JP2003147009A - Method for producing olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefinic polymer by which the α-olefin polymer can be produced at a low cost by using only ethylene as a raw material. SOLUTION: This method for producing the olefinic polymer comprises carrying out an oligomerizing reaction of the ethylene in the presence of an olefin polymerization catalyst (I) consisting essentially of (A) at least one kind of a specific group 8-10 transition metal compound of the periodic table, providing an α-olefin and then polymerizing the produced α-olefin or copolymerizing the α-olefin with the ethylene in the presence or absence of the olefin polymerization catalyst (I) and in the presence of an olefin polymerizing catalyst (II) consisting essentially of (A') at least one kind of a group 4-6 transition metal compound of the periodic table.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an olefin polymer, more specifically, an α-olefin polymer and an ethylene / α-olefin copolymer are produced by a simple method from a raw material containing only ethylene. The present invention relates to a method for producing an olefin polymer that can be used.

[0002]

2. Description of the Related Art Conventionally, α has been useful as a synthetic lubricating oil or the like.
Various proposals have been made for producing an olefin polymer, for example, a method of polymerizing 1-decene with a Friedel-Crafts catalyst using aluminum chloride or boron trifluoride (US Pat. No. 3,149,149). No. 178, No. 3,382,291).

However, the obtained α-olefin polymer has a low molecular weight, and boron trifluoride has an environmental problem that fluorine which is corrosive to the equipment is discharged in addition to being expensive. Further, the α-olefin polymer is produced by cationic polymerization or coordination anionic polymerization using expensive α-olefin as a raw material, but has many branches, and when used for a lubricating oil or the like, there is a problem in physical properties. there were. Furthermore, an expensive catalyst may be used or the polymerization activity may be low. Therefore, a method for producing an α-olefin polymer by an inexpensive method using only ethylene as a raw material has been desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is a method for producing an olefin-based polymer capable of inexpensively producing an α-olefin polymer by using only ethylene as a raw material. It is intended to provide.

[0005]

The present inventors have used a specific transition metal compound of Group 8 to 10 of the periodic table as a catalyst in the first step, and used a catalyst of a group 4 to 6 of the periodic table in the second step. By using a transition metal compound as a catalyst and polymerizing ethylene, it was found that the object of the present invention can be effectively achieved,
Based on this, the present invention has been completed.

That is, the gist of the present invention is as follows. 1. (A) The following general formula (1)

[0007]

[Chemical 5]

[In the formula, M represents a transition metal of Groups 8 to 10 of the periodic table, and R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number. 1 to
20 halogenated hydrocarbon groups or groups containing heteroatoms, which may be bonded to each other to form a ring. R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may form a ring with each other. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶
₂ or SR ¹⁶ (wherein R ¹⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms having a group containing a hetero atom).
Indicates. However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom. X represents a covalent bond group or an ionic bond group, and when there are a plurality of groups, they may be the same or different. n represents the valence of M. ] At least one transition metal compound of Groups 8 to 10 of the periodic table represented by the following formula: (B) (b-1) organoaluminum oxy compound and (b-2) transition metal compound of the component (A) or In the presence of an olefin polymerization catalyst (I) containing at least one compound selected from a compound capable of reacting with a derivative thereof to form an ionic complex, an oligomerization reaction of ethylene is carried out to obtain an α-olefin, Next, in the presence or absence of the olefin polymerization catalyst (I), (A ′) at least one transition metal compound of Groups 4 to 6 of the periodic table,
(B ') (b'-1) selected from organoaluminum oxy compounds and (b'-2) compounds capable of reacting with the transition metal compound of the component (A') or a derivative thereof to form an ionic complex. The method for producing an olefin-based polymer, which comprises polymerizing the α-olefin produced above in the presence of an olefin polymerization catalyst (II) containing at least one of 2. (A) The following general formula (1)

[0009]

[Chemical 6]

[In the formula, M represents a transition metal of Groups 8 to 10 of the periodic table, and R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number. 1 to
20 halogenated hydrocarbon groups or groups containing heteroatoms, which may be bonded to each other to form a ring. R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may form a ring with each other. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶
₂ or SR ¹⁶ (wherein R ¹⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms having a group containing a hetero atom).
Indicates. However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom. X represents a covalent bond group or an ionic bond group, and when there are a plurality of groups, they may be the same or different. n represents the valence of M. ] At least one transition metal compound of Groups 8 to 10 of the periodic table represented by the following formula: (B) (b-1) organoaluminum oxy compound and (b-2) transition metal compound of the component (A) or In the presence of an olefin polymerization catalyst (I) containing at least one compound selected from a compound capable of reacting with a derivative thereof to form an ionic complex, an oligomerization reaction of ethylene is carried out to obtain an α-olefin, Next, in the presence or absence of the olefin polymerization catalyst (I), (A ′) at least one transition metal compound of Groups 4 to 6 of the periodic table,
(B ') (b'-1) Organoaluminum oxy compound and (b'-2) selected from compounds capable of reacting with the transition metal compound of the component (A') or a derivative thereof to form an ionic complex. In the presence of an olefin polymerization catalyst (II) containing at least one of
-A method for producing an olefin-based polymer, which comprises copolymerizing an olefin. 3. In the general formula (1), at least one of R ⁴ and R ⁵ is an aryl group or a substituted aryl group.
Or the method for producing an olefin-based polymer described in 2. 4. In the general formula (1), the method for producing an olefin polymer according to any one of 1 to 3 above, wherein the transition metal M is iron or cobalt. 5. The component (A ′) is represented by the following general formula (9) or (10)

[0011]

[Chemical 7]

[0012]

[Chemical 8]

(Wherein R^{twenty five}~ R³⁶And X¹~ X^FourIs that
Independently hydrogen atom, halogen atom, carbon number 1-20
Hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group
Indicates a group or phosphorus-containing group and forms a ring with an adjacent group.
May be made. 3 R³³And 3 R³⁴Are each
They may be the same or different from each other. Y¹~ Y^FourIs it
A divalent group that independently binds two ligands,
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
Containing hydrocarbon group, silicon containing group, germanium containing
Group, tin-containing group, -O-, -CO-, -S-, -SO
₂-, -NR³⁷-, PR³⁷-, -P (O) R³⁷-, -B
R³⁷-Or-AlR³⁷-Indicates R³⁷Is a hydrogen atom, halo
Gen atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to carbon atoms
20 halogen-containing hydrocarbon groups are shown. M ^FourAnd M
^FiveAre independently selected from transition metals of Groups 4 to 6 of the periodic table.
Show. ) The above-mentioned 1 to 4 which is a transition metal compound represented by
The method for producing an olefin polymer according to any one of claims. 6. In the general formula (9) or (10), M^FourAnd M^Five
The olefin-based polymerization as described in 5 above, wherein is zirconium.
Body manufacturing method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises (A) a transition metal compound of Groups 8 to 10 of a specific periodic table, (B) an organoaluminum oxy compound (b-1), and (b-2) said (A). ) Oligomerization reaction of ethylene is carried out in the presence of an olefin polymerization catalyst (I) containing at least one compound selected from compounds capable of forming an ionic complex by reacting with the metal transfer compound of component (1) or a derivative thereof. To obtain an α-olefin, and then in the presence or absence of the olefin polymerization catalyst (I), (A ′) at least one transition metal compound of Groups 4 to 6 of the periodic table, and (B ′) ( b′-1) an organoaluminum oxy compound and (b′-2) at least one compound selected from compounds capable of reacting with the transfer metal compound of the component (A ′) or a derivative thereof to form an ionic complex. Olefin polymerization catalyst containing (I I) in the presence of the α-olefin produced, in the presence or absence of ethylene,
A method for producing an olefin-based polymer, which comprises polymerizing.

The term α-olefin as used in the present invention means
Refers to a polymer (oligomer) having a vinyl group at the terminal with a molecular weight of 10,000 or less, and shows the original characteristics of the polymer. It has different physical properties and uses from a normal ethylene polymer having a higher molecular weight. . Hereinafter, the present invention will be described in detail. (1) Olefin Polymerization Catalyst (I) The olefin polymerization catalyst (I) includes (A) a transition metal compound of Group 8 to 10 of the specific periodic table, (B) (b-1) an organoaluminum oxy compound, and (B). b-2) At least one selected from the compounds capable of reacting with the metal transfer compound of the component (A) or a derivative thereof to form an ionic complex. The transition metal compound of Group 8 to 10 of the periodic table of the component (A) has the following general formula (1).

