) o Oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Ckell 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) oxa Phosphorus] 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 {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyloxazo ] 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-tert-butyl -5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-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 {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -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 Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -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-fur Nyl-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 di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-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 Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -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-benzene Dil-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 di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide, and the enantiomers of the above compounds, the asymmetric carbon configuration of one oxazoline ring of the bisoxazoline type compound is reversed. As well as “dibromide” as “difluoride”, “dichloride”, “diaiod” Id "," dimethyl "," diethyl "," diisopropyl "," diphenyl "," dibenzyl "," dimethoxide "," diethoxide "," di-n-propoxide "," diisopropoxide "," diphenoxide " Or a compound substituted with “di (pentafluorophenoxide)”.

（式中、Ｒ³はいずれも２，６−ジイソプロピルフェニル基を表し、Ｒ⁴はそれぞれ独立に水素原子またはメチル基あるいは２つのＲ⁴が互いに結合したアセナフテン基を表し、Ｘ²はそれぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基を表す。）
また、上記のニッケル化合物において、「ニッケル」を「パラジウム」、「コバルト」、「ロジウム」、または「ルテニウム」に置き換えた化合物も同様に例示することができる。 Examples of the compound represented by the formula [1] in which the transition metal atom is a nickel atom include compounds represented by the following structural formula.

(In the formula, each R ³ represents a 2,6-diisopropylphenyl group, each R ⁴ independently represents a hydrogen atom or a methyl group, or an acenaphthene group in which two R ⁴ are bonded to each other, and each X ² independently represents , Fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methoxy group, ethoxy group, or phenoxy group. )
In addition, in the above nickel compound, compounds in which “nickel” is replaced with “palladium”, “cobalt”, “rhodium”, or “ruthenium” can be exemplified as well.

  Examples of the compound represented by the formula [1] whose 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 and 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, and these Examples include compounds in which “dichloride” of the compound is replaced with “difluoride”, “dibromide”, “diaiodide”, “dimethyl”, “diethyl”, “dimethoxide”, “diethoxide”, or “diphenoxide”. .

  Examples of the [mu] -oxo type transition metal compound of the transition metal compound represented by the formula [1] include [mu] -oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], [mu] -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-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) Titanium chloride], μ-oxobis [isopro Liden (tetramethylcyclopentadienyl) (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 ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chlora And [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and "chloride" of these compounds as "fluoride" , “Bromide”, “iodide”, “methyl”, “ethyl”, “isopropyl”, “phenyl”, “benzyl”, “methoxide”, “ethoxide”, “n-propoxide”, “isopropoxide”, Mention may be made of compounds substituted with “phenoxide” or “pentafluorophenoxide”.

As transition metal compounds (B) other than the compound represented by the formula [1], [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, and [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride, as well as the “chloride” of these compounds can be referred to as “bromide”, “iodide”, “methyl”, “ethyl”, “allyl”, Mention may be made of compounds substituted with “methallyl”, “methoxide” or “ethoxide”.
In addition, in the above nickel compound, a compound in which “nickel” is replaced with “iron” or “cobalt” can be exemplified similarly.

  Examples of the compound in which the transition metal atom is a nickel atom include 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, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bi (Diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenyl) Mention may be made of phosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, and nickel phthalocyanine.

Similarly, examples of the compound whose transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, and vanadium oxytrichloride.
Examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
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.

The transition metal compound represented by the formula [1] is preferably a transition metal compound belonging to Group 4 of the periodic table in which M ¹ is an element. In this case, a is an integer that satisfies 1 ≦ a ≦ 3, b is an integer that satisfies 1 ≦ b ≦ 3, and a + b ≦ 4. The transition metal compound represented by the formula [1] is more preferably a transition metal compound represented by the following formula [4], formula [5], formula [6] or formula [7].

L ² _c M ² X ³ _d [4]
(Wherein, M ² is .L ² representing the periodic table group IV transition metal atom of the element represents a group having a cyclopentadiene type anion skeleton, if L ² is more, they are same as each other The plurality of L ² may be directly bonded to each other or bonded via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. X ³ is a hydrogen atom, a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), a hydrocarbon oxy group, a substituted silyl group, a hydrocarbon thio group, a disubstituted amino group, or Represents a hydrocarbon phosphino group, and when there are a plurality of X ^{2 s} , they may be the same or different from each other, c represents an integer satisfying 1 ≦ c ≦ 3, and d satisfies 1 ≦ d ≦ 3 Represents an integer, One represents the c + d ≦ 4.)

（式中、Ｍ³は元素の周期律表の第４族の遷移金属原子を表し、Ａ¹は元素の周期律表の第１６族の原子を表し、Ｊ¹は炭素原子またはケイ素原子を表す。Ｃｐ¹はシクロペンタジエン形アニオン骨格を有する基を表す。Ｘ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基（ただし、シクロペンタジエン形アニオン骨格を有する基を除く。）、炭化水素オキシ基、置換シリル基、炭化水素チオ基、２置換アミノ基または炭化水素ホスフィノ基を表す。Ｒ⁵はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、複数のＲ⁵のうち隣接する２つの置換基は任意に結合して環を形成していてもよい。Ｒ⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、２つのＲ⁶は互いに結合して環を形成していてもよい。）

(Wherein M ³ represents a transition metal atom of Group 4 of the periodic table of elements, A ¹ represents an atom of Group 16 of the periodic table of elements, and J ¹ represents a carbon atom or a silicon atom. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton X ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), hydrocarbon oxy Represents a group, a substituted silyl group, a hydrocarbon thio group, a 2-substituted amino group or a hydrocarbon phosphino group, wherein R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, 2 Represents a substituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group, and two adjacent substituents out of a plurality of R ⁵ may be optionally combined to form a ring, each R ⁶ being independently Hydrogen atom, Represents a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group or a hydrocarbon seleno group, and two R ^{6 s} may be bonded to each other to form a ring. .)

（式中、Ｎ・・・・・Ｍ⁴は一般的には配位していることを示すが、配位していてもしていなくてもよい。Ｍ⁴は元素の周期律表の第４族の遷移金属原子を表し、ｅは、１≦ｅ≦３を満たす整数を表し、Ｒ⁷は、下記式［６−１］または［６−２］で表され、Ｒ⁸はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、複数のＲ⁸のうち隣接する２つの置換基は任意に結合して環を形成していてもよい。また、ｅが２以上の場合にはＲ⁸で表される基のうち２個の基が結合されていてもよい（但し、Ｒ⁷同士が結合されることはない）。ｆは、１≦ｅ≦３を満たす整数を表し、かつ、ｅ＋ｆ≦４を表す。Ｘ⁵は、水素原子、ハロゲン原子、炭化水素基（ただし、シクロペンタジエン形アニオン骨格を有する基を除く。）、炭化水素オキシ基、置換シリル基、炭化水素チオ基、２置換アミノ基または炭化水素ホスフィノ基を表す。ｆが複数ある場合は、それらは互いに同じであっても異なってもよい。）

(Where N... M ⁴ is generally coordinated, but may or may not be coordinated. M ⁴ is the ^fourth element in the periodic table of elements. A transition metal atom of the group, e represents an integer satisfying 1 ≦ e ≦ 3, R ⁷ is represented by the following formula [6-1] or [6-2], and R ⁸ is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, disubstituted amino group, a hydrocarbon thio group or a hydrocarbon seleno group, two substituents adjacent among the plurality of R ⁸ is optionally In the case where e is 2 or more, two groups represented by R ⁸ may be bonded to each other (provided that R ⁷ is bonded to each other). F is an integer satisfying 1 ≦ e ≦ 3 and e + f ≦ 4 X ⁵ is a hydrogen atom, halogen atom, carbon A hydrogen fluoride group (excluding a group having a cyclopentadiene type anion skeleton), a hydrocarbon oxy group, a substituted silyl group, a hydrocarbon thio group, a disubstituted amino group, or a hydrocarbon phosphino group. May be the same or different from each other.)

(Wherein R ⁹ represents a hydrogen atom, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and R ¹⁰ each independently represents a hydrogen atom or a methyl group.)

(Wherein either the dashed line two C ^alpha binds directly, the number 1 or more hydrocarbon group having a carbon indicates that which is bound to two C ^alpha.)

（式中、Ｍ^５は、元素の周期律表の第４族の遷移金属原子を表し、Ｃｐ^２はシクロペンタジエン形アニオン骨格を有する基を表し、Ｊ^２は炭素原子またはケイ素原子を表し、Ｘ⁶は水素原子、ハロゲン原子、炭化水素基（ただし、シクロペンタジエン形アニオン骨格を有する基を除く。）、炭化水素オキシ基、置換シリル基、炭化水素チオ基、２置換アミノ基または炭化水素ホスフィノ基を表し、ｈは１または２を表し、ｈが２を表す場合は、２つのＸ⁶は互いに同じであっても異なっていてもよく、Ｒ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、２つのＲ¹¹は任意に結合して環を形成していてもよい。ｇは１または２を表す。Ｒ¹²は、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表を表す。）

(Wherein M ⁵ represents a transition metal atom of Group 4 of the periodic table of elements, Cp ² represents a group having a cyclopentadiene-type anion skeleton, J ² represents a carbon atom or a silicon atom, and X ⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), a hydrocarbon oxy group, a substituted silyl group, a hydrocarbon thio group, a disubstituted amino group, or a hydrocarbon phosphino group. H represents 1 or 2, and when h represents 2, the two X ^{6 s} may be the same or different from each other, and each R ¹¹ independently represents a hydrogen atom, a halogen atom, a carbon atom, Represents a hydrogen group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group or a hydrocarbon seleno group, and two R ¹¹ may be optionally bonded to form a ring. 1 or 2 R ¹² represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group.)

Examples of the group 4 transition metal atom in the periodic table of the M ² element of the formula [4] include a titanium atom, a zirconium atom, and a hafnium atom, and a zirconium atom is preferable.
Examples of the group having a cyclopentadiene-type anion skeleton of L ² include the same groups as those exemplified as the group having a cyclopentadiene-type anion skeleton of L ^{1 in} the above formula [1].
Halogen atoms X ^3, a hydrocarbon group, a hydrocarbon oxy group, a substituted silyl group, hydrocarbon thio group and the 2-substituted amino group and a hydrocarbon phosphino group, the same as those exemplified as X ¹ in the formula [1] Things can be mentioned.
c and d are preferably 2.

Among the transition metal compounds represented by the above formula [4], M ² is a zirconium atom, c is 2, d is 2, and a group having two cyclopentadiene-type anion skeletons is a carbon atom, silicon Zirconium compounds bonded through a residue containing an atom, oxygen atom, sulfur atom or phosphorus atom are preferred.

Examples of the group 4 transition metal atom in the periodic table of the element M ³ in the formula [5] include a titanium atom, a zirconium atom, and a hafnium atom, and a titanium atom or a zirconium atom is preferable.
Examples of A ¹ include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.
Halogen atoms X ^4, a hydrocarbon group, a hydrocarbon oxy group, a substituted silyl group, hydrocarbon thio group and the 2-substituted amino group and a hydrocarbon phosphino group, the same as those exemplified as X ¹ in the formula [1] Things can be mentioned.

Examples of the group having a Cp ¹ cyclopentadiene anion skeleton in the formula [5] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl Enyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, tert-butyl Dimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, n-propylindenyl group, isopropylindenyl group, n-butylindenyl group, tert-butylindenyl , Phenylindenyl group, methylphenylindenyl group, naphthylindenyl group, trimethylsilylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl group, tert-butylfluorenyl group, Examples thereof include di-tert-butylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, trimethylsilylfluorenyl group, bistrimethylsilylfluorenyl group, and preferably cyclopentadienyl group, methylcyclo A pentadienyl group, an n-butylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, or a fluorenyl group.

The polydentate η of the group having a cyclopentadiene type anion skeleton of Cp ¹ in the formula [5] is not particularly limited, and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

As the halogen atom, hydrocarbon group, substituted silyl group, hydrocarbon oxy group, disubstituted amino group, hydrocarbon thio group and hydrocarbon seleno group of R ⁵ and R ⁶ in the formula [5], the above formula [3] The same thing as illustrated as R < ² > can be mentioned.

R ^{5 is} preferably a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

R ⁶ is preferably a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

Examples of the group 4 transition metal atom in the periodic table of the element M ⁴ in the formula [6] include a titanium atom, a zirconium atom, and a hafnium atom, and a titanium atom or a zirconium atom is preferable.

Examples of the aliphatic hydrocarbon group represented by the above formula [6-1] or [6-2] of R ^{7 in} the formula [6] include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, tert-amyl, 1,2-dimethylpropyl group, isoamyl group, 1-methylbutyl group, 2-methylbutyl group, neopentyl group, n-hexyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 1-methylheptyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n- Xadecyl group, n-heptadecyl group, n-octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, adamantyl group, Examples include a methylenecyclopropyl group, a methylenecyclobutyl group, a methylenecyclopentyl group, a methylenecyclohexyl group, and a 1-cyclohexylethyl group, preferably a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, and an n-octadecyl group. Group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 4-tert-butylcyclohexyl group, methylenecyclohexyl group, isopropyl group, 1-methylhexyl group or 1,5-dimethylhexyl group.

As the halogen atom, hydrocarbon group, substituted silyl group, hydrocarbon oxy group, disubstituted amino group, hydrocarbon thio group and hydrocarbon seleno group of R ⁸ in the formula [6], as R ^{2 in the} above formula [3] The same thing as what was illustrated can be mentioned.

  e is preferably 1 or 2.

As the halogen atom, hydrocarbon group, hydrocarbon oxy group, substituted silyl group, hydrocarbon thio group, disubstituted amino group and hydrocarbon phosphino group of X ⁵ in formula [6], X ^{1 in the} above formula [1] The same thing as what was illustrated can be mentioned.

Examples of the group 4 transition metal atom in the periodic table of the element M ⁵ in the formula [7] include a titanium atom, a zirconium atom, and a hafnium atom, and a titanium atom or a zirconium atom is preferable.

Examples of the group having a Cp ² cyclopentadiene anion skeleton in the formula [7] include the same groups as those exemplified as the group having a Cp ¹ cyclopentadiene anion skeleton in the formula [5].