[0016]

[Chemical 9]

[Wherein M represents a transition metal of Groups 8 to 10 of the Periodic Table, and R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number. 1 to
20 halogenated hydrocarbon groups or groups containing heteroatoms, which may be bonded to each other to form a ring. R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may form a ring with each other. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶
₂ or SR ¹⁶ (wherein R ¹⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hetero atom-containing hydrocarbon group). However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom. X represents a covalent bond group or an ionic bond group, and when there are a plurality of groups, they may be the same or different. n represents the valence of M. ] It is a metal transition compound represented by.

In the formula, M represents a transition metal of Groups 8 to 10 of the Periodic Table, preferably iron or cobalt. R ^{1 to} R ³
Are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 represents a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, which may be bonded to each other to form a ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number 7 To 20 arylalkyl groups and the like. 1 to 2 carbon atoms
Specific examples of the straight-chain or branched alkyl group of 0 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups. Group, various hexyl groups, various octyl groups, various decyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, and the like. Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Incidentally, a suitable substituent such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. Also,
Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and methylnaphthyl group. As the arylalkyl group having 7 to 20 carbon atoms, specifically, a benzyl group,
Examples thereof include a phenethyl group.

The halogenated hydrocarbon group having 1 to 20 carbon atoms is a hydrocarbon group obtained by halogenating the aforementioned hydrocarbon group having 1 to 20 carbon atoms. Examples of the group containing a hetero atom include an alkoxy group represented by —OR ¹⁷ and —NR ¹⁷ ₂
And an silyl group represented by —SiR ¹⁷ ₃ and the like. However, R ¹⁷ has 1 carbon atom
~ 20 hydrocarbon groups. The above-mentioned thing can be mentioned as a C1-C20 hydrocarbon group. Among them, R ^{1 to} R ³ are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.

R ⁴ and R ⁵ are hydrogen atoms or have 1 to 2 carbon atoms.
It is preferable that at least one of them represents an aryl group or a substituted aryl group. The above-mentioned thing can be mentioned as a C1-C20 hydrocarbon group. As the aryl group, a phenyl group, 1-
Examples thereof include a naphthyl group and a 2-naphthyl group.
Examples of the substituted aryl group include those in which at least one hydrocarbon group or halogen atom is a substituent in the above aryl group. For example, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group,
4-ethylphenyl group, 2-n-propylphenyl group,
3-n-propylphenyl group, 4-n-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-isobutylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group Group, 2-tert-butylphenyl group,
3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,3-dimethylphenyl group, 2,4-
Dimethylphenyl group, 2,5-dimethylphenyl group,
2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,5-diter
Those in which a linear or branched alkyl group such as t-butylphenyl group or 2,4,6-trimethylphenyl group is a substituent, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenyl Aromatic group such as phenyl group as a substituent, 2-fluorophenyl group, 3-
Fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3
-Iodophenyl group, 4-iodophenyl group, 2,3-
Difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,
3,4,5,6-pentafluorophenyl group, 3,5-
Examples thereof include those in which a halogen atom such as a bis (trifluoromethyl) phenyl group is a substituent.

R ^{7 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. As the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms or the group containing a hetero atom, the same groups as described above can be mentioned. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. As the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms or the group containing a hetero atom, the same groups as described above can be mentioned.

R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ which are the characteristics of the transition metal compound used in the present invention are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶ ₂ or S.
R ¹⁶ (here, R ¹⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms having a group containing a hetero atom). However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom.

R⁶, R^Ten, R¹¹, R¹⁵And R¹⁶The halo
The hydrogen atom and the hydrocarbon group having 1 to 20 carbon atoms are listed above.
You can get it. Also, R¹⁶Contains heteroatoms of
Containing a hetero atom of a hydrocarbon group having 1 to 20 carbon atoms.
The above-mentioned groups are also included in the hydrocarbon group having 1 to 20 carbon atoms.
You can get it. NR¹⁶ ₂And PR¹⁶ ₂About
A cyclic compound such as a pyrrole group or a morpholyl group.
It doesn't matter. R⁶, R ^Ten, R¹¹And R¹⁵Out of which
Specific examples include chlorine atom, bromine atom, and iodine atom.
Elementary atom, dimethylamino group, methoxy group, phenoxy
Group, methylthio group, pyrrole group, piperidino group, morpho
A ryl group etc. can be mentioned. More preferable one
It is a chlorine atom.

X represents a covalent bond or ionic bond group, and when there are a plurality of groups, they may be the same or different. Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10), an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10),
An amino group, a phosphorus-containing group having 1 to 20 carbon atoms (preferably 1 to 12) (for example, diphenylphosphino group), a silicon-containing group having 1 to 20 carbon atoms (preferably 1 to 12) (for example, trimethylsilyl group or Trimethylsilylmethyl group), or a halogen-containing boron anion (eg, -BF
₄ ) can be mentioned. Among these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable. Examples of the halogen atom include chlorine, bromine and iodine, and among them, chlorine atom is preferable.

N is the valence of M, and specifically, 0 to
It is 3. With the preferred combination in the general formula (1)
The following is the case. R¹~ R³Is a hydrogen atom
R^FourAnd R^FiveIs hydrogen atom, phenyl group, 2,5-di
Methylphenyl group or 2,4,6-trimethylphenyl
Group, R⁷~ R ⁹Is a hydrogen atom, a methyl group or ter
a t-butyl group, R¹²~ R¹⁴Is hydrogen atom, methyl group
Or a tert-butyl group, R⁶, R^Ten, R¹¹as well as
R¹⁵Is a hydrogen atom, chlorine atom, bromine atom or iodine atom.
X is a monovalent anion of a halogen atom. Next before
Specific examples of the transition metal compound represented by the general formula (1) are shown below.
In that case, the following compounds 1 to 10 may be mentioned.

[0026]

[Chemical 10]

Preferred among these are compound 1 and compound 2. Next, an example of a method for producing the transition metal compound represented by the general formula (1) will be described. As a method for synthesizing the ligand (diimine compound) in the transition metal compound of the present invention, there is a method of reacting a ketone compound represented by the following general formula (2) with an aniline compound represented by the following general formula (3). Can be mentioned.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

When the reaction is carried out, an organic acid such as formic acid may be used as a catalyst. Further, the ligand (diimine compound) obtained above contains a halide of the transition metal M (MX _n ,
X: halogen) or a hydrate thereof can be used to produce the transition metal compound represented by the general formula (1). The component (B) is at least one selected from the components (b-1) and (b-2).
As the organoaluminum oxy compound of the component (b-1), the following general formula (4)

[0031]

[Chemical 13]

(In the formula, R ¹⁸ is an alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms;
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and a represents an average degree of polymerization and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁸ may be the same or different. ), A chain aluminoxane,
And the following general formula (5)

[0033]

[Chemical 14]

A cyclic aluminoxane represented by the formula (wherein R ¹⁸ and a are the same as those in the general formula (4)) can be mentioned. As the method for producing the aluminoxane,
A method of bringing the alkylaluminum into contact with a condensing agent such as water is mentioned, but the means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, an inorganic substance Or a method of reacting water adsorbed on an organic substance with an organoaluminum compound,
There is a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and then reacting with water. As aluminoxanes, methylaluminoxane,
Alkylaluminoxanes such as ethylaluminoxane and isobutylaluminoxane are preferred. Among them, methylaluminoxane is more preferable. These aluminoxanes may be used alone or in combination of two or more.

On the other hand, as the component (b-2),
By reacting with the transition metal compound (A) or its derivative
Any compound that can form an ionic complex can be used.
Any of the following general formulas (6) and (7) can be used.           ([L¹-R¹⁹]^{k +})_b([Z]^-)_c        ... (6)           ([L²]^{k +})_b([Z]^-)_c              ... (7) (However, L²Is M¹, R²⁰R^{twenty one}M², R^{twenty two} ₃C or R
^{twenty three}M²Is. ) [(6), (7), L¹Is Lewis
Base, [Z]^-Is a non-coordinating anion [Z ¹]^-Or
[Z²]^-, Where [Z¹]^-Has multiple groups bound to an element
Anion, that is, [M³G¹G²... G^m]
^-(Where M³Is an element of Groups 5 to 15 of the Periodic Table, preferably
Or elements of Groups 13 to 15 of the Periodic Table. G¹~ G^mIs
Hydrogen atom, halogen atom, carbon atom of 1 to 20
Alkyl group, dialkylamino group having 2 to 40 carbon atoms, carbon
C1-20 alkoxy group, C6-20 aryl
Group, aryloxy group having 6 to 20 carbon atoms, 7 to 4 carbon atoms
0 alkylaryl group, C7-40 aryla group
Alkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms,
C1-C20 acyloxy group or organic metalloid group
Or a hydrocarbon group containing a hetero atom having 2 to 20 carbon atoms
You G¹~ G^mTwo or more of them may form a ring.
m is [(central metal M³Valence of +1)
You ), [Z²]^-Is the logarithm of the reciprocal of the acid dissociation constant (pK
a) Bronsted acid having -10 or less alone or Bronsted acid
Conjugate base of a combination of Ted acid and Lewis acid, or in general
A conjugate base of an acid, which is defined as a super strong acid. Also,
The chair base may be coordinated. Also, R ¹⁹Is hydrogen
Child, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms
Reel group, alkylaryl group or arylalkyl group
Indicates R²⁰And R^{twenty one}Are each cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group or phenyl group
Ruorenyl group, R^{twenty two}Is an alkyl group having 1 to 20 carbon atoms,
Reel group, alkylaryl group or arylalkyl group
Indicates. R^{twenty three}Is tetraphenylporphyrin, phthalocyanine
A macrocyclic ligand such as anine is shown. k is [L¹-R¹⁹],
[L²] Is an integer of 1 to 3 and b is an integer of 1 or more.
The number, c = (k × b). M¹Is the first to the periodic table
M, which contains elements of groups 3, 11 to 13 and 17
²Indicates an element belonging to groups 7 to 12 of the periodic table. ]]
What is suitable can be used.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁹ include hydrogen, methyl group,
Examples thereof include an ethyl group, a benzyl group, and a trityl group. Specific examples of R ²⁰ and R ²¹ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopenta group. A dienyl group etc. can be mentioned. As a specific example of R ²² ,
Examples thereof include phenyl group, p-tolyl group, p-methoxyphenyl group, and the like. Specific examples of R ²³ include tetraphenylporphyrin, phthalocyanine, allyl group, methallyl group, and the like. Further, specific examples of M ¹ include Li, Na, K, Ag, Cu, Br, I and I.
_{3 and the} like. Specific examples of M ² include M
Examples thereof include n, Fe, Co, Ni and Zn.

[Z ¹ ] ^- , that is, [M ³ G ¹ G
² ... G ^m ] ^- , specific examples of M ³ are:
B, Al, Si, P, As, Sb and the like, preferably B and Al can be mentioned. Also, G ¹ , G ^{2 to} G ^m
Examples of dialkylamino group include dimethylamino group and diethylamino group, and alkoxy group or aryloxy group include methoxy group, ethoxy group, n-
As a hydrocarbon group such as a propoxy group and a phenoxy group,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n
-Eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group and the like, as a halogen atom, fluorine, chlorine, bromine, iodine, a hydrocarbon group containing a hetero atom. As a p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis Examples of the organic metalloid group such as (trimethylsilyl) methyl group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group and the like.

Further, a non-coordinating anion, that is, pK
a is -10 or less Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combination conjugate base [Z ^{2] -} Examples of trifluoromethanesulfonic acid anion (CF ₃ SO ₃₎ -, bis (trifluoperazine Rhomethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ).
^-, trifluoroacetic acid anion (CF ₃ COO) ^-, hexafluoroantimony anion (SbF ₆₎ ^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / 5- Antimony fluoride (FSO ₃ / SbF ₅ )
-, Fluorosulfonate anion / 5-arsenic fluoride (F
SO ₃ / AsF ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^-
And so on.

Specific examples of such a component (b-2) compound include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, and tetraethylammonium tetraphenylborate. , Methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, tetraphenyl Trimethylanilinium borate, Methylpyridinium tetraphenylborate, Benzylpyridinium tetraphenylborate, Methyl (2-cyanopyridinium) tetraphenylborate, Tetrakis ( Triethylammonium borate, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium , Tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Methyldiphenylammonium borate, tetrakis (pentafluorophenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluoro) Phenyl) borate methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis (pentafluorophenyl) borate methylpyridinium, tetrakis (pentafluorophenyl) boro Acid benzylpyridinium tetrakis (pentafluorophenyl) borate methyl (2-cyanopyridinium), tetrakis (pentafluorophenyl) benzyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium) ), Triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanis tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate Rinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1, 1'-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Lithium acid, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, Examples thereof include silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The component (b-2) may be used alone,
Moreover, you may use it in combination of 2 or more type. When the component (b-1) is used as the component (B), the usage ratio of the component (A) and the component (B) in the first step of the present invention is preferably a molar ratio of 1: 1 to 1. : 100,00
0, more preferably 1: 100 to 1: 10,000,
When the component (b-2) is used, the molar ratio is preferably 1: 1 to 1: 100,000, more preferably 1: 2.
˜1: 10,000. As the component (B), (b-1) and (b-2) may be used alone or in combination of two or more.

The above-mentioned olefin polymerization catalyst (I) in the present invention may be composed of the above-mentioned components (A) and (B), and further, as the (C) component,
It may contain an organoaluminum compound. Here, the organoaluminum compound as the component (C) is represented by the general formula (8) R ²⁴ _d AlQ _3-d (8) (wherein, R ²⁴ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group or a halogen atom, and d is an integer of 1 to 3. ) Is used.

Specific examples of the compound represented by the general formula (8) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The ratio of the component (A) and the component (C) used is a molar ratio, preferably 1: 1 to 1: 1.
It is 0, more preferably 1: 1 to 1: 5. This (C)
By using the component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

(2) Regarding Method for Producing α-Olefin (First Step) In the first step, the oligomerization reaction of ethylene is carried out in the presence of the olefin polymerization catalyst (I). The method for carrying out this reaction is not particularly limited, and it is possible to adopt any method such as a solution reaction method using a solvent, a liquid phase solvent-free reaction method using substantially no solvent, a gas phase reaction method, It may be a continuous reaction or a batch reaction. When a solvent is used, the solvent may be pentane, hexane,
There may be mentioned hydrocarbon solvents such as heptane, cyclohexane, benzene and toluene, and these solvents may be used alone or in combination of two or more kinds. When a solvent is used, the amount of the catalyst used is usually in the range of 0.1 to 100 μmol, preferably 1 to 20 μmol of the transition metal component per liter of the solvent from the viewpoint of reaction activity. It is advantageous.

The reaction conditions are not particularly limited,
The reaction temperature is generally -78 to 200 ° C, preferably room temperature to
It is in the range of 150 ° C. The ethylene pressure of the reaction system is usually 0.1 to 15 MPa · G, preferably 0.8 to
The range is 7 MPa · G. Further, the molecular weight during the reaction can be adjusted by a known means such as selection of temperature and pressure. The α-olefin produced by the above method is subjected to the polymerization in the second step after being separated from the olefin polymerization catalyst (I) or without being separated.

(3) Olefin Polymerization Catalyst (II) The olefin polymerization catalyst (II) is (A ')
To at least one transition metal compound of Group 6 to (B ′)
(B'-1) Organoaluminum oxy compound and (b '
-2) At least one compound selected from the compounds capable of reacting with the transition metal compound of the component (A ') or a derivative thereof to form an ionic complex.

The component (A ') of the transition metal compound of Groups 4 to 6 of the periodic table is not particularly limited, but as a particularly preferable compound, the following general formula (9) or (10) is used.

[0048]

[Chemical 15]

[0049]

[Chemical 16]

(In the formula, R^{twenty five}~ R³⁶And X¹~ X^FourIs that
Independently hydrogen atom, halogen atom, carbon number 1-20
Hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group
Indicates a group or phosphorus-containing group and forms a ring with an adjacent group.
May be made. 3 R³³And 3 R³⁴Are each
They may be the same or different from each other. Y¹~ Y^FourIs it
A divalent group that independently binds two ligands,
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
Containing hydrocarbon group, silicon containing group, germanium containing
Group, tin-containing group, -O-, -CO-, -S-, -SO
₂-, -NR³⁷-, PR³⁷-, -P (O) R³⁷-, -B
R³⁷-Or-AlR³⁷-Indicates R³⁷Is a hydrogen atom, halo
Gen atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to carbon atoms
20 halogen-containing hydrocarbon groups are shown. M ^FourAnd M
^FiveAre independently selected from transition metals of Groups 4 to 6 of the periodic table.
Show. ), A metal transition compound represented by
It As the compound represented by the general formula (9),
Specifically, the following general formula (9A), (9B) or (9
Examples of transition compounds of Groups 4 to 6 of the periodic table represented by C)
You can

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19]

In the formula, R ^{38 to} R ⁶⁵ and X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, It represents a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and may be bonded to adjacent groups to form a ring. Y ¹ and Y ² each independently represent a divalent group that bonds two ligands and has 1 to 2 carbon atoms.
0 hydrocarbon group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, germanium-containing group, tin-containing group,
-O -, - CO -, - S -, - SO 2 -, - NR 66 -,
^{-PR 66 -, - P (O} ) R 66 -, - BR 66 - or -Al
R ⁶⁶ - indicates, R ⁶⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. M ⁴ represents a transition metal of Groups 4 to 6 of the periodic table.