In the formula [7], the halogen atom, hydrocarbon group, substituted silyl group, hydrocarbon oxy group, disubstituted amino group, hydrocarbon thio group and hydrocarbon seleno group of R ¹¹ and R ¹² are those represented by the above formula [3]. The same thing as what was illustrated as R < ² > can be mentioned.

As the halogen atom, hydrocarbon group, hydrocarbon oxy group, substituted silyl group, hydrocarbon thio group, disubstituted amino group and hydrocarbon phosphino group of X ⁶ in the formula [7], as X ^{1 in the} above formula [1] The same thing as what was illustrated can be mentioned.

  The transition metal compounds represented by the formula [1] are disclosed in JP-A-6-340684, JP-A-7-258321, JP-A-9-87313, JP-A-11-315109, JP-A-07-070223. It is possible to manufacture by the manufacturing method as described in Gazette No., International Patent Publication No. 95/00562, and EP 08744005A1.

  The component (C) is the component (C-1) and / or the component (C-2).

  Component (C-1) is a solid catalyst component formed by bringing the component (a) into contact with the component (b).

  The organometallic compound belonging to Group 13 of the periodic table of the elements (a-1) used in component (a) is preferably an organoaluminum compound. Examples of organoaluminum compounds include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride, alkyl (dialkoxy) aluminum, dialkyl (alkoxy) aluminum, alkyl (diaryloxy) aluminum, and dialkyl (aryloxy) aluminum. Etc.

  Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

  Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride.

  Examples of the alkyl aluminum dichloride include methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride, and the like.

  Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

  Examples of the alkyl (dialkoxy) aluminum include methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and methyl (di-tert-butoxy) aluminum.

  Examples of the dialkyl (alkoxy) aluminum include dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, methyl (tert-butoxy) aluminum, and the like.

  Examples of the alkyl (diaryloxy) aluminum include methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, and methyl bis (2,6-diphenylphenoxy) aluminum.

Examples of the dialkyl (aryloxy) aluminum include dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

  The organoaluminum compound is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum. More preferred is triisobutylaluminum or tri-n-octylaluminum.

  Examples of the organoaluminum oxy compound of the component (a-2) used for the component (a) include a cyclic aluminoxane represented by the following formula [8], a linear aluminoxane represented by the following formula [9], and the like. Is mentioned.

{—Al (R ¹³ ) —O—} _i [8]
(In the formula, R ¹³ represents a hydrocarbon group, and a plurality of R ¹³ may be the same as or different from each other. I represents an integer of 2 or more.)

R ¹⁴ {—Al (R ¹⁴ ) —O—} _j AlR ¹⁴ ₂ [9]
(Wherein R ¹⁴ represents a hydrocarbon group, and a plurality of R ¹⁴ may be the same or different from each other. J represents an integer of 1 or more.)

The hydrocarbon group represented by R ¹³ in formula [8] and R ^{14 in} formula [9] is preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. It is. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, and a neopentyl group. , Methyl group or isobutyl group.

  I in Formula [8] is preferably an integer of 2 to 40, and j in Formula [9] is preferably an integer of 1 to 40.

  The cyclic aluminoxane represented by the formula [8] and the linear aluminoxane represented by the formula [9] can be produced by various methods. Their production methods are not particularly limited, and may be known production methods. As a production method, a method in which a solution obtained by dissolving a trialkylaluminum such as trimethylaluminum in an appropriate organic solvent such as benzene and an aliphatic hydrocarbon is brought into contact with water, a trialkylaluminum such as trimethylaluminum is produced. An example is a method of producing by contacting with a metal salt containing water of crystallization such as copper sulfate hydrate. These organoaluminum oxy compounds may be used alone or in combination of two or more. Preferred are organoaluminum oxy compounds prepared from trimethylaluminum or triisobutylaluminum.

As the component (a-3) boron compound used for the component (a), (c-1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (c-2) a general formula G ⁺ (BQ ¹ A boron compound represented by Q ² Q ³ Q ⁴ ) ⁻ , (c-3) one selected from boron compounds represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ The above boron compound is used.

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

  Specific examples of the compound (c-1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl). Examples include borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and most preferably tris ( Pentafluorophenyl) borane.

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

Specific examples of G ⁺ which is an inorganic cation in the compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation, etc. However, examples of G ⁺ that is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.

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

In the boron compound (c-3) represented by the general formula (L—H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L is a neutral Lewis base, and (L—H) ⁺ is a Bronsted acid, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (c-1).

Specific examples of (LH) ⁺ which is a Bronsted acid in the compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include trialkyl-substituted ammonium, N, N - dialkylanilinium, dialkylammonium and triarylphosphonium ^{mentioned, (BQ 1 Q 2 Q 3} Q 4) - as include the same as described above.

  Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ) Ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2 , 4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate.

  Component (a) is preferably an organoaluminum oxy compound of component (a-2).

  The solid carrier used for the component (b) is an inorganic or organic compound and is a granular or fine particle solid. Each of the above components is supported on a solid carrier as described below. Yes.

  Among these, examples of the inorganic compound include porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds. Preferably, the following porous oxides and inorganic chlorides can be used. .

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Can be used. Of these, those containing SiO ₂ as the main component are preferred.

Note that the inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 0.2 to 300 μm, preferably 1 to 200 μm, and a specific surface area of 50. ~1200m ² / g, preferably in the range of 100~1000m ² / g, it is desirable that the pore volume is in the range of 0.3~30cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvents, such as alcohol, what was made to precipitate in the shape of a fine particle with a depositing agent can also be used.
The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂・ H ₂ O, α-Sn (HPO ₄ ) ₂・ H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of 20 cc or more with a radius of 20 cc or more as measured by a mercury intrusion method, and particularly preferably 0.3 to 5 cc / g. Here, the pore volume is measured in a pore radius range of 20 to 3 × 10 4 by a mercury intrusion method using a mercury porosimeter.

  When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such a bulky ion plays a role of a pillar supporting the layered structure, and is usually called a pillar. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Etc. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, etc. can also coexist. Examples of the pillar include oxides produced by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after water is newly added and adsorbed, or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene are mainly used. The (co) polymer produced | generated as a component, and those modifications can be illustrated.

  The contact between the component (a) and the component (b) is chemically combined by the reaction between the reaction site in the component (a) and the reaction site in the component (b), and the contact between the component (a) and the component (b). Things are formed. The contact time between component (a) and component (b) is usually 20 hours or less, preferably 10 hours or less, and the contact temperature is usually -50 to 200 ° C, preferably -20 to 120 ° C. If the initial contact between the component (a) and the component (b) is abruptly performed, the component (b) collapses due to the reaction heat generation or reaction energy, and the morphology of the resulting solid catalyst component deteriorates. When used, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between component (a) and component (b), it is preferable to contact at a low temperature or to react slowly for the purpose of suppressing reaction heat generation. The molar ratio of contact between component (a) and component (b) (component (a) / component (b)) can be arbitrarily selected, but the higher the molar ratio, the greater the contact amount of component (B). The activity per solid catalyst component can be improved, which is preferable.

  As a preferred range, the molar ratio of component (a) to component (b) [= molar amount of component (a) / molar amount of component (b)] is usually 0.2 to 2.0, particularly preferably 0.4 to 2.0. .

  The component (C-1) is preferably a solid catalyst component formed by bringing an organoaluminum oxy compound and silica into contact with each other, more preferably a cyclic aluminoxane represented by the above formula [8] or the above It is a solid catalyst component formed by contacting linear aluminoxane represented by the formula [9] and silica.

  Component (C-2) is a modified clay mineral formed by bringing an organic compound and a clay mineral into contact with each other. As a clay mineral, the same thing as what was illustrated as a clay mineral of the said component (b) can be mentioned.

  As an organic compound used by a component (C-2), the compound represented by following formula [10], following formula [11], or following formula [12] is mentioned, for example. Among these, a compound represented by the following general formula [10] is preferable.

[R ²⁰ R ²¹ _x-1 M ⁶ H] _m1 [A ² ] _n1 [10]
(Wherein [A ² ] represents an anion, [R ²⁰ R ²¹ _x-1 M ⁶ H] represents a cation, M ⁶ represents an atom of Group 15 or Group 16 of the periodic table of elements, R ²⁰ represents a hydrocarbon group, R ²¹ each independently represents a hydrogen atom or a hydrocarbon group, x represents 3 when M ⁶ is a Group 15 element, and M ⁶ represents a Group 16 element. In this case, it represents 2. m1 and n1 represent integers selected so that charges are balanced.)
[C] _m2 [A ³ ] _n2 [11]
(In the formula, [A ³ ] represents an anion, and [C] represents a carbonium cation or a tropylium cation. M2 and n2 represent an integer selected so that charges are balanced.)
[M ⁷ L ³ _y ] _m3 [A ⁴ ] _n3 [12]
(Wherein [A ⁴ ] represents an anion, M ⁷ represents a cation of a lithium atom, an iron atom or a silver atom, and L ³ each independently represents a Lewis base or a substituted or unsubstituted cyclopentadienyl group. Y represents 0 ≦ y ≦ 2, and m3 and n3 represent integers selected so that charges are balanced.)

Examples of the anions of A ^{2 to} A ⁴ include fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, and succinate ion. Tetrafluoroborate ion hexafluorophosphate ion and the like.

Examples of the atom in Group 15 of the periodic table of M ⁶ include a nitrogen atom and a phosphorus atom. Examples of the atom in Group 16 of the periodic table of the element M ⁶ include an oxygen atom and a sulfur atom.

The hydrocarbon group for R ²⁰ and R ²¹ of M ⁶ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4 -Methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, 2-methylcyclohexyl group, -Methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert-octyl group, 2,3-dimethylcyclohexyl group 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, n-tridecyl group, n-tetradecyl group Group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, oleyl group, Behenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl 3-ethylphenyl group, 4-ethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-tert-butylphenyl group, 4-n-butylphenyl group, 4-sec -Butylphenyl group, 4-tert-butylphenyl 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, 2,6-diethylphenyl group, 2-isopropyl-6-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2,3-dihydroindene-5 -Yl group, 2-biphenyl group, 4-biphenyl group, p-trimethylsilylphenyl group and the like. R ²⁰ and R ²¹ may be bonded to each other.

Of the compounds represented by the formula [10], when M ⁶ represents a nitrogen atom, for example, methylamine hydrochloride, ethylamine hydrochloride, n-propylamine hydrochloride, isopropylamine hydrochloride, n-butylamine hydrochloride , Isobutylamine hydrochloride, tert-butylamine hydrochloride, n-pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tert-pentylamine hydrochloride, n-hexylamine hydrochloride Salt, isohexylamine hydrochloride, n-heptylamine hydrochloride, n-octylamine hydrochloride, n-nonylamine hydrochloride, n-decylamine hydrochloride, n-undecylamine hydrochloride, n-dodecylamine hydrochloride, n -Tetradecylamine hydrochloride, n-hexadecylamine hydrochloride, n-octadecyl amine Mine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2- Aminoheptane hydrochloride, 3-aminoheptane hydrochloride, n-heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, n-octylamine hydrochloride, tert-octylamine hydrochloride , Nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, heptadecylamine hydrochloride, Octadecylamine salt Salt, nonadecylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride , Cyclododecylamine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride Salt, didecylamine hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tert-butylcyclohexylamine hydrochloride, N-allyl Hexylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyl-n-tetradecylamine hydrochloride, N, N-dimethyl-n-hexadecylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride, N, N-dimethyl-n-eicosylamine hydrochloride, N, N-dimethyl-n-docosylamine Hydrochloride, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecyl Amine hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylcyclo Hexylamine hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3-methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2, 2,6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2,2,6,6- Hydrochloric acid hydrochlorides such as pentamethylpiperidine hydrochloride, aniline hydrochloride, N-methylaniline Acid salt, N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N-methyl-o- Toluidine hydrochloride, N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-ethyl-m-toluidine hydrochloride, N-ethyl-p- Toluidine hydrochloride, N-allyl-o-toluidine hydrochloride, N-allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N-propyl-o-toluidine hydrochloride, N-propyl-m- Toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5-dimethylaniline hydrochloride 2,6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4-ethylaniline hydrochloride, N, N-diethylaniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tert-butylaniline hydrochloride, 4-n-butylaniline hydrochloride, 4-sec-butylaniline hydrochloride, 4- tert-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline hydrochloride, 2- Bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o-anisidine hydrochloride, m-a Nisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphthalene hydrochloride, 1-aminofluorene hydrochloride, 2 -Aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoindane hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N, 2,3-trimethylaniline hydrochloride Salt, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethylaniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3 5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N-methyl-3-ethylaniline hydrochloride, N Methyl-4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4-isopropylaniline hydrochloride, N-methyl-2 -Tert-butylaniline hydrochloride, N-methyl-4-n-butylaniline hydrochloride, N-methyl-4-sec-butylaniline hydrochloride, N-methyl-4-tert-butylaniline hydrochloride, N-methyl -2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylaniline hydrochloride, N-methyl-p-anisidine hydrochloride, N-ethyl-2,3-anisidine hydrochloride, N, N -Dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-teto Methylaniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride, N, N, 2,5-tetramethylaniline hydrochloride, N, N, 2,6-tetramethylaniline hydrochloride, N, N , 3,4-tetramethylaniline hydrochloride, N, N, 3,5-tetramethylaniline hydrochloride, N, N-dimethyl-2-ethylaniline hydrochloride, N, N-dimethyl-3-ethylaniline hydrochloride N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride, N, N-dimethyl-2-isopropylaniline hydrochloride, N, N-dimethyl-4 -Isopropylaniline hydrochloride, N, N-dimethyl-2-tert-butylaniline hydrochloride, N, N-dimethyl-4-n-butylaniline hydrochloride, N, N-dimethyl-4-sec-butyla Niline hydrochloride, N, N-dimethyl-4-tert-butylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride, N, N-dimethyl-2-isopropyl-6-methylaniline hydrochloride N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N-dimethyl-2-bromoaniline Hydrochloride, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoaniline hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N-dimethyl-m-anisidine Hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride, N, N-dimethyl-m-phenetidine hydrochloride, N, N-dimethyl- -Phenethidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl- 2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5-aminoindane hydrochloride, N, N- Hydrochlorides of aromatic amines such as dimethyl-2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl-p-trimethylsilylaniline hydrochloride, and hydrochlorides of the above compounds are used. Examples thereof include compounds substituted with hydrohalide, hydrobromide, hydroiodide or sulfate.