Examples of the compound represented by the general formula (9A) include (1,1′-ethylene) (2,2′-ethylene) bisindenylzirconium dichloride,
(1,1′-ethylene) (2,2′-ethylene) bis (3-methylindenyl) zirconium dichloride,
(1,1′-ethylene) (2,2′-ethylene) bis (4-methylindenyl) zirconium dichloride,
(1,1′-ethylene) (2,2′-ethylene) bis (5-methylindenyl) zirconium dichloride,
(1,1'-ethylene) (2,2'-ethylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) bis (4,5) -Benzoindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2 ') -Ethylene)
Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-Dimethylsilylene) bisindenyl zirconium dichloride, (1,1′-dimethylsilylene)
(2,2'-Dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bis (4
-Methylindenyl) zirconium dichloride, (1,
1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (5-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (5,6- Benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,1 ′)
-Dimethylsilylene) (2,2'-dimethylsilylene)
Bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-
Dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2 2'-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-ethylene) bis (4-methylindenyl) zirconium dichloride, (1,1'- Dimethylsilylene) (2,2'-ethylene) bis (5-methylindenyl) zirconium dichloride, (1,1'-
Dimethylsilylene) (2,2'-ethylene) bis (5,5
6-benzoindenyl) zirconium dichloride,
(1,1′-Dimethylsilylene) (2,2′-ethylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2 ′
-Ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-ethylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1 '
-Ethylene) (2,2'-dimethylsilylene) bisindenyl zirconium dichloride, (1,1'-ethylene) (2,2'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1) '-Ethylene) (2,2'-dimethylsilylene) bis (4-methylindenyl) zirconium dichloride, (1,1'
-Ethylene) (2,2'-dimethylsilylene) bis (5
-Methylindenyl) zirconium dichloride, (1,
1'-ethylene) (2,2'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-dimethylsilylene) bis (4,5- Benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2 '-Isopropylidene) bisindenyl zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) ( 2,2'-isopropylidene) bis (4-methylindenyl) zirconium dichloride,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) bis (5-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2
2'-isopropylidene) bis (5,6-benzoindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene) bis (4
5-benzoindenyl) zirconium dichloride,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) bis (5,6-dimethylindenyl) zirconium dichloride and other dichloro compounds, and the dimethyl, diethyl, dihydro and diphenyl compounds of the above compounds. Examples thereof include dibenzyl compounds and their titanium and hafnium complexes.

Examples of the compound represented by the general formula (9B) include (1,1′-ethylene) (2,2′-ethylene) indenyl (3,5-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) indenyl (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,1'-ethylene) (2,2'-ethylene) indenyl (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) (4-methylindene Nil) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (1,
1'-ethylene) (2,2'-ethylene) (4-methylindenyl) (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2
2'-ethylene) (5-methylindenyl) (3,5-
Dimethylcyclopentadienyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene)
(5-Methylindenyl) (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) (3-trimethylsilylindenyl) (3-methylcyclopentadienyl) ) Zirconium dicloside, (1,1'-dimethylsilylene)
(2,2'-isopropylidene) indenyl (3,5-
Dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) indenyl (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-
Dimethylsilylene) (2,2'-isopropylidene) indenyl (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-isopropylidene) (4-methylindenyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene)
(2,2′-isopropylidene) (4-methylindenyl) (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2
2'-isopropylidene) (5-methylindenyl)
(3,5-Dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,
2'-isopropylidene) (5-methylindenyl)
Examples thereof include dichloro compounds such as (3-methylcyclopentadienyl) zirconium dichloride and dimethyl compounds, diethyl compounds, dihydro compounds, diphenyl compounds and dibenzyl compounds of the Group 4 transition metal compounds.

Examples of the compound represented by the general formula (9C) include (1,2'-ethylene) (2,1'-ethylene) bisindenylzirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) bis (3-methylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) bis (4-methylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) bis (5-methylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) bis (4,5) -Benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1 ') -Ethylene)
Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1'-Dimethylsilylene) bisindenyl zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-Dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4
-Methylindenyl) zirconium dichloride, (1,
2'-Dimethylsilylene) (2,1'-dimethylsilylene) bis (5-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6- Benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2 ′)
-Dimethylsilylene) (2,1'-dimethylsilylene)
Bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) bisindenylzirconium dichloride, (1,2′-dimethylsilylene) (2,2) 1′-ethylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) bis (4-methylindenyl) zirconium dichloride, (1,2′- Dimethylsilylene) (2,1'-ethylene) bis (5-methylindenyl) zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1'-ethylene) bis (5,5
6-benzoindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-ethylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 ′
-Ethylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1'-ethylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2 '
-Ethylene) (2,1'-dimethylsilylene) bisindenyl zirconium dichloride, (1,2'-ethylene) (2,1'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2 ') '-Ethylene) (2,1'-dimethylsilylene) bis (4-methylindenyl) zirconium dichloride, (1,2'
-Ethylene) (2,1'-dimethylsilylene) bis (5
-Methylindenyl) zirconium dichloride, (1,
2'-ethylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-dimethylsilylene) bis (4,5- Benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 '-Isopropylidene) bisindenyl zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) ( 2,1′-isopropylidene) bis (4-methylindenyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-isopropylidene) bis (5-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,2
1'-isopropylidene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (4
5-benzoindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) bis (5,6-dimethylindenyl) zirconium dichloride and other dichloro compounds, and the above compounds including dimethyl compound, diethyl compound, dihydro compound, diphenyl compound, Examples thereof include dibenzyl compounds and their titanium and hafnium complexes.

In the general formula (9), R ²⁵
When R ³⁰ does not form a ring with an adjacent group, for example, (dimethylsilylene) (isopropylidene) bis (cyclopentadiene) zirconium dichloride,
Bis (dimethylsilylene) bis (cyclopentadienyl) zirconium dichloride, bis (ethylene) bis (cyclopentadienyl) zirconium dichloride,
(Dimethylsilylene) (isopropylidene) bis (cyclopentadienyl) dimethylzirconium, (dimethylsilylene) (isopropylidene) bis (cyclopentadienyl) dibenzylzirconium, (dimethylsilylene) (isopropylidene) bis (cyclopentadiene) (Enyl) bis (trimethylsilyl) zirconium, (dimethylsilylene) (isopropylidene) bis (cyclopentadienyl) bis (trimethylsilylmethyl) zirconium, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3 -Methylcyclopentadienyl)
(5′-Methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 ′
-Dimethylsilylene) (3-methylcyclopentadienyl) (5'-cyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (3-methylcyclopentadienyl) (5'-methylcyclopentadienyl) dichloro body such as zirconium dichloride and dimethyl body, diethyl body of the above compounds,
Examples thereof include a dihydro body, a diphenyl body, a dibenzyl body, and titanium and hafnium complexes thereof. More specifically, examples of the compound represented by the general formula (10) include transition compounds represented by the following general formulas (10A) and (10B), which are represented by the fourth to sixth periodic tables.

[0059]

[Chemical 20]

[0060]

[Chemical 21]

In the formula, R ^{67 to} R ⁸⁸ and X ³ and X ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, It represents a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and may be bonded to adjacent groups to form a ring. Y ³ and Y ⁴ are each a divalent group that independently binds two ligands and has 1 to 2 carbon atoms.
0 hydrocarbon group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, germanium-containing group, tin-containing group,
-O -, - CO -, - S -, - SO 2 -, - NR 89 -,
-PR ⁸⁹ -,-P (O) R ⁸⁹ -,-BR ⁸⁹ -or-Al
R ⁸⁹ - indicates, R ⁸⁹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. M ⁵ represents a transition metal of Groups 4 to 6 of the periodic table.

Examples of the compound represented by the general formula (10A) include (1,1'-ethylene) (7,7'-
Ethylene) bisindenyl zirconium dichloride,
(1,1'-ethylene) (7,7'-ethylene) bis (2-methylindenyl) zirconium dichloride,
(1,1′-ethylene) (7,7′-ethylene) bis (3-methylindenyl) zirconium dichloride,
(1,1'-dimethylsilylene) (7,7'-dimethylsilylene) bisindenyl zirconium dichloride,
(1,1′-Dimethylsilylene) (7,7′-dimethylsilylene) bis (2-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (7,
7'-Dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-ethylene)
(7,7'-Dimethylsilylene) bisindenyl zirconium dichloride, (1,1'-ethylene) (7,7 '
-Dimethylsilylene) bis (2-methylindenyl) zirconium dichloride, (1,1'-ethylene) (7,
7′-Dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (7,7′-ethylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene)
(7,7'-ethylene) bis (2-methylindenyl)
Zirconium dichloride, (1,1′-dimethylsilylene) (7,7′-ethylene) bis (3-methylindenyl) dichloro body such as zirconium dichloride and the above 4
Examples thereof include a dimethyl body, a diethyl body, a dihydro body, a diphenyl body, and a dibenzyl body of a group transition metal compound.

Examples of the compound represented by the general formula (10B) include (1,1′-ethylene) (2,7′-).
Ethylene) (fluorenyl) (indenyl) zirconium dichloride, (1,1′-ethylene) (2,7′-ethylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2 ，
7'-ethylene) (fluorenyl) (3-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-ethylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1, 1 '
-Ethylene) (2,7'-ethylene) (9-methylfluorenyl) (indenyl) zirconium dichloride,
(1,1'-ethylene) (2,7'-ethylene) (8-
Methylfluorenyl) (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,7′-
Ethylene) (fluorenyl) (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2
7'-ethylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-ethylene) (fluorenyl)
(3-methylindenyl) zirconium dichloride,
(1,1′-Dimethylsilylene) (2,7′-ethylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,7'-ethylene) (9-methylfluorenyl)
(Indenyl) zirconium dichloride, (1,1'-
Dimethylsilylene) (2,7'-ethylene) (8-methylfluorenyl) (indenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-dimethylsilylene) (fluorenyl) (indenyl) zirconium dichloride , (1,1'-ethylene) (2,7'-dimethylsilylene) (fluorenyl) (2-methylindenyl) zirconium dichloride, (1,1'-ethylene)
(2,7'-dimethylsilylene) (fluorenyl) (3
-Methylindenyl) zirconium dichloride, (1,
1'-ethylene) (2,7'-dimethylsilylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1'-ethylene) (2,7'-dimethylsilylene) (9-methylfluorene Nyl) (indenyl) zirconium dichloride, (1,1′-ethylene)
(2,7'-dimethylsilylene) (8-methylfluorenyl) (indenyl) zirconium dichloride, (1,
1'-dimethylsilylene) (2,7'-dimethylsilylene) (fluorenyl) (indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-dimethylsilylene) (fluorenyl) (2-methylindene) Nyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'-dimethylsilylene) (fluorenyl) (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,7'- Dimethylsilylene) (fluorenyl) (6-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,7′-dimethylsilylene) (9-methylfluorenyl) (indenyl) zirconium dichloride, (1 , 1′-Dimethylsilylene) (2,7′-dimethylsilylene) (8-methylfluorenyl) (yne ) Zirconium dichloride, dichloro body and dimethyl member of the Group 4 transition metal compounds such as diethyl body, dihydro derivative, diphenyl body, it can be exemplified dibenzyl and the like.

As the component (A '), so-called metallocene is used.
Compounds called compounds can also be used. Metalloc
Is a Japanese Patent Laid-Open No. 58-19309 and Japanese Patent Laid-Open No. 61-
130314, JP-A-3-163088,
JP-A-4-300887, JP-A-4-21169
No. 4 publication, special table 1-502036 publication, etc.
Such as cyclopentadienyl group, substituted cyclopentadiene
An enyl group, an indenyl group, a substituted indenyl group, etc.
A transition metal compound having two ligands, and the ligand having a geometric shape
A transition metal compound that is controlled biologically,
Among them, the following general formula (11) or (1
The metallocene represented by 2) is preferable. Q¹ _e(C_FiveH_5-efR⁹⁰ _f) (C_FiveH_5-egR⁹¹ _g) M⁶X^Five _pY^Five _q(11) Q² _e(C_FiveH_5-ehR⁹² _h) Z³M⁶X^Five _pY^Five _q... (12) [In the formula, Q¹Is two conjugated five-membered ring ligands (C_FiveH_5-ef
R⁹⁰ _f) And (C_FiveH_{Five- eg}R⁹¹ _g) Crosslinking
Shows the group, Q²Is a conjugated five-membered ring ligand (C_FiveH_{5-e- h}R⁹²
_h) And Z³The bonding group which bridge | crosslinks a group is shown. R⁹⁰, R⁹¹Over
And R⁹²Is a hydrocarbon group, halogen atom,
Xy group, silicon-containing hydrocarbon group, phosphorus-containing hydrocarbon group,
Showing a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group,
e is 0 or 1. f, g and h are such that when e = 0,
Each is an integer from 0 to 5, and when e = 1, 0 to 4 respectively
Indicates an integer. p + q = [(M⁶Valence of 2) -2]
It M ⁶Indicates a transition metal of Groups 4 to 6 of the Periodic Table. Also,
X^Five, Y^Five, Z³Are covalent or ionic bonds, respectively
Represents a polar ligand, X^FiveAnd Y^FiveAre each other
It may combine with each other to form a ring structure. ]

Specific examples of Q ¹ and Q ² are:
(1) C1-C4 alkylene group such as methylene group, ethylene group, isopropylene group, methylphenylmethylene group, diphenylmethylene group, cyclohexylene group, cycloalkylene group or side chain lower alkyl or phenyl substitution product thereof, (2) silylene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group or other silylene group, oligosilylene group or side chain lower alkyl or phenyl substitution product thereof, (3) ( CH ₃ ) ₂ Ge group,
(C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) ₂ P group, (C
₆ H ₅ ) ₂ P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N
Groups, (CH ₃₎ B group, (C ₄ H ₉₎ B group, (C ₆ H ₅₎
A hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum such as B group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower group (Alkoxy group), etc.]
And so on. Among these, an alkylene group and a silylene group are preferable from the viewpoint of activity.

In addition, (C_FiveH_5-efR⁹⁰ _f), (C_FiveH
_5-egR⁹¹ _g) And (C_FiveH_5-ehR⁹² _h) Is a conjugated five member
R is a ring ligand⁹⁰, R⁹¹And R⁹²Are each carbonized
Hydrogen group, halogen atom, alkoxy group, silicon-containing hydrocarbon
Elementary group, phosphorus-containing hydrocarbon group, nitrogen-containing hydrocarbon group or boron
Represents a hydrogen atom-containing hydrocarbon group, and e is 0 or 1. f, g
And h are integers of 0 to 5 when e = 0, e =
When it is 1, each represents an integer of 0 to 4. Where carbonization
The hydrogen group preferably has 1 to 20 carbon atoms,
Further, those having 1 to 12 carbon atoms are preferable. This hydrocarbon group
As a monovalent group, cyclopentadiene which is a conjugated five-membered ring group
It may be bonded to a nyl group, and there are multiple
Two of them are bound to each other by cyclopentadiene
A ring structure may be formed together with a part of the enyl group. You
That is, a typical example of the conjugated five-membered ring ligand is a substituted or non-substituted
Cyclopentadienyl group, indenyl group and fluoro
It is a renyl group. Halogen atoms include chlorine, bromine,
Iodine and fluorine atoms are mentioned, and as an alkoxy group
The group preferably has 1 to 12 carbon atoms. silicon
Examples of the contained hydrocarbon group include -Si (R⁹³)
(R⁹⁴) (R⁹⁵) (R⁹³, R⁹⁴And R⁹⁵Has 1 to 2 carbon atoms
4 hydrocarbon groups) and the like, and phosphorus-containing hydrocarbons
Groups, nitrogen-containing hydrocarbon groups and boron-containing hydrocarbon groups
Are -P (R ⁹⁶) (R⁹⁷), -N (R⁹⁶) (R
⁹⁷) And -B (R⁹⁶) (R⁹⁷) (R⁹⁶And R⁹⁷Is the carbon number
1-18 hydrocarbon groups) and the like. R⁹⁰, R⁹¹
And R⁹²If there are multiple Rs⁹⁰， Duplicate
Number R⁹¹And multiple R⁹²Are the same in each
Or they may be different. Also, a conjugated five-membered ring ligand
(C_FiveH_{Five- ef}R⁹⁰ _f) And (C_FiveH_5-egR⁹¹ _g) Is
It may be the same or different.