Among the compounds represented by the formula [10], when M ⁶ represents a phosphorus atom, for example, triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, tri (p-tolyl) phosphine hydrochloride, Examples thereof include compounds such as trimesitylphosphine hydrochloride, and compounds obtained by substituting hydrochloride of the above compound with hydrofluoride, hydrobromide, hydroiodide or sulfate.

Of the compounds represented by the formula [10], when M ⁶ represents an oxygen atom, for example, methyl ether hydrochloride, ethyl ether hydrochloride, n-butyl ether hydrochloride, tetrahydrofuran hydrochloride, phenyl ether hydrochloride, etc. Examples thereof include compounds in which the hydrochloride of the compound and the above compound is substituted with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

Of the compounds represented by the formula [10], when M ⁶ represents a sulfur atom, for example, diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, dimethyl chloride Examples include sulfonium, dimethylsulfonium bromide, and dimethylsulfonium iodide.

  Examples of the compound represented by the above formula [11] include trityl bromide, trityl chloride, trityl tetrafluoroborate, trityl hexafluorophosphate, tropylium bromide, tropylium chloride, tropylium tetrafluoroborate, hexafluoroline. Examples include tropylium acid.

Examples of the L ³ Lewis base include ethers, aliphatic amines, aromatic amines, and phosphines.

  Examples of the compound represented by the formula [12] include ferrocenium bromide, ferrocenium chloride, ferrocenium tetrafluoroborate, and ferrocenium hexafluorophosphate.

  In the contact between the organic compound and the clay mineral in the component (C-2), it is preferable to perform the contact by selecting the conditions of the clay mineral concentration of 0.1 to 30% by weight and the contact temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay mineral and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay mineral. Examples of the contact solvent include aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, halogenated hydrocarbons, ketones, water, and the like. Examples of the aliphatic hydrocarbons include pentane, hexane, heptane and the like. Examples of aromatic hydrocarbons include benzene and toluene. Examples of alcohols include ethyl alcohol and methyl alcohol. Examples of ethers include ethyl ether, n-butyl ether, tetrahydrofuran, 1,4-dioxane and the like. Examples of halogenated hydrocarbons include methylene chloride and chloroform. Examples of ketones include acetone. These contact solvents may be used alone or in combination of two or more. Among these contact solvents, alcohols or water are preferable.

  Component (C) is preferably a solid catalyst component formed by contacting an organoaluminum oxy compound and silica or a modified clay mineral formed by contacting an organic compound and clay mineral, more preferably A solid catalyst component formed by bringing an organoaluminum oxy compound and silica into contact with each other, or a compound represented by the above formula [10], the above formula [11] or the above formula [12] with a clay mineral. It is a modified clay mineral formed, more preferably a solid catalyst component formed by contacting an organoaluminum oxy compound and silica, and particularly preferably a cyclic aluminoxane represented by the above formula [8] Alternatively, it is a solid catalyst component formed by bringing linear aluminoxane represented by the above formula [9] into contact with silica.

The amount of component (B) used is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, more preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol, relative to 1 g of component (C). mol.

  The olefin polymerization catalyst of the present invention is formed by contacting the component (B) with the component (C) in the presence of the component (A). In the presence of the component (A), the component (B) The contact with the component (C) means that the component (B) and the component (C) are not contacted in advance in the absence of the component (A).

Specific examples of the contact method of component (A), component (B) and component (C) include the following contact methods.
(1) A contact method in which a contact product between the component (A) and the component (C) is brought into contact with the component (B).
(2) A contact method in which a contact product between the component (A) and the component (B) is brought into contact with the component (C).
(3) A contact method in which a contact product between the component (A) and the component (B) is brought into contact with a contact product between the component (A) and the component (C).

Further, the olefin polymerization catalyst of the present invention is in the presence of the component (A) in the contact of the component (A), the component (B), the component (C), and the component (D) below. It is formed by bringing the component (B) and the component (C) into contact with each other.
Component (D): Organoaluminum compound

  Examples of the organoaluminum compound of component (D) include the same compounds as those exemplified as the organoaluminum compound of component (a-1).

  The amount of component (D) used is 0.01 to 10,000 as the molar ratio (D) / (B) of the aluminum atom of the component (D) organoaluminum compound to the transition metal atom of the component (B) transition metal compound. Is more preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  In the presence of the component (A), the contact between the component (B) and the component (C) means that the component (B) and the component (C) are not contacted in the absence of the component (A). Means.

  In the contact of the component (A), the component (B), the component (C) and the component (D), the contact order of the component (D) is arbitrary, and the component (D) is changed to the component (A), the component (B) or Each of the components (C) may be contacted in advance, the contact product of the components (A) and (B) and the component (D) may be contacted, and the components (A) and (C) The contact product between the component (D) and the component (D) may be contacted, or the contact product between the component (A), the component (B), and the component (C) may be contacted with the component (D).

Specifically, the following contact methods can be exemplified.
(1) A contact method in which a contact product between the component (A) and the component (B) is brought into contact with the component (C) and further brought into contact with the component (D).
(2) A contact method in which a contact product between the component (A) and the component (B) is brought into contact with the component (D) and further brought into contact with the component (C).
(3) A contact method in which the contact product between the component (A) and the component (C) is brought into contact with the component (B), and the component (D) is further brought into contact.
(4) A contact method in which the contact product between the component (A) and the component (C) is brought into contact with the component (D), and the component (B) is further brought into contact.
(5) A contact method in which a contact product between the component (A) and the component (D) is brought into contact with the component (B), and the component (C) is further brought into contact.
(6) A contact method in which the contact product between the component (A) and the component (D) is brought into contact with the component (C), and the component (B) is further brought into contact.
(7) A contact method in which a contact product between component (B) and component (D) is brought into contact with component (A) and further brought into contact with component (B).
(8) A contact method in which a contact product between the component (C) and the component (D) is brought into contact with the component (A) and further brought into contact with the component (B).
Of these contact methods, the contact method (5) or (6) is preferred.

  Moreover, when manufacturing the olefin polymerization catalyst of this invention, you may use an electron-donating compound (component (E)). As such an electron-donating compound, a compound containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom is preferable, and examples thereof include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound and a sulfur-containing compound. Compounds or nitrogen-containing compounds are preferred. Examples of the oxygen-containing compound include alkoxy silicons, ethers, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, acid amides of organic acids or inorganic acids, acid anhydrides, and the like. Of these, alkoxysilicones or ethers are preferable. Examples of the nitrogen-containing compound include amines, nitriles, isocyanates, and the like, and amines are preferable.