On the other hand, M⁶Is a transition metal of Groups 4 to 6 of the Periodic Table
Indicates an element, and specific examples include titanium and zirconium
Mu, hafnium, vanadium, niobium, molybdenum, ta
You can mention Nung Sten, but among these
Titanium, zirconium and hafnium in terms of activity
Is preferred. Z³Is a covalent ligand,
Is a halogen atom, oxygen (-O-), sulfur (-S-),
An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
Thioalkoxy having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Group, nitrogen-containing carbon having 1 to 40, preferably 1 to 18 carbon atoms
Hydrogen group, phosphorus having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms
Indicates a contained hydrocarbon group. X^FiveAnd Y^FiveAre each
They may be bonded to each other to form a ring structure. That is, X^Five
They may combine with each other to form a ring structure, or
Y^FiveThey may combine with each other to form a ring structure.
Ruai again X^FiveAnd Y^FiveCombine with each other to form a ring structure
May be. X^FiveAnd Y^FiveAre covalently coordinated
Child or a binding ligand, specifically, a hydrogen atom,
Rogen atom, carbon having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
Hydrogen group, an alkane having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
Coxy group, amino group, 1 to 20 carbon atoms, preferably 1 to
12 phosphorus-containing hydrocarbon groups (eg, diphenylphosphine
1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
A silicon-containing hydrocarbon group (for example, a trimethylsilyl group
Etc.), hydrocarbons having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Group or halogen-containing boron compound (eg B (C₆H
_Five)_Four  , BF_Four) Is shown. Among these, halogen atoms and
And hydrocarbon groups are preferred. This X ^FiveAnd Y^FiveTo each other
It may be the same or different.

Represented by the general formula (11) or (12)
A preferred typical example of the transition metal compound is
Medium, Q¹Is two conjugated five-membered ring ligands (C_FiveH_5-efR⁹⁰
_f) And (C_FiveH_5-egR⁹¹ _g) A linking group that bridges
Show, Q²Is a conjugated five-membered ring ligand (C_FiveH_5-ehR⁹² _h)
And Z³Q represents a bonding group that crosslinks the group,¹And is Q²But
An alkylene group or a silylene group, R⁹⁰, R⁹¹as well as
R⁹²Are a hydrocarbon group, a halogen atom, and an alkoxy group, respectively.
Si group, silicon-containing hydrocarbon group, phosphorus-containing hydrocarbon group, nitrogen
Containing hydrocarbon group or boron containing hydrocarbon group, e is 0
Or 1, and f, g and h are each when e = 0
Is an integer of 0-5, and when e = 1, is an integer of 0-4.
, P + q = [(M⁶Valence of 2) -2], and M⁶
Represents a transition metal of Groups 4 to 6 of the Periodic Table, and M⁶Is Titaniu
Aluminum, zirconium or hafnium, X^Five，
Y^Five, Z³Are covalent or ionic bonds, respectively.
Represents the order, X^FiveAnd Y^FiveAre bound to each other
To form a ring structure, X ^FiveAnd Y^FiveIs a halogen source
A child or a hydrocarbon group, Z³Is an alkane having 1 to 10 carbon atoms
Coxy group, C1-C12 thioalkoxy group, carbon number
1-18 nitrogen-containing hydrocarbon groups or 1-18 carbon atoms
It is a hydrocarbon group containing phosphorus.

The following compounds may be mentioned as specific examples of the transition metal compound represented by the general formula (11) or (12). Bis (cyclopentadienyl) zirconium dichloride, Bis (methylcyclopentadienyl) zirconium dichloride, Bis (dimethylcyclopentadienyl) zirconium dichloride, Bis (trimethylcyclopentadienyl) zirconium dichloride, Bis (tetramethylcyclopentadiene (Enyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) Zirconium chlorohydride, bis (cyclopentadienyl) methyl zirconium chloride, bis (cyclopentadienyl) ethyl zirconium chloride Lido, bis (cyclopentadienyl) phenyl zirconium chloride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dineopentyl zirconium, bis (cyclopentadienyl) Transitions having two conjugated five-membered ring ligands, such as (enyl) dihydrozirconium, (cyclopentadienyl) (indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, which do not have a bridging linking group Metal compounds,

Methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, methylenebis (indenyl) zirconium chlorohydride, ethylenebis (indenyl) methylzirconium chloride, ethylenebis (indenyl) methoxychlorozirconium, ethylenebis (indenyl) zirconium Diethoxide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2-
Methyl-4-trimethylsilylindenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-5,5)
6,7-Trihydroindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, ethylene (2-methyl-4-t)
-Butylcyclopentadienyl) (3'-t-butyl-
5'-methylcyclopentadienyl) zirconium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2 -Methylindenyl) zirconium dichloride, isopropylidene bis (indenyl) zirconium dichloride, isopropylidene bis (2,4-dimethylindenyl zirconium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3'5 '
-Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) zirconium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chlorohydride, methylene (cyclopentadienyl) (3,4-Dimethylcyclopentadienyl) dimethylzirconium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenylzirconium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium Dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopenta Dienyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl)
(3,5-Dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (3,4-Diethylcyclopentadienyl)
Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,
2,7-trimethylindenyl) zirconium dichloride and other conjugated five-membered ring ligands bridged with an alkylene group
A transition metal compound having

Dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene Bis (2-methylindenyl) zirconium dichloride, dimethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, dimethylsilylene bis (2,4-dimethylcyclopentadienyl) (3 ′,
5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4,5)
-Benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium Dichloride, phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, phenylmethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadiene (Enyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethyl Clopentadienyl) zirconium dichloride, phenylmethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, diphenylsilylene bis (2-methylindenyl)
Zirconium dichloride, tetramethyldisilylene bis (indenyl) zirconium dichloride, tetramethyldisilylene bis (cyclopentadienyl) zirconium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( Tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclo) Pentadienyl) (2,7-di -
t-Butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,2) 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2
-Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ', 7'- Di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2 ′,
7'-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl)
Zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) zirconium dichloride, dimethylsilylene (Dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorene Nil) transition metal compound having two silylene group-bridged conjugated five-membered ring ligands such as zirconium dichloride,

Dimethylgermylene bis (indenyl)
Zirconium dichloride, dimethyl germylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylaluminene bis (indenyl) zirconium dichloride, phenylamylene bis (indenyl) zirconium dichloride, phenylphosphylene bis (indenyl) zirconium dichloride, ethylborene bis ( Indenyl) zirconium dichloride, phenylamylene bis (indenyl) zirconium dichloride, phenylamylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, etc. germanium, aluminum, boron, phosphorus or nitrogen-containing conjugated bridges A transition metal compound having two five-membered ring ligands,

(Pentamethylcyclopentadienyl)
Diphenylaminozirconium dichloride, (indenyl) diphenylaminozirconium dichloride, (pentamethylcyclopentadienyl) bis (trimethylsilyl) aminozirconium dichloride, (pentamethylcyclopentadienyl) phenoxyzirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) T-Butylaminozirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] zirconium Dichloride, dimethylgermylene (tetramethylcyclopentadienyl Phenylamino zirconium dichloride, pentamethylcyclopentadienyl zirconium tri-methoxide, transition metal compounds having one conjugated five-membered ring ligands such as pentamethylcyclopentadienyl zirconium trichloride,

Furthermore, in the compounds described in the above-mentioned, chlorine atoms of these compounds are replaced by bromine atom, iodine atom, hydrogen atom, methyl group, phenyl group, benzyl group,
Replaced by methoxy group, dimethylamino group, etc.,
And / or those in which the zirconium atom is replaced with titanium, hafnium or the like.

Next, regarding the component (B '), (b'
-1) component and / or (b'-2) component. Examples of the component (b'-1) include the same as the component (b-1) in the first step, and the component (b'-1) is (b-
It may be the same as or different from the component 1). Further, the component (b'-2) may be the same as the component (b-2) of the first step, and the component (b'-2) may be the same as the component (b-2). Good or different.

When the component (b'-1) is used as the component (B '), the ratio of the component (A') and the component (B ') used is a molar ratio, preferably 1: 1 to 1. : 1,00
10,000, more preferably 1:10 to 1: 10,00
When using 0, the component (b'-2), the molar ratio is preferably 10: 1 to 1: 100, more preferably 2 :.
1 to 1:10. Further, as the component (B '),
The component (b'-1) and the component (b'-2) may be used alone or in combination of two or more.

The olefin polymerization catalyst (II) in the second step of the present invention may be composed of the above-mentioned component (A ') and component (B'), or as the component (C '), It may contain an organoaluminum compound. Examples of the component (C ′) include the same as the component (C) in the first step, and the component (C ′) may be the same as or different from the component (C).