The alkoxysilicones are preferably alkoxysilicon compounds represented by the following formula [13].
R ²² _k Si (OR ²³ ) _4-k [13]
(In the formula, R ²² represents a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom-containing substituent, R ²³ represents a hydrocarbon group having 1 to 20 carbon atoms, and k is 0 ≦ k. If .R ²² represents an integer that satisfies ≦ 3 there is more than one, if a plurality of R ²² have a plurality of good .OR ²³ be the same or different and a plurality of OR ²³ is the same May be different.)

Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ²² and R ²³ include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, an isopropyl group, and a sec-butyl group. Branched alkyl groups such as tert-butyl group and tert-amyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, aryl groups such as phenyl group and tolyl group, etc. It is done.
Examples of the hetero atom of the hetero atom-containing substituent of R ²² include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, perhydro Examples thereof include an isoindolyl group, a perhydroquinolyl group, a perhydroisoquinolyl group, a perhydrocarbazolyl group, a perhydroacridinyl group, a furyl group, a pyranyl group, a perhydrofuryl group, and a thienyl group. Preferably, R ²² and R ²³ are alkyl groups, more preferably R ²² and R ²³ are alkyl groups, and i is 2 or 3.

  Specific examples of the alkoxy silicons include tetramethoxy silane, methyl trimethoxy silane, ethyl trimethoxy silane, normal propyl trimethoxy silane, isopropyl trimethoxy silane, normal butyl trimethoxy silane, isobutyl trimethoxy silane, sec-butyl tri Methoxysilane, tert-butyltrimethoxysilane, normal pentyltrimethoxysilane, tert-amyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dinormalbutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, methyl Ethyl dimethoxy silane, methyl normal propyl dimethoxy silane, methyl normal butyl dimethoxy silane, methyl isobutyl Methoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylnormalpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylnormalbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-amyl Methyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amylnormalpropyldimethoxysilane, tert-amylnormalbutyldimethoxysilane, isobutylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylmethyldimethoxysilane, cyclobutylethyldimethoxysilane, Cyclobutylisopropyldimethoxysilane, cyclobutylnor Rubutyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylnormalpropyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylnormalbutyldimethoxysilane, cyclopentylisobutyldimethoxysilane , Cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylnormalpropyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylnormalbutyldimethoxysilane, silane Cyclohexyl isobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylnormalpropyldimethoxysilane, phenylisopropyldimethoxysilane, phenyl Normal butyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (Perhydroquinolino) Hydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane, Hydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxysilane, (perhydroisoquinolino) (tert- Butyl) dimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trinormalpropylmethoxysilane, triisopropylmethoxysilane, trinormalbutylmethoxysilane, triisobutylmethoxysilane, tri-t rt- butyl methoxysilane, and the like. Examples thereof also include compounds in which methoxy in these compounds is replaced with ethoxy, propoxy, normal butoxy, isobutoxy, tert-butoxy, or phenoxy. Dialkyl dialkoxysilane or trialkyl monoalkoxysilane is preferable, and trialkylmonoalkoxysilane is more preferable.

  Examples of ethers include dialkyl ethers, alkylaryl ethers, diaryl ethers, diether compounds, cyclic ethers and cyclic diethers.

  Specific examples include dimethyl ether, diethyl ether, dinormal propyl ether, diisopropyl ether, dinormal butyl ether, diisobutyl ether, di-tert-butyl ether, dicyclohexyl ether, diphenyl ether, methyl ethyl ether, methyl normal propyl ether, methyl isopropyl ether, methyl. Normal butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl cyclohexyl ether, methyl phenyl ether, ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1, 2-diethoxyethane, 1,2-diisobutoxyethane, , 2-dimethoxypropane, 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2, 2-dipropyl-1,3-dimethoxypropane, 2-isopropyl 2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1 , 3-dimethoxypropane, 1,2-dimethoxybenzene, 1.3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,3-dioxolane, 1,4-dioxane, 1,3-dioxane, and the like. it can. Preferred are diethyl ether, dinormal butyl ether, methyl normal butyl ether, methyl phenyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, and more preferred are diethyl ether and dinormal butyl ether. Or tetrahydrofuran.

  Specific examples of the carboxylic acid esters include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatics. Carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, normal butyl acetate, isobutyl acetate, tert-butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, Methyl benzoate, ethyl benzoate, normal butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, dimethyl succinate, diethyl succinate, succinic acid Dinormal butyl, dimethyl malonate, diethyl malonate, dinormal butyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dinormal butyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, phthalate Diethyl propyl, dinormal phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, diphthalate Normal octyl, di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dimethyl isophthalate, diethyl isophthalate, dinormal butyl isophthalate, diisobutyl isophthalate, di-tert-butyl isophthalate, Examples thereof include dimethyl terephthalate, diethyl terephthalate, di-normal butyl terephthalate, diisobutyl terephthalate, and di-tert-butyl terephthalate. Preferred is methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, di-normal butyl phthalate, diisobutyl phthalate, dimethyl terephthalate or diethyl terephthalate, more preferably benzoic acid Methyl, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate or dimethyl terephthalate.

  Examples of amines include trihydrocarbylamine, and examples include trimethylamine, triethylamine, tripropylamine, trinormalbutylamine, triisobutylamine, trihexylamine, trioctylamine, tridodecylamine, and triphenylamine. Triethylamine or trioctylamine is preferable.

  As the electron donating compound (E), a compound having active hydrogen can be used. Among the compounds having active hydrogen, alcohols, phenols, carboxylic acids, thiols, thiophenols, thiocarboxylic acids, sulfonic acids, ammonia, primary amines, secondary amines, anilines, imines Amides, pyrroles, pyrrolidines, piperidines, hydroxyamines, silanols may be used. Among these, compounds having an N—H bond are preferably used, and ammonia, primary amines, secondary amines, anilines, pyrrolidines or piperidines are more preferably used, and particularly primary amines, primary amines, Secondary amines or anilines are preferably used.

  Specific examples of the primary amine include methylamine, ethylamine, normal propylamine, isopropylamine, normal butylamine, isobutylamine, t-butylamine, hexylamine, octylamine, and dodecylamine.

  Specific examples of secondary amines include dimethylamine, diethylamine, dinormalpropylamine, diisopropylamine, dinormalbutylamine, diisobutylamine, di-t-butylamine, dihexylamine, dioctylamine, didodecylamine, diphenylamine, ethylmethylamine. Etc.

  As anilines, anilines having an N—H bond can be used, and specific examples thereof include aniline, N-methylaniline, N-ethylaniline, 4-methylaniline, and 2,6-dimethylaniline.

  As pyrrolidines, pyrrolidines having an N—H bond can be used, and specific examples thereof include pyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, and the like, and piperidines Can be used piperidines having an N—H bond, and specific examples thereof include piperidine, 4-methylpiperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine and the like. .

  Among these exemplified compounds having active hydrogen, methylamine, ethylamine, dimethylamine, diethylamine, aniline, N-methylaniline, 2,5-dimethylpyrrolidine, or 2,6-dimethylpiperidine is more preferably used. In particular, ethylamine, diethylamine or N-methylaniline is preferably used.

  As the electron donating compound (E), alkoxysilicones, ethers or amines are preferably used. Furthermore, amines are more preferably used. These electron donating compounds (E) may be used alone or in combination of two or more.

2) Manufacturing method of olefin polymerization catalyst The manufacturing method of the olefin polymerization catalyst of this invention makes the said component (B) and said component (C) contact in presence of the said component (A). Moreover, the manufacturing method of the olefin polymerization catalyst of this invention is the manufacturing method of the olefin polymerization catalyst which contacts the said component (A), the said component (B), the said component (C), and the said component (D). The contact includes a step of bringing the following component (B) into contact with the following component (C) in the presence of the following component (A).

  Examples of the method of bringing the components into contact include a method of bringing the components into contact with each other in the polymerization vessel by charging them into the polymerization vessel, and a method of bringing the components into contact with each other in an inert solvent outside the polymerization vessel. Etc.

  Specific examples of the inert hydrocarbon medium used for the preparation of the olefin polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclo Examples thereof include alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

3) Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention polymerizes an olefin in the presence of the olefin polymerization catalyst. Since the olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention uses an olefin as the component (A), the olefin polymerization catalyst can be prepared in the reaction system to produce the olefin polymer.

  Examples of the polymerization method include a gas phase polymerization method, a slurry polymerization method, and a bulk polymerization method. A gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  When olefin is vapor-phase polymerized, the polymerization temperature is usually lower than the temperature at which the olefin polymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C. An inert gas may be introduced into the polymerization reaction tank, and hydrogen may be introduced as a molecular weight regulator. Further, an electron donating compound may be introduced.

  The method for producing an olefin polymer of the present invention is suitable for copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms. As a combination of ethylene and α-olefin, ethylene and 1-butene are used. , Ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, ethylene and 1-octene, ethylene, 1-butene and 1-hexene, ethylene and Examples thereof include a combination of 1-butene and 4-methyl-1-pentene, a combination of ethylene, 1-butene and 1-octene, a combination of ethylene, 1-hexene and 1-octene, and preferably ethylene and 1 -A combination of hexene, a combination of ethylene and 4-methyl-1-pentene, a combination of ethylene, 1-butene and 1-hexene. A combination of ethylene, 1-butene and 1-octene, and a combination of ethylene, 1-hexene and 1-octene.

  Further, in the polymerization of olefin, if necessary, another monomer may be introduced into the polymerization reaction tank, and the other monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of the other monomers include diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, α, β-unsaturated carboxylic acids, and the like.

  Specific examples thereof include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2 -Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene , 1,3-cyclooctadiene, 1,3-cyclohexadiene and other diolefins; cyclopentene, Chlohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclo Hexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene Cyclic olefins such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; Alkenylbenzene such as tylene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-second Alkyl styrene such as grade butyl styrene, bisalkenyl benzene such as divinylbenzene, alkenyl aromatic hydrocarbon such as alkenyl naphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride Acid, bicyclo (2,2,1) -5-heptene-2, Α, β-unsaturated carboxylic acids such as 3-dicarboxylic acids; metal salts of α, β-unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, acrylic acid α such as n-propyl, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Β-unsaturated carboxylic acid alkyl esters; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Vinyl ester; acrylic acid Rishijiru, glycidyl methacrylate, and unsaturated carboxylic acid glycidyl ester of itaconic acid monoglycidyl ester.

4) Prepolymerization In the method for producing an olefin polymer of the present invention, the component (A), the component (B), the component (C), and the necessary components are used in the preparation of the olefin polymerization catalyst by using a small amount of the olefin of the component (A). The olefin is polymerized using a prepolymerized solid catalyst component (hereinafter referred to as prepolymerization) obtained by contacting the component (D) and / or the component (E) according to the polymerization catalyst component or polymerization catalyst. Is preferred.

  Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more. Preferably, ethylene alone, or a combination of ethylene and α-olefin, more preferably ethylene alone, or at least one α-olefin selected from 1-butene, 1-hexene and 1-octene, and ethylene Is used in combination.

  The content of the prepolymerized polymer in the prepolymerized solid catalyst component is preferably 0.01 to 1000 g, more preferably 0.05 to 500 g, and still more preferably 0, per 1 g of component (C). .1 to 200 g.

  The preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method. As a method of charging component (A), component (B), component (C), and optionally component (D) and / or component (E) into a polymerization reactor for performing prepolymerization, nitrogen is usually used. In addition, an inert gas such as argon, hydrogen, ethylene, or the like is used, and a method in which each component is dissolved or diluted in a solvent and a solution or slurry is used.

  When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. . These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  Moreover, when prepolymerization is performed by the slurry polymerization method, as the slurry concentration, the amount of the component (C) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed, but the temperature at which the prepolymerization is started is preferably 45 ° C. or less, and preferably 40 ° C. or less. Moreover, the partial pressure of olefins in the gas phase part during the prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  As a method of supplying the prepolymerized prepolymerized solid catalyst component to the polymerization reaction tank, a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a state free from moisture, each component Is dissolved or diluted in a solvent and supplied in a solution or slurry state.

5) Olefin polymer As the olefin polymer obtained by the method for producing an olefin polymer of the present invention, an ethylene homopolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4- Methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene- Examples include 1-butene-1-octene copolymer, ethylene-1-hexene-1-octene copolymer, and preferably ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer Copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer, ethylene-1-hexene-1-octene copolymer It is a polymer.

  Moreover, it is preferable that content of the monomer unit based on ethylene in an olefin polymer is 50 weight% or more with respect to the total weight (100 weight%) of an olefin polymer.

6) Molded product The olefin polymer obtained by the method for producing an olefin polymer of the present invention comprises an extrusion load during molding, bubble stability during inflation film molding, neck-in during T-die film molding, and hollow molding. Excellent processability such as parison shape retention, and excellent mechanical strength. Further, the transparency of the molded product can be excellent.

  The olefin polymer is molded by a known molding method, for example, an extrusion molding method such as an inflation film molding method or a T-die film molding method, a hollow molding method, an injection molding method, or a compression molding method. As the molding method, an extrusion molding method and a hollow molding method are preferably used, and an inflation film molding method, a T-die film molding method, and a hollow molding method are particularly preferably used.

  The olefin polymer is used after being molded into various forms. Although the form of a molded article is not specifically limited, it is used for a film, a sheet, a container (tray, bottle, etc.), etc. The molded article is also suitably used for applications such as food packaging materials; pharmaceutical packaging materials; electronic component packaging materials used for packaging semiconductor products and the like; surface protection materials.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Density (d, unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Number of short chain branches (SCB, unit: 1 / 1000C)
The content of the monomer unit derived from the α-olefin in the copolymer is determined using a calibration curve from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation). This was expressed as SCB by determining the number of short chain branches (SCB) per 1000 carbon atoms.