The ratio of the component (A ') to the component (C') used is a molar ratio, preferably 1: 1 to 1:10:00.
It is 0, more preferably 1: 5 to 1: 2,000. By using this component (C '), the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

(4) Polymerization of α-olefin (second step) The α-olefin produced in the first step may be separated from the olefin polymerization catalyst (I) or without separation.
In the second step, polymerization is carried out in the presence of the olefin polymerization catalyst (II) or copolymerization with ethylene is carried out. There is no particular limitation on the method for polymerizing α-olefin or copolymerizing with ethylene, and slurry polymerization method, solution polymerization method,
Any polymerization method such as a gas phase polymerization method, a bulk polymerization method and a suspension polymerization method can be adopted. The solution polymerization method is preferred. It may be a continuous reaction or a batch reaction. When using a polymerization solvent, benzene, toluene,
Hydrocarbons such as xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene and halogenated hydrocarbons can be mentioned. These may be used alone or in combination of two or more.

When a solvent is used, the amount of the catalyst used is such that the component (A ') is usually 0.1 to 100 μmol, preferably 0.5 to 1 liter of the solvent.
It is advantageous to carry out in the range of 25 μmol from the viewpoint of polymerization activity and reactor efficiency. The polymerization conditions are not particularly limited, but the reaction temperature is usually -50 to 250.
C, preferably in the range of normal temperature to 150 ° C. The pressure is usually in the range of normal pressure to 20 MPa · G. The molecular weight in the reaction can be controlled by known means, selection of the type of each catalyst component, usage amount, temperature, pressure and the like, introduction of hydrogen and the like.

[0081]

[Example 1]

(1) Catalyst Preparation Synthesis of Ligand Precursor 2,6-di (2,5-xyloyl) pyridine In a 200 ml two-necked round bottom flask equipped with a reflux condenser, 12.2 g (91.5 mmol of 91.5 mmol of AlCl _3). ) Was added and the atmosphere was replaced with nitrogen. To this, 6.12 g (30.0 mmol) of 2,6-pyridinedicarbonyldichloride was added.
-Xylene solution (50 ml of p-xylene) was added dropwise. Then, the mixture was heated with stirring and refluxed for 5 hours. After allowing to cool, add NaHCO ₃ aqueous solution gradually to add Al.
The Cl ₃ was quenched. The reaction solution was extracted with toluene, the organic layer was dried over anhydrous MgSO ₄ , and the solvent was distilled off. The product was purified using silica gel column chromatography (hexane / ethyl acetate volume ratio = 10/1), and the ligand precursor 2,6-di (2,5-xyloyl) pyridine was added to 10.1.
g was obtained (yield 98%). · ¹ H-NMR measurement results (a) Measurement conditions: 270 MHz, solvent; CDCl _3, chloroform reference (δ7.24) (b) _{Attribution: δ2.16 (6H, CH 3,} s), δ2.
21 (6H, CH ₃ , s), δ 6.69 to 7.20 (6
H, benzene ring, m), δ8.09 (1H, pyridine ring 4 position, t), δ8.26 (2H, pyridine ring 3, 5 position,
d)

Ligand 2,6-di (2,5-xyloyl) obtained in the synthesis of 2,6-di (2,5-xyloyl) pyridine-di (3,5-ditert-butylphenyl) imine )
515 mg (1.5 mmol) of pyridine and 1,540 mg (7.5 mmol) of 3,5-ditert-butylaniline were dissolved in 30 ml of toluene. To this was added 53 mg of paratoluenesulfonic acid monohydrate, and the mixture was refluxed for 5 hours while removing water produced. After allowing to cool, 2 g of Na ₂ CO ₃ was added to the resulting liquid, and the mixture was further stirred for 1 hour, and then a solid substance was separated by filtration to remove paratoluenesulfonic acid. The filtrate was concentrated by an evaporator and further distilled for the purpose of removing excess 3,5-ditert-butylaniline. The product was purified by silica gel column chromatography (toluene) and recrystallized from hexane to obtain 776 mg of the desired product (yield 72%). · ¹ H-NMR measurement results (a) Measurement conditions: 270 MHz, solvent; CDCl _3, chloroform reference (δ7.24) (b) Attribution: δ1.14 (36H, tert-Bu ,
s), δ1.58 (6H, CH ₃ , s), δ2.07
(6H, CH ₃ , s), δ 6.55 to 6.93 (12
H, benzene ring, m), δ7.93 (1H, pyridine ring 4th position, t), δ8.32 (2H, pyridine ring 3rd position, d)

Synthesis of Iron Complex (Compound 1; supra) 2,6-di (2,5-xyloyl) pyridine-di (3
5-ditert-butylphenyl) imine 108 mg
35.0 mg (0.177 mmol) of ferrous chloride tetrahydrate in a dichloromethane solution containing (0.150 mmol)
Was added to a methanol solution. A complex was formed immediately and the reaction solution turned blue-green. The solvent was distilled off, and the residue was extracted with dichloromethane to obtain 108 mg of an iron complex (Compound 1) (yield 85%).

(2) Polymerization To a heated and dried 1 liter autoclave, 200 ml of n-heptane, 4 mmol of methylaluminoxane and 0.5 micromol of compound 1 were added, and the temperature was raised to 50 ° C. with stirring to give ethylene 0.8 MPa. -G was continuously supplied for 30 minutes. Furthermore, 4 micromoles of zirconocene dichloride was added, and then ethylene 0.8
MPa · G was continuously supplied for 15 minutes. After the completion of the polymerization reaction, it was dried to obtain 29 g of an olefin polymer. The physical properties of the olefin polymer are shown in Table 1.

Example 2 (1) Preparation of Catalyst Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride In a Schlenk bottle ( 3.0 g of 1,2′-dimethylsilylene) (2,1′-dimethylsilyle) -bis (indene) lithium salt
(6.97 mmol) was dissolved in 50 ml of tetrahydrofuran and cooled to -78 ° C. Then 2.1 ml of iodomethyltrimethylsilane (14.
(2 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, 50 ml of diethyl ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase is dried to remove the solvent, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) 3.04 g
(5.88 mmol) was obtained (84% yield) Next, in a Schlenk bottle under a nitrogen stream, the (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) obtained above was placed in a Schlenk bottle. 3.04 g (5.88 mmol) of bis (3-trimethylsilylmethylindene) and 50 ml of diethyl ether were added. It cooled to -78 degreeC and n-BuLi n-hexane solution (1.54M, 7.6).
Milliliter (1.7 mmol)) was added dropwise. After raising the temperature to room temperature and stirring for 12 hours, diethyl ether was distilled off. The obtained solid was washed with 40 ml of n-hexane and the lithium salt was used as an ether adduct to give 3.06.
g (5.07 mmol) was obtained (yield 73%).

¹ H-NMR (90 MHz, THF-
d ₈₎ measurement results of the, δ0.04 (s, 18H, trimethylsilyl); 0.48 (s, 12H, dimethylsilylene); 1.10 (t, 6H, methyl); 2.59
(S, 4H, methylene); 3.38 (q, 4H, methylene), 6.2-7.7 (m, 8H, Ar-H). The lithium salt obtained under a nitrogen stream was dissolved in 50 ml of toluene. 1.2 g of zirconium tetrachloride cooled to −78 ° C. and previously cooled to −78 ° C.
A suspension of toluene (20 milliliters) (5.1 mmol) was added dropwise. After the dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The resulting residue was recrystallized with dichloromethane to give (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride 0.9 g (1. 33 mmol) was obtained (yield 26%).

¹ H-NMR (90 MHz, CDCl ₃ )
7. The measurement result according to 1. is δ0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene);
It was 1-7.6 (m, 8H, Ar-H).

(2) Polymerization To a 1 liter autoclave which was heated and dried, 200 ml of n-heptane, 4 mmol of methylaluminoxane and 0.5 micromol of Compound 1 were added, and the temperature was raised to 50 ° C. with stirring to obtain ethylene 1 MPa · G. Was continuously fed for 10 minutes. Then, the supply of ethylene was stopped, and 10.5 μmol of the compound was added and polymerization was carried out for 10 minutes. Furthermore, the temperature was set to 120 ° C., hydrogen was introduced at 0.05 MPa · G, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride 2 μmol In addition, it was polymerized for 30 minutes. After the completion of the polymerization reaction, it was dried to obtain 5 g of an olefin polymer. The physical properties of the olefin polymer are shown in Table 1.