(3) Molecular weight distribution (Mw / Mn, Mz / Mw)
Using gel permeation chromatograph (GPC) method, measure z-average molecular weight (Mz), weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions (1) to (8) Mw / Mn and Mz / Mw were obtained. The baseline on the chromatogram is a stable horizontal region with a sufficiently long retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points.
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

(4) Number of long chain branch points (LCB; unit is the number of branch points / 1000 C)
A carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and determined by the following calculation method. (Reference: Scientific literature "Macromolecules", (USA), American Chemical Society, 1999, Vol. 32, p.3817-3819)
<Measurement conditions>
Apparatus: AVANCE600 manufactured by Bruker
Measuring solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed liquid Measurement temperature: 130 ° C
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Trimethylsilane Window function: Negative exponential function <Calculation method>
The peak area of the peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined with the sum of all peaks observed at 5 to 50 ppm being 1000. The peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side. In the measurement of the ethylene-1-octene copolymer under the present conditions, the position of the peak top of the peak derived from methine carbon to which a branch having 6 carbon atoms was bonded was 38.21 ppm.

Example 1
(1) Preparation of solid catalyst component Silica (Sypolol 948 manufactured by Devison, Inc .; average particle size) in a 50-liter reactor equipped with a nitrogen-replaced stirrer and heated at 300 ° C. under nitrogen flow as component (b) solid support = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 9.68 kg was added. After adding 100 liters of toluene, it was cooled to 2 ° C. To this, 26.3 liters of a toluene solution of methylalumoxane (2.9M) was added dropwise over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 40 ° C., the mixture was allowed to stand for 40 minutes to allow the solid component to settle, and the upper slurry portion was removed. As a washing operation, 100 liters of toluene was added thereto, and the mixture was stirred for 10 minutes. Then, the stirring was stopped and the mixture was allowed to stand to settle the solid component. Similarly, the upper slurry portion was removed. The above washing operation was repeated 3 times in total. Furthermore, after adding 100 liters of toluene and stirring, it filtered simultaneously with stopping stirring. After repeating this operation once more, 110 liters of hexane was added, and filtration was performed in the same manner. This operation was repeated once more. Then, 12.6 kg of solid catalyst components were obtained by performing drying at 70 degreeC under nitrogen circulation for 7 hours. As a result of elemental analysis, it was Al = 4.4 mmol / g.

(2) Polymerization The inside of an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon after drying under reduced pressure was evacuated, 30 g of 1-butene and 720 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 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 1-butene = 2.2 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (D) was added. Next, 5.6 mg of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride as the transition metal compound (B) was added to 2 ml of toluene and 0.5 ml of the above hexane solution of triisobutylaluminum, and the mixture was stirred. 0.78 ml (0.005 mmol in terms of Zr atom) of the solution was added, and then 48.4 mg of the solid catalyst component obtained in Example 1 (1) was added as the component (C). Polymerization was carried out at 70 ° C. for 3 hours while feeding ethylene gas so as to keep the total pressure constant. As a result, 18 g of an olefin polymer was obtained.

Example 2
(1) Polymerization The inside of an autoclave with a stirrer with an inner volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.0015 MPa, 30 g of 1-butene, butane as a polymerization solvent 720 g was charged and the temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 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 = 0.13 mol% and 1-butene = 2.2 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (D) was added. Next, a toluene solution of dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride as the transition metal compound (B) (racemic / meso = 49.2: 50.8) (0.002 mmol / mL in terms of Zr atom) ), And then 14.2 mg of the solid catalyst component obtained in Example 1 (1) was added as component (C). Polymerization was carried out at 70 ° C. for 90 minutes while feeding ethylene gas so as to keep the total pressure constant. As a result, 32 g of an olefin polymer was obtained.

Comparative Example 1
(1) Preparation of catalyst component (X-1) To a nitrogen-substituted 10 mL glass Schlenk flask was charged 2.5 mL of toluene, and 167 mg of the solid catalyst component prepared in Example 1 was charged. Next, 2.3 mL of a toluene solution (0.02 mmol / mL in terms of Zr atom) of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride was added dropwise as the transition metal compound (B) and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with heptane to obtain catalyst component (X-1) as a heptane slurry.

(2) Polymerization The inside of an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon after drying under reduced pressure was evacuated, 30 g of 1-butene and 720 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 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 1-butene = 1.7 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (D). Next, the entire amount of the heptane slurry of the catalyst component (X-1) prepared in Comparative Example 1 (1) was charged. Polymerization was carried out at 70 ° C. for 3 hours while feeding ethylene gas so as to keep the total pressure constant. As a result, 44 g of an olefin polymer was obtained.

Comparative Example 2
(1) Preparation of catalyst component (X-2) 1 mL of toluene was placed in a nitrogen-substituted 10 mL glass Schlenk flask, and 160 mg of the solid catalyst component prepared in Example 1 was charged. Next, 5.7 mg of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride was added as a transition metal compound (B) and reacted at room temperature for 1 hour to obtain a catalyst component (X-2) as a toluene slurry.

(2) Polymerization The inside of an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon after drying under reduced pressure was evacuated, 30 g of 1-butene and 720 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 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 1-butene = 1.4 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (D) was added. Next, the entire amount of the toluene slurry of the catalyst component (X-2) prepared in the comparative example (1) was charged. Polymerization was carried out at 70 ° C. for 3 hours while feeding ethylene gas so as to keep the total pressure constant. As a result, 216 g of an olefin polymer was obtained.

(a)：ジメチルシリレンビス（シクロペンタジエニル）ジルコニウムジクロリド
(b)：ジメチルシリレンビス（３−フェニルシクロペンタジエニル）ジルコニウムジクロリド

(a): Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride
(b): Dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride

  The olefin polymers obtained in Examples 1 and 2 are excellent in molding processability because of their large LCB.

Claims (5)

An olefin polymerization catalyst formed by contacting the following component (B) with the following component (C) in the presence of the following component (A).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier Component (C-2): Organic compound Modified clay mineral formed by contacting clay mineral with water In the contact of the following component (A), the following component (B), the following component (C), and the following component (D), in the presence of the following component (A), the following component (B) and the following component ( An olefin polymerization catalyst formed by contacting with C).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier component (C-2): Organic compound Modified clay mineral component (D) formed by bringing clay into contact with clay mineral: Organoaluminum compound The manufacturing method of the olefin polymerization catalyst which makes the following component (B) and the following component (C) contact in presence of the following component (A).
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier Component (C-2): Organic compound Modified clay mineral formed by contacting clay mineral with water A method for producing an olefin polymerization catalyst in which the following component (A), the following component (B), the following component (C), and the following component (D) are brought into contact with each other, wherein the contact is the presence of the following component (A) Below, the manufacturing method of the olefin polymerization catalyst including the process of making the following component (B) and the following component (C) contact.
Component (A): Olefin component (B): Periodic table of elements Group 3 to Group 11 or transition metal compound of lanthanoid series Component (C): Component (C-1) and / or Component (C- 2)
Component (C-1): Solid catalyst component formed by contacting the following component (a) with the following component (b) Component (a): (a-1) Group 13 of the periodic table of elements At least one compound selected from the group consisting of an organometallic compound, (a-2) an organoaluminum oxy compound, and (a-3) a boron compound. Component (b): Solid carrier component (C-2): Organic compound Modified clay mineral component (D) formed by bringing clay into contact with clay mineral: Organoaluminum compound   The manufacturing method of the olefin polymer which superposes | polymerizes an olefin in presence of the olefin polymerization catalyst of Claim 1 or 2.