Example 3 (1) Preparation of catalyst Ligand 2,6-di (2,5-xyloyl) pyridine-
Synthesis of di (2-chloro-4-methylphenyl) imine In (1) of Example 1, in place of 3,5-ditert-butylaniline, 2-chloro-4-methylaniline 1,062 mg (7. (5 mmol), except that the same operation was performed. As a result, the target product was 487 mg.
Obtained (yield 55%). · ¹ H-NMR measurement results (a) Measurement conditions: 270 MHz, solvent; CDCl _3, chloroform reference (δ7.24) (b) _{Attribution: δ1.67 (6H, CH 3,} s), δ2.
09 (6H, CH ₃ , s), δ 2.18 (6H, C
H ₃ , s), δ 6.32 to 7.20 (12H, benzene ring, m), δ 7.96 (1H, pyridine ring 4 position, t),
δ 8.48 (2H, 3-position of pyridine ring, d)

Synthesis of Iron Complex (Compound 2; Above) In (1) of Example 1, 2,6-di (2,5-xyloyl) pyridine-di (3,5-ditert-butylphenyl) imine Was replaced by 2,6-di (2,5-xyloyl) pyridine-di (2-chloro-4-methylphenyl) imine 139 mg (0.235 mmol) and ferrous chloride tetrahydrate The amount of 48.7mg
The same operation was performed except that the amount was (0.245 mmol). As a result, dark green iron complex (Compound 2) 155 m
g was obtained (yield 92%).

(2) Polymerization To a heated and dried 1 liter autoclave, 200 ml of n-heptane, 16 mmol of methylaluminoxane and 4 μmol of Compound 2 were added, the temperature was raised to 50 ° C. with stirring, and ethylene 2 MPa · G was continuously added. To 1
Feed for 0 minutes. Then, the ethylene supply was stopped and the polymerization was carried out for 20 minutes. Further, the temperature is set to 120 ° C., and hydrogen of 0.
After introducing 05 MPa · G, 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 60 minutes. After completion of the polymerization reaction, the olefin polymer 1 is dried by drying.
5 g was obtained. The physical properties of the olefin polymer are shown in Table 1.

Regarding the physical properties of the olefin polymers obtained in the examples, the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn) and the number of side chain branches (methyl branch, (Ethyl branch, butyl branch, long-chain branch of hexyl or more) is represented by the number / number of 1,000 carbons. Measurement of number of side chains / ¹³ C-NMR measurement conditions Samples were collected in a 10 mmφ NMR sample tube, and 1, 2, 4
-3 ml of trichlorobenzene / deuterated benzene (90/10% by volume) was added and homogeneously dissolved at 140 ° C. ¹³ C-NMR was measured with a 400 MHz NMR apparatus. The conditions are pulse repetition time; 15 seconds, measured temperature;
The temperature was 130 ° C., the number of integrations was 3,000, and the BF was 1.0. Methyl branching at 20.1 ppm (a), 10.9 p
An ethyl branching peak was observed in pm (b), and 14.
At 2 ppm (e), peaks of butyl branch and long-chain branch of hexyl or more are observed.

The index of branch number (methyl carbon number) is
The ratio of total methyl carbon intensity and total carbon peak intensity was calculated by the following formula. Methyl carbon number = (a + b + e) / total carbon peak intensity ×
1,000 (pieces / total 1,000 carbons) Subsequently, the number of side chain branches was determined from the ratio with each side chain peak.

[0094]

[Table 1]

From Table 1, it is possible to inexpensively supply an α-olefin polymer and an ethylene / α-olefin copolymer having methyl, ethyl, butyl and hexyl branches in the polymer chain from a raw material containing only ethylene. I know there is.

[0096]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a method for producing an olefin polymer which can produce an α-olefin polymer at low cost by using only ethylene as a raw material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07F 15/02 C07F 15/02 17/00 17/00 (72) Inventor Hidetoshi Ohno Shingu Town, Tokuyama City, Yamaguchi Prefecture No. 1 No. 1 F-term (reference) 4H049 VN01 VN06 VP05 VQ07 VR12 VR23 VU14 4H050 AA03 AB40 WB21 4J011 AA01 AC05 BA01 BA09 BB01 BB03 BB11 4J028 AA01A AB00A AB02A AC01A AC10A AC28A AC31A AC39A AC41A AC44A BA00A BA01B BA02B BB00A BB01B BC12B BC25B EB02 EB03 EC01 EC02 FA01 FA02 FA04 FA06 FA07 FA10

Claims (6)

[Claims] 1. (A) The following general formula (1): [In the formula, M represents a transition metal of Groups 8 to 10 of the periodic table,
R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom,
It represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, which may be bonded to each other to form a ring. R ⁴ and R
⁵ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ⁹ are each independently a hydrogen atom,
It represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may form a ring with each other. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. R
⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶ ₂ or SR.
¹⁶ (where R ¹⁶ is a hydrogen atom, a halogen atom, or a carbon number 1
A hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom. ) Is shown. However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom. X represents a covalent bond group or an ionic bond group, and when there are a plurality of groups, they may be the same or different. n represents the valence of M. ] At least 1 type of transition metal compound of 8-10 groups of the periodic table represented by these,
(B) at least one selected from (b-1) an organoaluminum oxy compound and (b-2) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex In the presence of an olefin polymerization catalyst (I) containing and, ethylene is subjected to an oligomerization reaction to obtain α-olefin, and then in the presence or absence of the olefin polymerization catalyst (I), (A ′) cycle. Table 4 ~
At least one transition metal compound of Group 6 and (B ′)
(B'-1) Organoaluminum oxy compound and (b '
-2) In the presence of an olefin polymerization catalyst (II) containing at least one selected from compounds capable of reacting with the transition metal compound of the component (A ') or a derivative thereof to form an ionic complex, A method for producing an olefin-based polymer, which comprises polymerizing the produced α-olefin. 2. (A) The following general formula (1): [In the formula, M represents a transition metal of Groups 8 to 10 of the periodic table,
R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom,
It represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, which may be bonded to each other to form a ring. R ⁴ and R
⁵ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ⁹ are each independently a hydrogen atom,
It represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may form a ring with each other. R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom, and may be bonded to each other to form a ring. R
⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, NR ¹⁶ ₂ , OR ¹⁶ , PR ¹⁶ ₂ or SR.
¹⁶ (where R ¹⁶ is a hydrogen atom, a halogen atom, or a carbon number 1
A hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms or a group containing a hetero atom. ) Is shown. However, at least one of R ⁶ , R ¹⁰ , R ¹¹ and R ¹⁵ is a hydrogen atom. X represents a covalent bond group or an ionic bond group, and when there are a plurality of groups, they may be the same or different. n represents the valence of M. ] At least 1 type of transition metal compound of 8-10 groups of the periodic table represented by these,
(B) at least one selected from (b-1) an organoaluminum oxy compound and (b-2) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex In the presence of an olefin polymerization catalyst (I) containing and, ethylene is subjected to an oligomerization reaction to obtain α-olefin, and then in the presence or absence of the olefin polymerization catalyst (I), (A ′) cycle. Table 4 ~
At least one transition metal compound of Group 6 and (B ′)
(B'-1) Organoaluminum oxy compound and (b '
-2) In the presence of an olefin polymerization catalyst (II) containing at least one compound selected from a compound capable of reacting with the transition metal compound of the component (A ') or a derivative thereof to form an ionic complex, A method for producing an olefin-based polymer, which comprises copolymerizing ethylene with the produced α-olefin. 3. The method for producing an olefin polymer according to claim 1, wherein in the general formula (1), at least one of R ⁴ and R ⁵ is an aryl group or a substituted aryl group. 4. The method for producing an olefin polymer according to claim 1, wherein the transition metal M in the general formula (1) is iron or cobalt. 5. The component (A ′) is represented by the following general formula (9) or
(10) [Chemical 3] [Chemical 4] (In the formula, R^{twenty five}~ R³⁶And X¹~ X^FourEach independently
Hydrogen atom, halogen atom, hydrocarbon having 1 to 20 carbon atoms
Group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon
Containing groups, oxygen containing groups, sulfur containing groups, nitrogen containing groups or
Group containing a group that forms a ring with an adjacent group.
Good. 3 R³³And 3 R³⁴Are the same as each other
But it can be different. Y¹~ Y^FourEach independently
A divalent group that bonds two ligands and has 1 to 1 carbon atoms.
20 hydrocarbon groups, halogen containing carbon atoms having 1 to 20 carbon atoms
Hydrogen group, silicon-containing group, germanium-containing group, tin-containing
Group, -O-, -CO-, -S-, -SO₂-, -NR³⁷
-, PR³⁷-, -P (O) R³⁷-, -BR³⁷-Or-A
lR³⁷-Indicates R³⁷Is hydrogen atom, halogen atom, carbon
C1-20 hydrocarbon group or C1-20 halogen
Indicates a contained hydrocarbon group. M ^FourAnd M^FiveAre independent
Shows transition metals of Groups 4 to 6 of the periodic table. )
A transition metal compound according to any one of claims 1 to 4.
Process for producing olefin polymer. 6. In the general formula (9) or (10), M
^The method for producing an olefin polymer according to claim ^{5, wherein 4} and M ⁵ are zirconium.